Catalysis

Volume 22
A Specialist Periodical Report
Catalysis
Volume 22
A Review of Recent Literature
Editors
James J. Spivey, Louisiana State University, USA
Kerry M. Dooley, Louisiana State University, USA
Authors
Nicolas Bion, University of Poitiers, France
Cristina Della Pina, University of Milan, Italy
Daniel Duprez, University of Poitiers, France
Florence Epron, University of Poitiers, France
Ermelinda Falletta, University of Milan, Italy
Jo zsef L. Margitfalvi, Institute of Surface Chemistry and Catalysis, Budapest,
Hungary
F. C. Meunier, University of Caen, France
Michele Rossi, University of Milan, Italy
Johannes W. Schwank, University of Michigan, USA
K. Seshan, University of Twente, The Netherlands
Andrew R. Tadd, University of Michigan, USA
Em lia Ta las, Institute of Surface Chemistry and Catalysis, Budapest, Hungary
ISBN 978-1-84755-951-7
DOI 10.1039/9781847559630
ISSN 0140-0568
A catalogue record for this book is available from the British Library
& The Royal Society of Chemistry 2010
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Preface
James J. Spivey
a
and Kerry M. Dooley
a
DOI: 10.1039/9781847559630-FP005
Recent research activity in catalysis has centered on energy related pro-
cesses, and the synthesis of higher value compounds using biomass as well
as conventional reactants. The work reported here addresses these two
important areas.
First, Nicolas Bion, Florence Epron, and Daniel Duprez (Universite
de Poitiers, France) provide a review of bioethanol reforming, particularly
as compared to conventional hydrocarbon reforming. Reforming of bio-
derived ethanol is an essential element in an overall process to deliver
hydrogen from renewable resources. The authors show important dier-
ences between reforming of an oxygenate such as ethanol and reforming of
conventional hydrocarbonse.g., deactivation.
Johannes Schwank and Andrew Tadd (Univ. Michigan) examine a
closely related reactioncatalytic reforming of liquid hydrocarbons, par-
ticularly for application to solid oxide fuel cells, which are being developed
commercially for use as auxiliary power systems. They consider steam re-
forming, catalytic partial oxidation, and autothermal reforming, each of
which has dierent challenges in terms of heat transfer, kinetics, and
catalyst deactivation.
Another energy-related subject is the use of spectroscopic methods to
study reactions of interest in environmental control systems. Specically,
Fred Meunier (CNRS, France) reviews spectrokinetic methods to study
reactions such as NOx reduction using IR spectroscopy. He also shows how
spectroscopy can be applied to the water-gas-shift reaction, and important
reaction in the catalysis of fuel reforming for hydrogen production. He
shows how DRIFTS can be combined with isotopic analysis to study the
dynamics of the active catalyst surface with a combination of these two
methods.
K. Seshan (Univ. Twente, Netherlands) reports on oxidative conversion
of low molecular weight alkanes to the corresponding olens. These olens
are important feedstocks for the chemical industry. This particular review
focuses solely on oxidative conversion of these alkanes to olens, which has
advantages in terms of thermodynamics and kinetics compared to alter-
native processes, primarily catalytic or steam cracking.
Asymmetric hydrogenation of activated ketones is a particularly de-
manding reaction, producing high-value, enantiopure products for the
specialty chemical industry. Jozef Margitfalvi and Emilia Ta las (Institute of
Surface Chemistry and Catalysis, Budapest) review in particular hetero-
geneous catalysts for these reactions, although homogeneous catalysts are
perhaps more widely used at present. However, homogeneous metal-based
catalysts are expensive due to the need for chiral ligands. This chapter shows
a
Gordon A. and Mary Cain Dept. Chemical Engineering, Louisiana State University, Baton
Rouge, LA 70803
Catalysis, 2010, 22, vvi | v
c
The Royal Society of Chemistry 2010
recent progress in development of heterogeneous catalysts, such as en-
capsulation of a chiral metal complex in micropores.
Finally, Cristina Pina, Ermelinda Falleta, and Michele Rossi (Universita`
di Milano, Italy) provides a review of gold catalysis. This focuses on
reactions such as selective oxidation of alcohols and carbohydrates, and
selective oxidation of hydrocarbons. Within this chapter, a more general
summary of gold catalysis in the synthesis of advanced materials (e.g., those
based on PAN) is provided.
We greatly appreciate the eorts of the authors who have contributed to
this volume. We thank the Royal Society of Chemistry for their support of
this series. Comments are welcome.
vi | Catalysis, 2010, 22, vvi
CONTENTS
Preface v
James J. Spivey and Kerry M. Dooley
Bioethanol reforming for H
2
production. A comparison with
hydrocarbon reforming
1
Nicolas Bion, Florence Epron and Daniel Duprez
1. Introduction 1
2. The steam reforming of hydrocarbons 2
3. Steam reforming of ethanol 23
4. Utilisation of crude bioethanol 37
5. Conclusions and recommendations 46
References 48
Catalytic reforming of liquid hydrocarbons for on-board solid
oxide fuel cell auxiliary power units
56
Johannes W. Schwank and Andrew R. Tadd
1. Introduction 56
2. Fuel properties and SOFC fuel requirements 58
3. Catalysts for reforming of liquid hydrocarbons 61
Cover
Image provided courtesy
of computational science
company Accelrys
(www.accelrys.com). An
electron density isosurface
mapped with the electrostatic
potential for an organometallic
molecule. This shows the
charge distribution across the
surface of the molecule with
the red area showing the
positive charge associated
with the central metal atom.
Research carried out using
Accelrys Materials Studios
s.
Catalysis, 2010, 22, viiix | vii
c
The Royal Society of Chemistry 2010
4. Fuel reforming methods 62
5. Deactivation of reforming catalysts 69
6. On-board reforming of fuels for SOFC APU applications 76
7. Systems engineering aspects of on-board fuel processing 81
8. Conclusions 84
Acknowledgments 85
References 85
Coupling kinetic and spectroscopic methods for the investigation of
environmentally important reactions
94
F. C. Meunier
1. Introduction 94
2. The bases of spectrokinetic analyses 95
3. Investigation of the selective reduction of NOx with propene
over Ag/Al
2
O
3
96
4. Spectrokinetic operando investigation of catalytic reactions 105
5. Overall conclusions 116
References 117
Oxidative conversion of lower alkanes to olens 119
K. Seshan
1. Introduction 119
2. Oxidative conversion of alkanes to olens over oxide
catalysts with redox properties
122
3. Oxidative conversion of alkanes over oxide catalysts with
no formal redox properties
126
4. Catalytic alkane oxidation at ambient conditions using cold
plasma CC, CH scission vs CC bond coupling
131
Acknowledgements 139
References 139
Asymmetric hydrogenation of activated ketones 144
Jozsef L. Margitfalvi and Emlia Talas
1. Introduction 144
2. Cinchona alkaloids 151
3. Alkaloids used in Oritoss reaction 160
4. Methods and approaches used 164
5. Specicity of Oritos reaction 178
viii | Catalysis, 2010, 22, viiix
6. Spectroscopic investigations 220
7. Theoretical calculations 235
8. Reaction mechanisms and related calculations 243
9. Conclusions 258
Abbreviations used 261
References 262
Gold catalysis in organic synthesis and material science 279
Cristina Della Pina, Ermelinda Falletta and Michele Rossi
1. Introduction 279
2. Gold catalysis in organic synthesis 280
3. Selective oxidation of carbohydrates 292
4. Selective oxidation of hydrocarbons 296
5. Gold catalysis in material science 300
6. Conclusions 313
References 314
Catalysis, 2010, 22, viiix | ix
Bioethanol reforming for H
2
production.
A comparison with hydrocarbon reforming
Nicolas Bion,
a
Florence Epron
a
and Daniel Duprez
a
DOI: 10.1039/9781847559630-00001
Hydrogen is essentially produced by steam reforming (SR) of hydrocarbon
fractions (natural gas, naphtha, . . .) on an industrial scale. Replacing fossil
fuels by biofuels for H
2
production has attracted much attention with an
increased interest for bioethanol steam reforming. Kinetics and mechanisms
of hydrocarbon-SR and alcohol-SR present some similarities but also some
very important dierences due to alcohol reactivity much more complex
than that of hydrocarbons. The scope of this report is to compare the two
processes in terms of reaction mechanisms. Attention will also be paid to the
case of crude bioethanol.
1. Introduction
Whereas hydrogen is the most abundant element of the Universe, it is
relatively rare on Earth (0.9 atom % in the outer shell of our planet).
1
Virtually, it does not exist as dihydrogen: it is associated with oxygen in
water, with carbon in fossil hydrocarbons, both with oxygen and carbon
in bioresources (carbohydrates, cellulosic and lignocellulosic matter,
lignin, . . .) and more rarely with other elements. Water is by far the main
source of hydrogen on Earth (Table 1).
The stock of hydrogen available in fresh waters (lakes and rivers) is then
of 1.3 10
13
tons while the total ressources in hydrogen in oceans ans seas
amount to 1.5 10
17
tons. Comparatively, the ressources in hydrogen
available in fossil fuels are modest (Table 2).
Assuming a mean H/C atomic ratio of 1.66 in crude oil,
6
of 3.8 in natural
gas
7
and of 0.8 in coal,
8
the stock of hydrogen in fossil fuels would not
exceed 111 10
9
T (23 in crude oil, 30 in natural gas and 58 GT in coal
reserves), i.e. two orders of magnitude less than the amount of hydrogen
contained in fresh waters. Unfortunately, water is a stable molecule needing
a high energy input to recover hydrogen as H
2
. This energy may be provided
by (i) a chemical source by oxidizing the carbon of an hydrocarbon into CO
and CO
2
(steam reforming); (ii) by electricity (water electrolysis) or (iii) by
photons (water splitting). Steam reforming is by far the main process for H
2
Table 1 Total volumes of water available on Earth and equivalent amount of H
2
2,3
Oceans and Seas 1 350 000 000 km
3
1.5 10
17
T H
2
Deep continental waters 36 000 000 km
3
4 10
15
T H
2
Fresh waters (easily accessible)
Lakes and Rivers 110 000 km
3
1.3 10
13
T H
2
Rivers 1700 km
3
1.9 10
11
T H
2
a
University of Poitiers & CNRS. LACCO, Laboratory of Catalysis in Organic Chemistry,
40Av. Recteur Pineau, 86022 Poitiers Cedex, France
Catalysis, 2010, 22, 155 | 1
c
The Royal Society of Chemistry 2010
production
9,10
and only this way of hydrogen production will be examined
in this Chapter. On an environmental point of view, steam reforming is not a
green process since all (or almost all) the carbon of the hydrocarbons is
transformed into carbon dioxide. To avoid this drawback, fossil fuels may
be replaced by biofuels. Carbon dioxide is still produced but it may be
recycled to new biomolecules by photosynthesis. The annual production
of biomass in the World would be comprised between 150 and 420 10
9
metric tons.
1113
The mean hydrogen content in biomass being comprised
between 5 and 7 wt-%,
13
the stock of hydrogen in this renewable matter
would be close to 1110
9
T/year. In other words, ten years of biomass
production would be sucient to recover all the hydrogen content of fossil
fuels. However, a great part of this biomass is composed of wood, dicult
to transform into valuable products. For that reason, only products
derived from cellulosic and hemicellulosic biomass have been considered
for hydrogen production. Since ten years, intensive researches have been de-
voted to the steam reforming of bioethanol which is a fuel well-adapted to the
production of hydrogen.
14
This Chapter deals for a great part with this
process, with a special attention paid to the use of crude bioethanol. In a rst
part, however, the steam reforming of hydrocarbons (aromatics and alkanes)
will be reviewed as the model of many mechanistic investigations. This will
allow one to compare the steam reforming of hydrocarbons with the steam
reforming of ethanol, an alcohol leading to more complex kinetic schemes.
2. The steam reforming of hydrocarbons
2.1 Thermodynamics
For methane, four main reactions can occur:
1518
1. The steam reforming reaction leading to CO and H
2
CH
4
H
2
O ! CO 3H
2
DH
0
298
206 kJ mol
1
1
2. The steam reforming reaction leading to CO
2
and H
2
CH
4
2H
2
O ! CO
2
4H
2
DH
0
298
165 kJ mol
1
2
3. The water gas shift reaction (WGS)
CO H
2
O ! CO
2
H
2
DH
0
298
41 kJ mol
1
3
4. The coking reaction
CH
4
! C 2H
2
DH
0
298
75 kJ mol
1
4
Table 2 World proven reserves and consumptions of fossil fuels in 2008
4,5
World proven reserves
(10
9
TOE)
Annual consumption
(10
9
TOE)
Number of years of
reserve
Oil 181 4.0 45
Gas 172 2.7 65
Coal 610 3.8 160
1 TOE (Ton Oil Equivalent)=7.33 barrels=1000 m
3
of gas=1.5 T of coal
2 | Catalysis, 2010, 22, 155
For higher hydrocarbons, a similar set of reactions may be written; for
instance the reactions of n-heptane and of toluene leading to CO and H
2
become:
C
7
H
16
7H
2
O ! 7CO 15H
2
DH
0
298
1107 kJ mol
1
5
C
7
H
8
7H
2
O ! 7CO 11H
2
DH
0
298
869 kJ mol
1
6
Except for the WGS reaction, all the reactions involved in the hydrocarbon
steam reforming are strongly endothermic with an increase of the number of
molecules. They are thus favored at high temperatures and low pressures.
The temperature eect is illustrated in Fig. 1 which shows the change with T
of the gas composition at equilibrium in the methane steam reforming
(initial conditions H
2
O/CH
4
=1, P=1 bar). Calculations were carried out
by minimizing the sum of the Gibbs free energies of formation
of all the compounds (reactants and products) while keeping constant the
number of moles of each element (here C, H and O). Details of the pro-
cedure are given in Perrys Handbook.
19
Thermodynamic data (molar
Gibbs free energy of each compound) are taken from Stull et al.
20
Maximal
H
2
production is observed around 700 1C. Above 700 1C, the H
2
mol% does
no longer increase because of the preferential formation of CO at high
temperature. This is coherent with the WGS equilibrium: reaction 3 being
exothermic, CO
2
is favored at low temperature while the reverse reaction
(RWGS) yielding CO is favored at high temperature. At 900 1C, total
conversion of methane can be achieved yielding quasi-exclusively a syngas
with the composition given in equation 1 (75% H
2
25% CO).
0%
10%
20%
30%
40%
50%
60%
70%
80%
100 300 500 700 900
M
o
l
e

%
T (C)
H
2
O
CH
4
H
2
CO
CO
2
Fig. 1 Equilibrium composition of the methane steam reforming (without C formation).
Initial state: H
2
O/CH
4
molar ratio of 1, P=1 bar
Catalysis, 2010, 22, 155 | 3
The equilibrium gas compositions in methane, n-heptane and toluene steam
reforming at 700 1C are compared in Table 3. The initial state is a steam/
hydrocarbon mixture with a molar ratio corresponding to the stoichiometry
of equations 1, 5, 6 written with H
2
and CO as products of steam reforming.
Methane and steam conversions are very high but not total even at
700 1C. The vol.% of hydrogen expected in dry gases amounts to 70%. The
formation of methane and CO is favored in the steam reforming of C7
compounds at 700 1C, which tends to decrease the hydrogen content in dry
gases. In every cases, the CO-to-CO
2
molar ratio is remarkably constant
(around 7.7) whathever the starting hydrocarbon. The conversion of C7
hydrocarbons (not reported in Table 3) is total whatever the temperature.
Thermodynamics predicts that H
2
production from C
2
hydrocarbons is
controlled by methane formation. If, kinetically, methane formation can
be avoided, the equilibrium gas composition is signicantly changed. An
example is shown in Fig. 2 for toluene steam reforming without CH
4
for-
mation. The complete conversion of toluene only occurs around 550600 1C
and the maximal H
2
formation is observed at 500 1C, much below the
corresponding value when methane can be formed. Interestingly, benzene
formation can then be observed with a maximum around 400 1C. If methane
formation may be avoided or suppressed, toluene dealkylation can occur in
the 400500 1C range of temperature: this is the so-called toluene steam
dealkylation (TSDA) which has been largely studied in the past as a way
to produce benzene from toluene
2128
(and more generally from alkylben-
zenes)
29,30
without H
2
consumption.
2.2 Kinetics and mechanisms
Methane being a very stable molecule, the steam reforming of natural gas
should be carried out at high temperatures (around 600700 1C) and it can
be expected that methane activation is a critical step of the reaction (see
Section 2.2.3). Heavier hydrocarbons are more reactive and there are many
indications in the literature that water activation may be the rate deter-
mining step in the steam reforming of these compounds, specially at lower
temperatures (400600 1C).
2.2.1 Aromatics
2.2.1.1 Reaction scheme and catalytic activity. Toluene will be chosen as
model hydrocarbon illustrating this class of compounds. As mentioned in
Table 3 Equilibrium gas compositions and number of moles of gas formed (n
G
) in the steam
reforming of methane, n-heptane and toluene at 700 1C (P=1 bar)
H
2
O H
2
CO CO
2
CH
4
n
G
Methane Wet % 5.46 65.62 18.69 2.39 7.84 3.46
Dry % 69.41 19.77 2.53 8.30
n-Heptane Wet % 4.91 58.04 25.51 3.32 8.23 18.89
Dry % 61.03 26.83 3.49 8.65
Toluene Wet % 4.14 50.52 32.90 4.15 8.29 15.44
Dry % 52.70 34.32 4.33 8.65
Initial conditions: H
2
O/CH
4
=1; H
2
O/n-C7=H
2
O/Tol=7
4 | Catalysis, 2010, 22, 155
Section 2.1, the toluene steam reforming may lead to dealkylation (7) in
the 400500 1C temperature range where methane formation is kinetically
unfavored (8, 9).
C
7
H
8
H
2
O ! C
6
H
6
CO 2H
2
DH
0
298
164 kJ mol
1
7
C
7
H
8
H
2
! C
6
H
6
CH
4
DH
0
298
42 kJ mol
1
8
C
7
H
8
10H
2
! 7CH
4
DH
0
298
574 kJ mol
1
9
Equations 8, 9 clearly show that methane formation decreases the hydrogen
yield. If the reactions leading to benzene, CO, CO
2
and CH
4
are considered
(i.e. 3, 5, 79), the following relationship between the product yields could
be established:
30
7Y
H2
3Y
B
11Y
CO
18Y
CO
2
10Y
CH
4
10
Intrinsic activity and selectivity to benzene of Group 8-9-10 metals (ex
Group VIII) supported on g-Al
2
O
3
(210 m
2
g
1
) are reported in Table 4.
All the catalysts deactivate with time-on-stream. It was shown that the
selectivities vary very little when the catalysts are deactivating and that
the ow rate of dry gases (H
2
COCO
2
CH
4
) is proportional to the
toluene conversion. This property allows one to extrapolate the running
activity to zero-time. Turnover frequencies given in Table 4 are the intrinsic
activities determined by this technique. The deactivation is due to a carbon
deposit on the catalyst (metal and support). It was proved that toluene
steam dealkylation is a relatively structure insensitive reaction: the
0%
10%
20%
30%
40%
50%
60%
70%
80%
100 200 300 400 500 600 700 800
M
o
l
e

%
T (C)
H
2
H
2
O
TOL
CO
BENZ
CO
2
Fig. 2 Equilibrium composition of the toluene steam reforming at 1 bar without C and
methane formation (initial conditions H
2
O/TOL=7).
Catalysis, 2010, 22, 155 | 5
carbon deposit does not change the turnover frequency per free metal
atom which remains very close to the turnover frequency extrapolated at
zero-time. Free metal surface area in coked catalysts were measured ac-
cording to a procedure detailed in refs.
31,32
Initial selectivity to benzene
is the selectivity extrapolated at zero conversion. An interesting feature of
the toluene steam dealkylation reaction is the increase of S
B
with con-
version. For instance, rhodium selectivity reaches 86% at 10% conversion
and 92% around 40% conversion. This is due to a complex behaviour of
the catalyst including two phenomena: (i) though the dealkylation is
structure insentive, the total steam reforming of toluene (6) is not and is
strongly poisoned by coke deposits; (ii) CO is an inhibitor of both deal-
kylation and total reforming but the former reaction is much less
aected than the latter one.
22,33
The relative activities reported in Table 4
show that the steam dealkylation reaction is not very sensitive to the nature
of metal: there is less than one order of magnitude dierence between
the most active metal (Rh) and the less active one (Ir). The metal ranking
found by Duprez et al.
27
is close to that reported by Grenoble
24
in similar
conditions (440 1C, alumina support of 175 m
2
g
1
), except the water-
to-toluene ratio (3.25 in the Grenobles study). The only dierence lies in
the position of Ru found more active by Grenoble. Kim showed that pro-
moting alumina by vanadium oxide did not change signicantly the metal
ranking.
34
2.2.1.2 Support eects and reaction mechanism on rhodium catalysts.
Contrasting with the low sensitivity to nature of metal, the steam deal-
kylation reaction appeared as very sensitive to nature of support. This is
illustrated in Table 5 with the rhodium as active metal. There are two to
three orders of magnitude dierence between the activity of rhodium
catalysts supported on chromia or aluminochromia catalysts
35
and those
supported on silica or carbon.
25,27
The data of Table 5 show that the dif-
ferences are not due to metal dispersion eects. Catalyst characterization
carried out after test also conrmed that there was no sintering during
the kinetic measurements aecting more certain supports. A bifunctional
mechanism was proposed by Grenoble
26
and Duprez et al.
27
to explain
this dramatic support sensitivity. In this mechanism schematized on Fig. 3,
Table 4 Intrinsic activity and selectivity to benzene of Group 8-9-10 metals supported on
g-Al
2
O
3
(reaction conditions: T=440 1C; P=1 bar; H
2
O/TOL molar ratio of 6). From ref.
27
Metal/g-Al
2
O
3
Turnover
frequency (h
1
)
Relative activity
(based on Rh=100)
Initial selectivity
to benzene (S
B
%)
0.6% Rh 470 100 81
0.6%Pd 134 29 97
1.1%Pt 88 19 98
5%Ni 77 17 59
5%Co 67 15 51
0.6%Ru 64 14 53
1.15%Ir 60 13 88
6 | Catalysis, 2010, 22, 155
the hydrocarbon molecule would be adsorbed and activated on metal sites
while the water molecule would be activated on support sites.
The molecule of toluene undergoes a dissociative chemisorption on a
metal site M leading to a molecule of benzene and an alkyl fragment (11).
This reaction should require two metal sites. However, benzene being less
strongly adsorbed than toluene on metals, it is immediately desorbed once
formed.
C
6
H
5
CH
3
M ! CH
x
M C
6
H
6

2x
2
H
2
11
Water is activated on support sites (SOS) according to equation 12:
H
2
O SOS ! 2SOH 12
The nal step is a transfer of OH groups to metal particles where they react
to form carbon oxides and hydrogen:
CHxM 2SOH ! CO
x
2
H
2
SOS M 13
Table 5 Support eect in toluene steam dealkylation at 440480 1C (base 100 for well dis-
persed Rh on g-Al
2
O
3
)
Support
Surface area
(m
2
g
1
)
Rh dispersion
(%)
Relative activity of
rhodium (per metal site) Reference
Cr
2
O
3
40 20 300400 35
g-Al
2
O
3
210 90100 100 23,25,27
a-Cr
2
O
3
10 90100 50 36
Al
2
O
3
-SiO
2
300 50 4050 30
TiO
2
10 30 20 27
Al
2
O
3
-SiO
2
110 40 15 37
SiO
2
330 40 20 27
SiO
2
260 90100 20 37
SiO
2
300 70 3 25
C 950 40 1 25
unsupported 5 1.2 0.1 25
Surface
migration
H
2
O
C
X
H
Y
metal
OH OH
CH
3
support
Fig. 3 Bifunctional mechanism of toluene steam dealkylation
Catalysis, 2010, 22, 155 | 7
The global reaction in this catalytic cycle is the dealkylation to benzene,
CO and H
2
. It is implicitely assumed that CO
2
is formed by water gas shift.
The reaction rate (per gram of catalyst) derived from equation 13 is:
r ky
CHx
x
2
OH
14
where y
CHx
is the surface coverage of CHx fragments on metal sites
while x
OH
is the OH group coverage on support sites. As step (13) implies a
transfer of OH groups through the metal/support interface, it is assumed
that k=KI
0
, I
0
being the length of the particle perimeter per gram of
catalyst. Surface coverages are deduced from equations 11, 12 and
Langmuir-type hyperbolic expressions for equilibium adsorption of mol-
ecules A can be approximated to power-law expressions using the following
equation:
K
A
P
A
1 K
A
P
A
aK
A
P
A

n
15
Inserting power-law expressions for the surface coverages in equation 14
leads to the following rate equation:
27,38
TOF
r
M
0
CS
2
0
l
0

1n
P
n
T
P
m1n
W
16
where M
0
and S
0
are the numbers of metal sites and of support sites, re-
spectively, per gram of catalyst; P
T
and P
W
are the partial pressures of
toluene and water. Knowing the weight loading (x
m
%) and the dispersion
D
0
(%) of metal, the specic perimeter I
0
can be calculated by:
I
0
bD
2
0
x
m
17
with b 1:6 10
7
rA
2
mol
M
cubic particles 18
r being the metal density (gm
3
), A
mol
the molar surface of metal (m
2
mol
1
) and M, the atomic weight (g mol
1
). For Rh, r=12.45 10
6
g m
3
,
A
mol
=47633 m
2
mol
1
(equidistribution of low index faces) and
M=102.9 g mol
1
, which gives b=4.28 10
5
mg
1
. It is worth noting that,
for a catalyst commonly used in steam reforming (0.6%Rh, mean dispersion
of 50%), I
0
amounts to 6.4 10
8
mg
1
, a length greater than the Earth-
Moon distance. This justies the great impact the reactions at metal/support
interfaces may have in Catalysis.
Equations 16, 17 shows that TOF values should be proportional to I
0
1 n
.
Grenoble reported kinetic orders of 0.08 and of 0.41 with respect to toluene
and to water.
25
Most authors found orders with respect to toluene com-
prised between 0.03 and 0.25 while those with respect to water are generally
close to 0.5.
30
One may thus expect TOF values to be proportional to I
0
.
Table 6 reports the results obtained on a series of Rh/Al
2
O
3
catalysts.
There is a complex variation of the intrinsic activity with the metal
loading and the dispersion (almost a factor 20 between the most active
catalyst and the less active one). Applying the bifunctional model with
n=0 reduces the variation to a factor 4 while a very good t is obtained
8 | Catalysis, 2010, 22, 155
for n=0.3 (factor 1.7 and less than 1.1 for nine of the ten samples). To
sum up, the kinetic model based on the bifunctional mechanism represents
adequately the changes of activity of Rh/Al
2
O
3
catalysts in toluene steam
dealkylation.
2.2.1.3 Other metals. The support eect evidenced for Rh catalysts
was investigated for other metals by comparing their activity on alumina
and silica
27
(Table 7). There are two groups of metals: those showing a
strong support eect in steam dealkylation (Pt, Rh, Pd and to a lesser
extent, Ir) and those having the same activity on alumina and silica (Ni;
Co and Ru).
In an investigation of multifuel reforming (including toluene), Wang and
Gorte conrmed the dramatic eect of the support in these reactions.
39
For
instance, Pd/CeO
2
was about 7 to 10 times more active than Pd/Al
2
O
3
in the
steam reforming of toluene between 400 and 500 1C. As a rule, ceria or
ceria-based oxides were found to be very good supports for metals in several
steam reactions (steam reforming and water-gas shift).
4043
The mechanism
of these reactions on ceria-based catalysts is likely to dier from that pro-
posed on alumina catalysts in equations 1113. Ceria is a reducible support
Table 6 Verication of the bifunctional mechanism in toluene steam
dealkylation (440 1C; P
T
=0.145 atm and P
W
=0.855 atm). From ref.
32
TOF
D
2
0
x
m

1n
Rh loading
(x
m
% Rh)
Dispersion
(D
0
%)
TOF
(h
1
) n=0 n=0.3
0.031 100 60 0.194 1.08
0.063 100 160 0.254 1.76
0.18 95 180 0.111 1.02
0.58 92 430 0.088 1.12
0.60 96 460 0.083 1.10
4.82 45 650 0.067 1.05
4.87 61 1070 0.059 1.12
10.1 13.7 200 0.106 1.02
10.3 32 700 0.066 1.07
Table 7 Support eects of dierent metals in toluene steam dealkylation
(reaction conditions: 440 1C, partial pressures: 0.145 bar of toluene and
0.855 bar of water)
Metal
TOF
(M/Al
2
O
3
) h
1
TOF
(M/SiO
2
) h
1
TOF ratio
(Al
2
O
3
/SiO
2
)
1.1%Pt 88 15 5.87
0.6% Rh 470 91 5.16
0.6%Pd 134 54 2.48
1.15%Ir 60 45 1.33
5%Ni 77 69 1.11
5%Co 67 64 1.05
0.6%Ru 64 62 1.03
Catalysis, 2010, 22, 155 | 9
able to dissociate the water molecule and to produce directly hydrogen in a
redox process. As proposed by Wang and Gorte,
39
hydrocarbon activation
would be very similar to equation 11 of the OH-migration mechanism while
equation 12, 13 should be replaced by the following steps:
H
2
O Ce
2
O
3
! 2CeO
2
H
2
19
CH
x
M 2CeO
2
! COM Ce
2
O
3

x
2
H
2
20
The possible occurrence of step 19 has been demonstrated by direct de-
composition of water over reduced ceria.
4446
The writing of equations 19,
20 is certainly oversimplied since Ce
2
O
3
very likely cannot be formed
under the conditions of steam reforming. There exist numerous sub-oxides
CeO
2 x
(with 0oxo0.5) whose existence is more probable in these
conditions.
47
Metals of class 2 (Ni, Co, Ru) are not support-sensitive. These metals
have the lowest M
n
/M1 electrochemical potential and can dissociate the
water molecule in steam reforming conditions. For these metals, a mono-
functional mechanism with all steps occuring on the metal was proposed.
27
equations 12, 13 are replaced by equations 21, 22 respectively
H
2
O M HO M
1
2
H
2
equilibriumconstant K
W
21
CH
x
M HO M ! CO
x
2
H
2
2M rate constant k 22
This mechanism led to the following rate equation:
TOF
k
T
P
T
1 K
1
k
T
P
T
kKM
0

23
k
T
being the rate constant of the dissociative adsorption of toluene (11) and
K is a constant depending on water dissociation equilibium (21):
K
K
W
P
H2O
P
1=2
H2
24
2.2.1.4 Isotopic exchange studies.
16
O/
18
O and H/D isotopic exchange
studies were performed to measure the rate of diusion of OH groups
involved in the bifunctional mechanism of steam reforming.
4851
The
principle of the measurement is depicted in Fig. 4.
Exchange experiments are typically performed with pure
18
O
2
at t=0. Two
conditions should be fullled: (i) adsorption/desorption of O
2
on the metal
particles (step 1) should be very fast. This is veried by measuring the rate of
isotopic equilibration between
18
O
2
and
16
O
2
on the metal; (ii) the rate of
direct exchange between
18
O
2
and the support (step 5) should be negligible.
This is veried by measuring the rate of exchange on bare supports. Similar
experiments were carried out with deuterium to measure the rate of hydrogen
migration. A simple kinetic model is sucient to calculate the coecient of
surface diusion D
S
for supports having moderate O or H mobility.
50
When
surface mobility is very fast, more complex kinetic models should be
used.
52,53
Several important conclusions could be drawn from these studies.
10 | Catalysis, 2010, 22, 155
1. While hydrogen is very mobile on most supports below 100 1C, oxygen
surface diusion is a relatively slow process and requires temperatures in the
300500 1C range to be measurable.
2. However, activation energy for oxygen surface diusion (50100 kJ
mol
1
) is signicantly higher than that for hydrogen (1020 kJ mol
1
). As a
consequence, oxygen and hydrogen migrations occur at similar rates around
5001C.
3. Rhodium is the best metal for oxygen activation.
54
Adsorption/de-
sorption of O
2
on this metal is very fast and is not very sensitive to the metal
particle size: it is slightly faster on small Rh clusters than on big particles.
By contrast, step 1 is not so fast on Pt. However, this step is very sensitive to
the metal particle size and, contrary to the case of Rh, it is much faster on
big Pt particles. Oxygen equilibration is very slow on Pd while Ru and Ir
could be good candidate for replacing Rh under certains conditions.
55
4. The relative values of coecients of surface diusion for oxygen and
hydrogen on selected oxides are given in Table 8.
Oxygen and hydrogen diusing at the same rate in the 400500 1C range
of temperature, it is very likely that there is a collective migration of OH
groups at these temperatures on most oxides. A crucial point is that OHs are
virtually immobile on silica while the coecient of diusion would be two
orders of magnitude higher on alumina. This result is in agreement with the
bifunctional mechanism with the slow step being the OH group migration
Table 8 Relative mobility of oxygen and hydrogen on oxide-supported
Rh catalysts (Rh is used here as a porthole for O and H diusion on oxide
surfaces). From ref.
48,51
Oxygen at 400 1C Hydrogen at 75 1C
CeO
2
2300 CeO
2
80
MgO 50 MgO 22
ZrO
2
28 CeO
2
/Al
2
O
3
16
CeO
2
/Al
2
O
3
18 Al
2
O
3
10
Al
2
O
3
10 ZrO
2
2.3
SiO
2
0.1 SiO
2
Very low
Surface
mobility
Metal
18
O
16
O
16
O
2
18
O
2
18
O
16
O
18
O
18
O
16
O
18
O
2
Support
Fig. 4
18
O
2
exchange with the
16
O of the support via the metal particles. Step 1: adsorption/
desorption of O
2
on metal particles; Step 2: O transfer from metal to support; Step 3: surface
migration; Step 4: place exchange of
18
O with
16
O Step 5: direct exchange gas/support.
Catalysis, 2010, 22, 155 | 11
from support to metal. This explains why silica is a poor support for steam
reforming reactions. Unfortunately, carbon supports could not be investi-
gated by isotopic exchange. There are some indication in the literature that
O species are quite mobile on carbon: for instance Lim et al. found that NO
decomposition was favored on Pt/C by continuous removal of O species
from the metal by the support itself.
56,57
The most probable explanation
for the low activity of carbon-supported metal catalysts might be the high
hydrophobicity of carbon surface which cannot easily activate the water
molecule.
2.2.1.5 Recent studies on fuel and tar reforming. In the last ten years,
much attention was paid to steam reforming reactions for hydrogen pro-
duction from gasoline, heavy oils, biomass and tars. Toluene was chosen as
model aromatic hydrocarbon in many studies with the objective to reform
totally the molecule and obviously not to produce benzene. However, steam
dealkykation could be observed when the steam reforming of aromatic-
reach fractions was used to produce hydrogen.
Fuel reforming. Hydrogen production for on-board applications was
investigated by Springmann et al.
58
at 600800 1C, 25 bar over rhodium
catalysts deposited on metallic monoliths. The reaction led essentially to a
syngas (30% H
2
12% CO) with small amounts of benzene, methane and
CO
2
. A detailed analysis of benzene reactivity supports the interpretation
that toluene is rst dealkylated to benzene which is then gasied. Due to
signicant formation of coke, the catalyst is not stable in toluene steam
reforming. Stable hydrogen production (with less carbon deposit) was
obtained in an autothermal ATR process (H
2
O:O
2
:TOL=14:3:1). Steam
reforming or ATR of iso-octane, hexene and gasoline were also investigated
on the same catalysts. These hydrocarbons were slightly more reactive than
toluene with higher amounts of CO
2
in the syngas at 675 1C (3.5% CO
2
instead of 1% with toluene).
Similar results were obtained by Qi et al. who studied gasoline auto-
thermal reforming at 650800 1C over a complex Rh catalyst (0.3%Rh/
3%MgO/20%CeO
2
-ZrO
2
) washcoated on a ceramic monolith.
59
The
authors showed that alkanes led to minor amounts of methane together with
the syngas while aromatics (e.g. toluene) rather led to methane-free syngas.
Qi et al. also pointed out the role of sulfur in promoting coke formation as
well as the detrimental eect of washcoating the catalyst on a ceramic
monolith of low thermal conductivity. This sulfur eect on coke formation is
not in agreement with previous results of Duprez et al. who showed that
sulfur might hinder coke formation in toluene steam dealkylation.
3132,60
The apparent discrepancy is likely coming from the dierences of tempera-
tures (440 1C in steam dealkylation and 650800 1C in ATR of gasoline).
Sulfur poisoning is a critical problem in steam reforming processes. SR is
operating on reduced catalysts under conditions where the sulfur organic
compounds are themselves steam reformed into hydrogen, carbon oxides
and dihydrogen sulde. Several studies were carried out to attempt solving
this drawback. Azad et al. have developped several catalyst formulation for
the steam reforming of jet fuels in the presence of large amounts of sulfur
12 | Catalysis, 2010, 22, 155
(up to 1000 ppm).
6163
The best support tested by Azad et al. was a ternary
oxide composed of 10 mol-% Gd
2
O
3
, 25 mol-% ZrO
2
and 65 mol-% CeO
2
doped or not by Y
2
O
3
or CuO. Active metals were Rh,
61,63
Pd
62
or com-
bination of both metals
61
tested in the steam reforming of toluene at 8251C
(with or without 50 ppmS as thiophene). Ceria was shown to play a sig-
nicant role in the catalyst thioresistance. Two reactions can occur (25, 26)
which help mitigate sulfur-led poisoning and long-term deactivation:
Reduction reaction:
CeO
2
s 2nH
2
g CeO
n
s 2nH
2
Og 25
Suldation reaction:
2CeO
n
s H
2
S 2n3H
2
g Ce
2
O
2
Ss 2n1H
2
Og 26
The specic role of ceria in sulfur resistance of Rh catalysts for jet fuel
reforming applications was conrmed by Strohm et al. who also showed
that Ni added to Rh reinforced the thioresistance of a Rh-CeO
2
-Al
2
O
3
catalyst.
64
Rhodium-based catalysts oered a better resistance to de-
activation than Pd-ones and the addition of Cu signicantly improved the
thioresistance of the GdZrCeOx support. This property may be paralleled
with the exceptional OSC (oxygen storage capacity) of Rh-CuCeOx cata-
lysts, showing the great mobility of oxygen (and probably sulfur) in these
materials.
65
To increase the hydrogen yield, combination of steam reforming (SR),
autothermal reforming (ATR) and water gas shift is often proposed in in-
tegrated processes.
66,67
Gasication of a fuel composed of methylcyclo-
hexane and toluene was studied by Wang et al. at 530 1C.
68
Combining SR
and WGS on a multifunctional catalyst (Ni-Re/Al
2
O
3
) allows to increase
the CO
2
/COCO
2
ratio up to 92% (at 16% conversion). This is coherent
with the excellent performances of Ni and Re in WGS as reported by
Grenoble et al.
69
These authors showed that the WGS reaction was very
sensitive both to nature of metal and to that of support (Table 9).
Table 9 Turnover frequency of alumina-supported metals and support
eect in water-gas shift reaction at 300 1C (24 vol-% CO32 vol-%
H
2
O). From ref.
69
Support eect
Metal/Al
2
O
3
TOF (h
1
) Catalyst Relative activity
Cu 43 400 Pt/Al
2
O
3
90
Re 1380 Pt/SiO
2
9
Co 890 Pt/C 1
Ru 695
Ni 370 Rh/Al
2
O
3
13
Pt, Os 225 Rh/SiO
2
1
Au 130
Fe, Pd 50
Rh 31
Ir 12
Catalysis, 2010, 22, 155 | 13
As WGS is an exothermic reaction, it is favored at low temperature. For
this reason, Wang et al. found better perfomances in a classical two-bed
process with ATR (instead of SR) at relatively high temperature and WGS
at low temperature. A Ni/Ce-ZSM5 was developped for this application.
The use of Ce as dopant could be anticipated, ceria being a very good
promoter of the WGS reaction.
40,41,70,71
Table 9 shows that Rh is a bad
WGS catalyst while it is considered as the best SR metal. Pt is a better WGS
catalyst than Rh but it is less active in steam reforming. Interestingly, Pd
has often intermediary properties between those of Pt and Rh in several
reactions with the following ranking: Rh WPd WPt in SR and Pt WPd
WRh in WGS. For these reasons, the most advanced catalyst formulation
for multifuel reforming applications include generally both Rh or Pd and a
WGS component (most often a ceria-based materials). Wang and Gorte
showed that their Pd/CeO
2
catalyst was active in the reforming of many
hydrocarbons: methane, ethane, n-butane, n-hexane, 2,4-dimethylhexane,
n-octane, cyclohexane, benzene, and toluene.
39
Nilsson et al. investigated the ATR of hydrocarbons, alcohols, gasoline
and E85 over a catalyst composed of Rh supported on Ce/La-doped g-Al
2
O
3
and deposited on cordierite monoliths.
72
Provided that the fuel is correctly
vaporized under the form of very ne droplets (the critical point of the
process), good hydrogen yields and selectivities may be obtained by ATR of
complex mixtures such as Diesel gasoils or gasolines. It should however be
mentionned that the swedish fuels used in this study contained low amounts
of sulfur and that the aromatics content of the diesel was comparatively
lower than in other countries. These factors allowed the catalyst to be more
resistant to sulfur poisoning and to coke formation than with more common
fuels.
Steam reactions (HCs steam reforming or WGS) are key-reactions in
Three-Way Catalysis (TWC) for converting pollutants in rich conditions
when O
2
concentration in gas phase falls below stoichiometry.
41,42,73,74
However, with aromatic gasolines, there is a risk to form benzene by steam
dealkylation. In the temperature window of 550730 1C, Bruelmann et al.
observed the net formation of benzene and toluene in the gases issued from
a Pd-Rh-CeZrOx-Al
2
O
3
TWC in real conditions.
75
The gasoline used in this
study contained 41.2% (wt.%) monoaromatics, including 3.4% benzene,
16.6% monoalkylated, 15.8% dialkylated, 5.2% trialkylated, and 0.3%
tetraalkylated benzenes, respectively. Whereas all the C8

alkylated com-
pounds decreased in the post-catalyst exhaust gases, it was shown that the
concentration of benzene and toluene increased. Bruelmann et al. studied in
detail the conversion of 12 alkylbenzenes representing 75% of all possible
benzene precursors in the post-catalyst exhaust gases. These alkylbenzenes
were individually spiked in the pre-catalyst chamber to follow their con-
version by chemical ionization mass spectrometry (CI-MS). Dealkylation
reactions of ortho-substituted dialkylbenzenes show a clear preference
towards benzene formation, whereas meta- and para-isomers mainly form
toluene at 630 1C with some shift of the product distribution towards ben-
zene at higher temperature (680 1C). Steam dealkylation is by far the most
important reaction leading to benzene formation even though some
hydrodealkylation cannot be discarded.
14 | Catalysis, 2010, 22, 155
Steam reforming can be applied in the Exhaust Gas Recirculation (EGR)
loop of cars to increase the hydrogen content in the gases reinjected into the
combustion chamber.
76
The combustion of the gasoline with a gas enriched
in H
2
leads to a signicant decrease of pollutants and to a better engine
yield.
Tar reforming. Gasication process of biomass leads to a variety of
products, specially tars which should be steam reformed to increase H
2
yields.
77
Again, benzene, toluene or oxygenated aromatics such as phenol or
cresols are often chosen as model compounds. In the 19701980s, con-
siderable attention was paid to the treatment of tars by CO/H
2
O mixtures,
hydrogen being in situ generated by the water-gas shift reaction.
78,79
In these
studies, the main objective was to hydrogenolyze CC bonds to produce
lighter hydrocarbons without paying attention to H
2
production. Steam or
oxy-steam gasication of tars was studied in the 90s over dierent dolo-
mites with the objective to favor syngas formation.
8082
These materials
were proved to oer a relatively good gasication activity while minimizing
the catalyst cost. They may be a good support for Ni to increase H
2
yield
while minimizing the coking rate.
83
However, their poor mechanical sta-
bility made them useless in uidized reactors. They were progressively
replaced by olivine, a Mg-Si-Fe ternary oxide very resistant to attrition.
84
Olivine is a natural mineral whose mean composition is 49 wt-% MgO,
42 wt-% SiO
2
, 8 wt-% Fe
2
O
3
and about 1% Al
2
O
3
and CaO, with a BET
area of 45 m
2
g
1
. It was used alone in biomass gasication or as a support
of metals (mainly Ni) to get more active catalysts.
85
A detailed investigation
of toluene steam reforming over Ni/olivine was performed by Swierczynski
et al.
86,87
The reaction temperature was varied in the 550850 1C range and
the H
2
O-to-toluene molar ratio was maintained between 7.5 and 24 with a
standard value of 16 for most kinetic studies. Total conversion of toluene is
reached at 650 1C over Ni/olivine while the reaction on the bare support
starts at 750 1C. Reaction selectivities are reported in Table 10 for standard
tests at 850 1C. The hydrogen yield is 82% on Ni catalyst and only 28% on
olivine (a 100% yield corresponds to 18 moles of H
2
produced per mole
of toluene injected). The thermodynamic limitation at high temperature
which tends to favor CO formation (only 11 moles H
2
per mole of toluene
according to eq. 6, i.e. a H
2
yield of 61%) is compensated by the high water/
toluene ratio. Moreover, on Ni/olivine, no hydrocarbon is detected which
proves that methane, benzene and polyaromatic hydrocarbons (still formed
on olivine) are totally converted.
Table 10 Comparison of catalytic perfomances of olivine and Ni/olivine in toluene steam
reforming at 850 1C (H
2
O/TOL=16). From ref.
87
Catalyst
Selectivities %
a
H
2
yield (%)
b
CO CO
2
CH
4
Benzene Polyaromatics
Olivine 69 5 2 6 14 28
Ni/olivine 66 31 0 0 0 82
a
dened as the % of C in the product per C in reacted toluene.
b
based on 100% for 18 moles
H
2
produced per mole of toluene injected.
Catalysis, 2010, 22, 155 | 15
A detailed characterization of the active sites of Ni/olivine was performed
by Swierczynski et al. by means of Mo ssbauer spectroscopy and several
other techniques (XRD, SEM, H
2
-TPR).
88
They showed that the good
activity of Ni/olivine was linked to the formation of a NiO-MgO solid so-
lution at the olivine surface during the oxidation and to Ni alloying by Fe
during the reduction. Both phenomena contribute to make the catalyst
more resistant to sintering and to coke formation. To increase activity in tar
gasication, Zhang et al. proposed to dope Ni/olivine with ceria.
89
The best
results for the steam gasication of benzene and toluene were obtained
between 700 and 830 1C on a 3% NiO-1%CeO
2
/olivine. Ceria allows to
increase benzene and toluene conversion and to form more H
2
and CO
2
and
less CO and methane (Table 11).
Other supports of Ni or Co were used for the steam reforming of model
tar compounds: ceria-zirconia,
90
Al-La coprecipitate in the presence of Ni
and Co
91
or Ni-Mg-Al-based commercial steam reforming catalysts.
92
These studies were carried out at relatively high temperatures.
Lamacz et al. investigated the toluene steam reforming over Ni or
Co/Ce
0.7
Zr
0.3
O
2
catalysts (100130 m
2
g
1
) from 400 to 900 1C.
90
They
found however a total conversion of toluene at 600 1C and above. Bona
et al. restricted their study to a temperature of 650 1C focusing their
investigation on the optimization of La/Ni and Co/Ni ratios.
91
Tempera-
tures from 700 to 875 1C were chosen by Coll et al.
92
to study the steam
reforming of ve aromatic compounds: benzene, toluene, naphthalene,
anthracene and pyrene representative of a biomass gasication tar whose
composition is given in Table 12.
Benzene and toluene are by far the most reactive of the compounds test-
ed, with conversions in the order of 1 g
HC
g
cat
1
min
1
at a H
2
O/C ratio
around 4. On the other hand, pyrene (H
2
O/C=12.6) and naphthalene
(H
2
O/C=4.2) are the least reactive compounds, with conversions varying
from 0.01 to 0.025 g
HC
g
cat
1
min
1
, depending on temperature. As a rule,
Table 11 Comparison of catalytic performances of 3%NiO/olivine (A) and 3%NiO-1%CeO
2
/
olivine (B) in steam reforming of benzene and toluene at 750 1C. Reaction conditions: S/C ratio
of 5; space velocity: 862 h
1
. From ref.
89
Catalyst Benzene steam reforming Toluene steam reforming
Conv. % H
2
% CO % CO
2
% CH
4
% Conv. % H
2
% CO % CO
2
% CH
4
%
A 40.5 61.3 32.5 6.3 0.01 45.9 61.2 28.9 10.2 0.16
B 60.5 63.6 23.8 12.6 0.01 64.8 63.6 22.5 14.6 0.11
Table 12 Typical composition of a biomass gasication tar. From ref.
92
Compound wt-% Compound wt-%
Benzene 37.9 Three-ring aromatics 3.6
Toluene 14.3 Four-ring aromatics 0.8
Other alkylbenzenes 13.9 Phenolic compounds 4.6
Naphthalene 9.6 Heterocyclic compounds 6.5
Alkylnaphthalenes 7.8 Other 1.0
16 | Catalysis, 2010, 22, 155
the gas composition in these studies
9092
follows the thermodynamic ten-
dency: decrease of CO
2
and CH
4
and increase of CO when the temperature
is increased.
Catalyst deactivation is one of the major problems encountered in tar
gasication. Bain et al. investigated tar reforming with a special attention
to benzene, toluene and light alkane transformation. They modeled the
kinetics of reforming and in parallel, the kinetics of deactivation of their
Ni-alkali-Al
2
O
3
catalyst at ve temperatures from 775 to 875 1C.
93
First-
order rate equations were found to represent both the kinetics of reforming
and that of deactivation. Large dierences in activation energies for
reforming and deactivation of total tar gasication on one hand and of
individual hydrocarbon gasication (benzene, ethane, methane, . . .) on the
other hand were observed. This shows that tar gasication is a complex
process and that modeling gasication of some hydrocarbons present in
these tars may not represent the total gasication kinetics. The most critical
parameter for coke formation is the H
2
O/C ratio. Interestingly, Coll et al.
92
gave the limit values of this parameter to prevent massive coke formation
when dierent aromatic hydrocarbons are gasied (Table 13).
2.2.2 Non-methanic alkanes. Less attention was paid to the steam
reforming of C
2

alkanes. Kikuchi et al. reported a detailed investigation of

the reforming of n-heptane at 5501C over Rh catalysts.
94
N-heptane may
be converted by two reactions: (i) gasication by steam reforming and (ii)
aromatisation into toluene. Toluene itself may be gasied by steam; how-
ever, if the reaction is carried out at relatively low space time, it is possible to
determine the initial selectivities to gasication and to aromatisation.
Interestingly, it can be seen on Fig. 5 that the intrinsic rates of steam re-
forming t well with the kinetic equation developped for the toluene steam
dealkylation (16, 17). In Fig. 5, the ratio TOF/D
2
0
x
m
is remarkably constant
when the metal loading in the catalysts (x
m
) was varied from 0.1 to 5% with
metal dispersion decreasing from 100% (0.1%Rh) to 45% (5%Rh).
Aromatisation is likely to occur on metal sites exclusively: no correlation
can be found between TOF of this reaction and the parameter represen-
tative of a bifunctional metal/oxide reaction.
The role of the support was conrmed by Muraki and Fujitani
95
who
proposed the following rate equation for n-heptane reforming over Rh/
MgAl
2
O
4
catalysts:
r k
K
c
P
c
1 K
c
P
c

K
W
P
W
1 K
W
P
W

27
Table 13 Experimental limit of H
2
O/C ratio for carbon
formation at the lower temperature studied. From ref.
92
Compound T (1C) Limit H
2
O/C ratio
Toluene 725 2.5
Naphthalene 795 3.7
Anthracene 790 6.6
Pyrene 790 8.4
Catalysis, 2010, 22, 155 | 17
where subscript C refers to n-C7 (adsorbed on metal sites) and W to
water (adsorbed on support sites). Wang and Gorte investigated the steam
reforming of dierent fuels over a Pd/CeO
2
catalyst (see Section 2.2.1.5 fuel
reforming).
39
The same catalyst was proved to be more active and more
stable than Pd/Al
2
O
3
in the steam reforming of n-butane with a remarkable
CO
2
selectivity even for a relatively low H
2
O/C ratio.
96
The specic role of ceria in steam reforming was linked to its redox prop-
erties, which led Wang and Gorte to extent to higher hydrocarbons the cycles
(27)(30) already proposed for ceria in the steam reforming of methane.
97
CH
4
s ! CH
x;ads
4 xH
ads
28
H
2
O Ce
2
O
3
! 2CeO
2
H
2
29
2H
ads
! H
2
s 30
CH
x;ads
2CeO
2
! CO x=2H
2
Ce
2
O
3
s 31
where s represents a metal site.
Steam is a cause of severe metal sintering in SR or ATR processes.
98
The
good performances of ceria as a support of steam reforming could be
improved by doping the support with other oxides such as Gd
2
O
3
: very
stable performances (for 160 h) were observed in iso-butane steam re-
forming on a Pt-Ce
0.8
Gd
0.2
O
1.9
catalyst.
99
Coke resistance of steam reforming catalysts is a key-point for aromatic
processing and also for light alkane gasication. A remarkable improve-
ment of coke resistance of Ni catalysts in propane steam reforming was
reported by Takenaka et al.
100
Three Ni catalysts (Ni/MgO, Ni/Al
2
O
3
and
Ni/SiO
2
) were prepared by conventional impregnation of pre-formed sup-
ports while a special catalyst was prepared by a microemulsion route in-
cluding both the Ni precursor, TEOS and hydrazine. The resulting material
prepared by microemulsion (named coat-Ni) consists in Ni particules of
homogeneous size coated with an external layer of silica (Fig. 6).
0
5
10
15
20
25
0 1 2 3 4 5 6
T
O
F
/
A
%Rh
Aromatisation
Steam reforming
Fig. 5 Reaction of steam with n-heptane at 550 1C on Rh/Al
2
O
3
catalysts: comparison of
steam reforming and aromatisation reactions
18 | Catalysis, 2010, 22, 155
The strong interaction of Ni metal particles with silica, in the silica-coated
Ni catalysts, prevents the sintering of Ni metal and carbon deposition
during the steam reforming of propane: the rate of coke formation at 600 1C
was decreased by a factor 2 to 3 on coat-Ni with propane conversion ap-
proaching 100%. Alumina was often used as support of Ni in alkane steam
reforming. Ni, Fe and Co are metals able to form carbides, precursors of
carbon laments, when they react in a hydrocarbon atmosphere.
101,102
Zhang et al. succeeded in preventing sintering and coke formation by
using a one-step sol-gel preparation.
103
Nickel nitrate and aluminium tri-sec
butoxide dissolved in ethanol were used as precursors. SG catalysts were
compared to conventional catalysts prepared by impregnation. SG samples
are characterized by smaller Ni particles strongly bound to alumina surface.
The formation of carbon laments requiring a detachment of Ni particles
from the surface
104106
is signicantly slowed down in SG catalysts.
2.2.3 Methane steam reforming (MSR). Natural gas reforming is the
main source of hydrogen in the World. Annual production od H
2
is esti-
mated to 400 billions m
3
, North America being the most important pro-
ducer (230 billions m
3
).
107
About 60% come from narural gas reforming
and the major part of rest from petroleum renery or naphtha reforming.
For this reason, methane steam reforming has been the subject of hundred
of papers and many reviews or monographies (see for instance thoses of
Rostrup-Nielsen,
15,16
Ross
108
and Inui).
109
Only the studies dealing with
mechanistic considerations will be reviewed here. The central question in
this section is: does methane reforming obey a specic mechanism, dierent
of that proposed for heavier hydrocarbons?
2.2.3.1 MSR mechanism with CH
4
activation as rate determining step.
Bodrov and Apelbaum were among the rst authors to show similarities
between the mechanisms of steam and dry reforming of methane (32).
110
They suggested that CO
2
was shifted to CO and water which could be the
main (or unique) reactant of methane gasication.
CH
4
CO
2
! 2CO 2H
2
32
Fig. 6 TEM images of 10 wt-%Ni/SiO
2
(a) and coat-Ni (10 wt-%) (b). Reprinted with per-
mission from ref. 100.
Catalysis, 2010, 22, 155 | 19
In 1993, Rostrup-Nielsen and Bak Hansen showed that methane steam
reforming (MSR, 1) and methane dry reforming (MDR, 32) had relatively
close rates on most metal catalysts (Ni, Ru, Rh, Pd, Ir, Pt) supported on
magnesia.
111
Turnover frequencies were compared at 550 1C in the following con-
ditions at the reactor inlet: 18.5 vol-% CH
4
, 74 vol-% CO
2
or H
2
O and
7.5 vol-%H
2
(Table 14). The CO
2
-H
2
reverse shift reaction was also in-
vestigated at 500 1C in similar conditions without methane in the inlet gases.
Except for Ni, the data of Table 14 seem not to support the conclusion of
Rostrup-Nielsen and Bak Hansen since the steam reforming reaction would
be 3 to 10 times faster than dry reforming on the other metals. Rostrup-
Nielsen and Bak Hansen explain this apparent discrepancy by the CO in-
hibition of both reactions. As dry reforming produces much more CO, the
reaction would be more aected by this inhibition. This explanation was
supported by a clear relationship between the CO inhibition factor and the
adsorption heat of CO on metal. Moreover, all metals being very active in
RWGS reaction (Table 14, last column), the tendency to form CO in dry
reforming would be the same for all the catalysts. The work of Rostrup-
Nielsen and Bak Hansen was qualitatively conrmed by Qin et al.
112,113
who
showed that steam and dry reforming had the same types of reaction
intermediates.
In 2004, Wei and Iglesia published a series or papers on the crucial role of
the CH
4
activation step both in methane steam reforming and in methane
dry reforming (MDR) on Ni,
114
Rh,
115
Ir,
116,117
Ru,
118
and Pt.
119,120
The
main conclusions of these studies at 600 1C are:

For all the metals, the reactions (MSR and MDR) are of rst-order in
CH
4
and virtually of zero-order in H
2
O and CO
2
.

For all these metal, the turnover frequency of the steam reforming is
very close to that of dry reforming, suggesting that neither H
2
O activation
nor CO
2
activation intervenes in the rate determining steps of methane
conversion.

These observations were corroborated by isotopic exchange studies

including the use of CD
4
,
13
CO and D
2
. The comparison of CH
4
and CD
4
reforming reveals a kinetic isotopic eect k(C-H)/k(C-D) close to 1.5 for all
the metals. Moreover, the rates of CH
4
/CD
4
cross-exchanges are signi-
cantly smaller than those of reforming reactions. All these features suggest
Table 14 Turnover frequency (molec. site
1
s
1
) of MgO-supported metals in steam and dry
reforming of methane. From Rostrup-Nielsen and Bak Hansen
111
Catalyst
Metal area
(m
2
g
1
)
H
2
O-CH
4
reforming
550 1C
CO
2
-CH
4
reforming
550 1C
H
2
O ref/CO
2
ref ratio
CO
2
-H
2
reverse shift
500 1C
1.4% Ni 1.1 2.2 1.9 1.2 5.3
1.4% Ru 3.0 8.9 2.9 3.1 8.7
1.1% Rh 2.2 8.1 1.9 4.3 5.4
1.2% Pd 1.4 1.6 0.18 8.9 8.0
0.9% Ir 1.3 4.5 0.44 10.2 8.6
0.9%Pt 1.0 2.0 0.36 5.6 7.2
20 | Catalysis, 2010, 22, 155
that the steps including CH breaking in methane are irreversible and are
the slow steps of the mechanism for both MSR and MDR.

Reactions with CH
4
/CO
2
/D
2
and CH
4
/CO
2
/
13
CO mixtures show that
H/D distributions in H-containing products (including water) and
12
C/
13
C
distributions in COx are very close to equilibrium. These results conrm
that both water and CO
2
activation are fast processes and as a rule, the
water gas shift reaction is equilibrated on all the metals at 600 1C.
Wei and Iglesia also found a strong particle size eect: turnover freqencies
in methane reforming generally increased when decreasing the cluster size of
metal. This was ascribed to the creation of a high number of low-co-
ordination metal sites on small particles favoring the CH cleavage of the
methane molecule. Finally, they showed that there was a moderate support
eect if any: for instance, TOF are very close when Rh or Pt are supported
on Al
2
O
3
, ZrO
2
or CeO
2
-ZrO
2
.
115,119
The crucial role of CH
4
activation in methane steam reforming on Rh/a-
Al
2
O
3
was conrmed by Tavazzi et al.
121
and Donazzi et al.
122,123
These
kinetic studies were carried out in an annular reactor avoiding any mass and
heat transfer artifact. Maestri et al. used the experimental data of Donazzi
to establish a hierarchy between the dierent kinetic models of methane
conversions (oxidation, steam reforming, dry reforming) by a microkinetic
approach including water-gas shift and reverse water gas shift reactions.
124
The main steps involved in methane conversions would be:
Methane activation steps (methane pyrolysis)
CH
4
2

! CH

3
H

33
CH

! CH

2
H

34
CH

! CH

35
CH

! C

36
Water or CO
2
activation steps
H
2
O 2

! OH

37
CO
2
2

! CO

38
CO
2
H

! CO

OH

39
Carbon oxidation steps
C

OH

! CO

40
C

! CO

41
CO

OH

! CO

2
H

42
This kinetic scheme is completed by CO, CO
2
desorption and H re-
combination and desorption steps. From the microkinetic data, Maestri
Catalysis, 2010, 22, 155 | 21
et al. concluded that CH
3
* decomposition (34) would be the slow step of
methane activation and very likely the rate-determining step of the whole
process. They also showed that all the steps including OH* are more
probable than those including O*: for instance CO
2
would be activated
via step 39 and not via step 38. The most abundant surface species are
CO* and H*. It is shown that CO coverage is signicantly higher in
dry reforming than in steam reforming while the reverse is expected
for H coverage. This strengthens the hypothesis of a CO inhibition
aecting more dry reforming than the steam reaction. However, the impact
of CO
2
in methane conversion remains questionnable. Donazzi et al.
concluded that CO
2
would not directly intervene in the kinetic of dry
reforming which would be a combination of reverse water gas shift
and steam reforming.
123
Xu and Saeys conrmed that carbon species would
be the most important intermediates in MSR on Ni(111).
125
Subsurface
carbon signicantly increases the methane dissociation barrier, thus
decreasing the rate of MSR reaction, while boron promoter has the
reverse eect.
126
2.2.3.2 MSR mechanisms with rate-determining steps including O species.
The works of Donazzi et al. and of Maestri et al. carried out on Rh
catalysts were tentatively extended to dierent metal/zirconia catalysts by
Jones et al.
127
A complete picture of the reactivity was established at 500 1C
by combining thermodynamic and kinetic models. The reaction is structure-
sensitive with turnover frequencies increasing with dispersion, suggesting
that the reaction is dominated by step and corner sites. For a given dis-
persion (40%) the following trend was observed: Ru ERh WNi EIr EPt
E Pd while thermodynamic and DFT calculations led to the following
ranking: Ru WRh WNi WIr WPt EPd, in excellent agreement with ex-
perimental results. It was conrmed that the critical steps having the highest
energy barriers on most metals were CH
4
dissociation (3336) and CO
formation (41). Contrary to the conclusions of the previous studies, CO
formation may be the rate determining step on most metals at 500 1C.
However, there is clear tendency that CH
4
dissociation becomes pre-
dominent at higher temperatures, in agreement with the conclusions of Wei
and Iglesia. A similar picture is proposed by Blaylock et al. who showed
that CH* would be the most important C-containing intermediate over
Ni(111) while CHO* and CHOH* cannot be excluded even though the
formation of these intermediates would be strongly dependent on the re-
action conditions.
128
Earlier studies in the 19701980s have already pro-
posed formaldehyde as an intermediate in methane steam reforming
according to the reactions:
108,129
CH

x
H
2
O x

! CH
2x
O

! CH
2
O

xH

43
CH
2
O

! CO H
2

44
Formaldehyde was detected in methane steam reforming over Ni/Al
2
O
3
above 400 1C with a maximum around 600 1C, which proves that it is not
only a key-intermediate at low temperature.
129
22 | Catalysis, 2010, 22, 155
The role of oxygen species has been evoked in many studies using ceria as
a support. Craciun et al. have investigated the steam reforming of methane
over ceria-supported Pd, Rh and Pt catalysts between 350 and 550 1C.
130
They found that all metal supported on ceria exhibited virtually the same
activity, 4 to 5 orders of magnitude higher than the activity of the silica-
supported catalyst. A similar result was observed over Pd-CeO
2
-Al
2
O
3
on
which MSR reaction rates is two orders of magnitude higher than on Pd-
Al
2
O
3
.
131
Oxygen species from the ceria support seem to play a major role in
this catalysis.
3. Steam reforming of ethanol
Alcohols are very reactive molecules whose decomposition over catalyst
surfaces (or in gas phase) is much faster than with hydrocarbons. In the
presence of steam, the reaction stoichiometry of alkanol steam reforming
(ASR) is:
C
n
H
2n1
OH n 1H
2
O ! nCO 2nH
2
45
Coupled with the WGS reaction, ASR may give carbon dioxide and
hydrogen:
C
n
H
2n1
OH 2n 1H
2
O ! nCO
2
3nH
2
46
The same reaction with alkanes (HSR) is:
C
n
H
2n2
nH
2
O ! nCO 2n 1H
2
47
In the alkane series, the C1 compound (methane) is the most stable one.
Contrary to hydrocarbons, the C1 alkanol (methanol) is the most reactive
alcohol. It decomposes spontaneously at relatively low temperatures with-
out water in the reacting gases (n=1 in 45). For this reason, methanol is
considered as a liquid syngas, much easier to transport than the syngas
itself.
The Gibbs free energy of reaction (45) per carbon atom (i.e. per mole of
CO2H
2
produced) is:
DG
0
T

1
n
DG
0
CO;T
n 1DG
0
H
2
O;T
DG
0
A;T
for alkanols 48
while that of reaction (47) will be:
DG
0
T

1
n
DG
0
CO;T
nDG
0
H
2
O;T
DG
0
HC;T
for alkanes 49
A comparison of the Gibbs free energy of the steam reforming reaction at
25 1C (298K) and 427 1C (700 K) is reported in Table 15 for n=1 to 4. The
steam reforming reaction is more facile on alcohols than on corresponding
alkanes. Data of Table 15 also conrmed that the thermodynamic tendency
is in the following order: C1 WC2 WC3 WC4 for alcohols and in the re-
verse order for alkanes.
However, the global reaction scheme is much more complex than the
simple reactions giving CO and H
2
. Replacing CO by CO
2
does not change
Catalysis, 2010, 22, 155 | 23
the thermodynamic tendency but, as seen later, the steamreforming reactions
can also produce methane, which modies signicantly the thermodynamic
equilibrium, CH
4
being the compound the most dicult to reform.
3.1 Thermodynamic of ethanol steam reforming (ESR)
Ethanol-steam mixtures can give rise to numerous reactions, the most
important being:
1. The steam reforming leading to CO and H
2
:
C
2
H
5
OH H
2
O ! 2CO 4H
2
DH
0
298
255 kJ mol
1
50
2. The steam reforming leading to CO
2
and H
2
:
C
2
H
5
OH 3H
2
O ! 2CO
2
6H
2
DH
0
298
173 kJ mol
1
51
3. The hydrogenolysis to methane
C
2
H
5
OH 2H
2
! 2CH
4
H
2
O DH
0
298
157 kJ mol
1
52
4. The ethanol dehydration to ethylene
C
2
H
5
OH ! C
2
H
4
H
2
O DH
0
298
45 kJ mol
1
53
5. The dehydrogenation to acetaldehyde
C
2
H
5
OH ! CH
3
CHO H
2
DH
0
298
68 kJ mol
1
54
6. The cracking to methane, CO and H
2
C
2
H
5
OH ! CH
4
CO H
2
DH
0
298
49 kJ mol
1
55
7. The cracking to methane and CO
2
:
C
2
H
5
OH !
1
2
CO
2

3
2
CH
4
DH
0
298
74 kJ mol
1
56
8. The cracking to carbon, CO and H
2
:
C
2
H
5
OH ! C CO 3H
2
DH
0
298
124 kJ mol
1
57
9. The cracking to carbon, water and H
2
:
C
2
H
5
OH ! 2C H
2
O 2H
2
DH
0
298
7 kJ mol
1
58
10. The cracking to carbon, methane and water:
C
2
H
5
OH ! CH
4
C H
2
O DH
0
298
82 kJ mol
1
59
Table 15 Gibbs free energy (kJ mol
1
) of the steamreforming reaction at 25 1C and 427 1C for
C1-C4 alkanols and C1-C4 alkanes. DG are given per mole of carbon
Alkanol DG
0
298
DG
0
700
Alkane DG
0
298
DG
0
700
Methanol 25.21 69.78 Methane 142.07 37.42
Ethanol 61.00 47.76 Ethane 107.72 12.29
Propan-1-ol 69.40 26.42 Propane 99.09 3.12
Butan-1-ol 71.80 24.52 Butane 95.56 0.66
24 | Catalysis, 2010, 22, 155
The equilibrium composition of the gases with a water/ethanol inlet
stoichiometry of 1 (corresponding to reaction 50) is shown in Fig. 7. Except
carbon, all compounds present in equations 5059 are included in the
thermodynamic calculations but acetaldehyde and ethylene are never
favored. Moreover, thermodynamics predicts that ethanol should be totally
converted in the whole range of temperature. At low temperatures (100
300 1C), the cracking into methane and carbon dioxide (56) is thermo-
dynamically favored. Hydrogen and CO contents progressively increase
with temperature; at 900 1C, the steam reforming to H
2
and CO (50) is the
only reaction to occur with a H
2
-to-CO molar ratio of 2. All the reactions
leading to methane are exothermic and are thus favored at low temperature.
As for heavy hydrocarbons, methane formation can severely limit the
hydrogen yield. If methane was not formed in ESR, the equilibrium
composition would change drastically (Fig. 8A). Ethanol is then not totally
converted below 300 1C and hydrogen is formed as of the lowest tempera-
tures (below 100 1C). The reaction favored at low temperature is the steam
reforming to CO
2
and H
2
. Carbon dioxide is very briey observed and
disappears by 350400 1C. Above this temperature, the steam reforming to
CO and H
2
would be the unique reaction observed in ESR.
Finally, the formation of carbon may also change the reaction thermo-
dynamics. Equilibrium compositions were calculated with possible formation
of all the compounds of equations 5059, including carbon (Fig. 8B). Carbon
and methane can be formed at low temperatures with a molar ratio of 1
suggesting that the reaction favored at low temperature is the ethanol
cracking to methane, carbon and water (59). An interesting fact is that
methane decreases more rapidly than in absence of carbon (compare Fig. 7
0%
10%
20%
30%
40%
50%
60%
70%
80%
100 300
M
o
l
e

%
T (C)
CH
4
H
2
H
2
O
CO
900 700 500
CO
2
Fig. 7 Equilibrium composition of gases in the reaction of ethanol with steam (without carbon
formation). Initial state: H
2
O/EtOH molar ratio=1, P=1 bar.
Catalysis, 2010, 22, 155 | 25
and 8B) while the carbon itself can be produced over a large range of tem-
perature. One should keep in mind that the initial state (H
2
O/EtOH=1)
strongly favors carbon formation. Most of experimental works were per-
formed with a H
2
O/EtOH ratio of 3 or higher. In this case, equilibrium gas
composition are closer to that of Fig. 7 even if carbon can ever be formed.
Equilibrium compositions were also calculated for dierent H
2
O/EtOH
molar ratio R and at higher pressures P. The results are reported in Table 16
for two temperatures: 600 and 700 1C. H
2
yield (Y
H
) is dened as the
number of moles of hydrogen produced per mole of ethanol entered:
Y
H
n
G

%H
2wet
100
60
Table 16 Equilibrium gas compositions, total number of moles of gas (n
G
) and H
2
yield (Y
H
)
in the steam reforming of ethanol at 600 and 700 1C for dierent values of R=H
2
O/EtOH and
dierent values of the total pressure P (bar)
T (1C) P (bar) R H
2
O H
2
CO CO
2
CH
4
n
G
Y
H
600 1 1 Wet % 10.75 41.81 15.89 10.39 21.15 4.22 1.76
Dry % 46.85 17.81 11.64 23.69
600 1 2 Wet % 18.29 46.15 11.62 11.71 12.22 5.62 2.59
Dry % 56.48 14.22 14.33 14.96
600 1 5 Wet % 33.89 44.81 6.18 11.89 3.21 9.39 4.21
Dry % 67.80 9.35 17.98 4.86
600 5 1 Wet % 18.87 25.55 7.71 14.49 33.37 3.60 0.92
Dry % 31.49 9.51 17.86 41.12
700 1 1 Wet % 4.76 56.40 27.07 3.51 8.26 5.15 2.90
Dry % 59.21 28.42 3.68 8.68
700 1 2 Wet % 11.59 58.19 20.93 6.40 2.88 6.62 3.85
Dry % 65.82 23.67 7.24 3.26
700 1 5 Wet % 30.83 49.05 10.08 9.73 0.31 9.94 4.86
Dry % 70.91 14.57 14.07 0.45
700 5 1 Wet % 12.18 40.80 18.16 8.33 20.51 4.25 1.73
Dry % 46.47 20.68 9.49 23.36
0%
10%
20%
30%
40%
50%
60%
70%
80%
100
(A) (B)
300 500 700 900
M
o
l
e

%
T (C)
CO
H
2
EtOH
H
2
O
CO
2
0%
10%
20%
30%
40%
50%
60%
70%
80%
100 300 500 700 900
M
o
l
e

%
T (C)
H
2
CH
4
H
2
O
CO C
CO
2
Fig. 8 Equilibrium composition of gases in the reaction of ethanol with steam. Initial state:
H
2
O/EtOH molar ratio=1, P=1 bar. A: without methane or C formation; B: with methane
and carbon formation
26 | Catalysis, 2010, 22, 155
The main conclusions are:

H
2
and CO
2
contents in dry gases increase with R while CO and CH
4
contents decrease. Though a maximum of the %H
2
in wet gases could be
observed, the H
2
yield always increases with R and tends to 6, the maximal
value of R corresponding to the stoichiometry of equation 51. In the
meanwhile, the amount of unreacted water increases with R, which implies
that the energy balance passes through an optimum when R is increased (the
better H
2
yield is compensated by the energy needed for gasifying a higher
amount of water).

Increasing the total pressure has a dramatic eect on the H

2
yield
which decreases by a factor 1.71.9 when the reaction is performed at 5 bar
instead of 1 bar. This is essentally due to a strong increase of the methane
yield at the expense of the CO yield. Increasing P has a moderate, positive
eect on the CO
2
yield. Of course, diluting the reactants (H
2
OEtOH) in
an inert gas has exactly the reverse eect: increase of Y
H
and correlative
decrease of Y
CH4
.

In conclusion, in those studies where the ethanol steam reforming is

carried out at a high R value and/or with dilute reactants, the catalyst
performances are articially improved and the results should be considered
with circumspection.
When C1 compounds are possibly formed, thermodynamics does never
favor dehydration or dehydrogenation of ethanol. And yet, there are
many indications in the literature that these reactions on alcohols can occur
at relatively low temperature on acid, basic or metal sites. To know the
thermodynamic tendency of each reaction, calculations were made in
absence of C1 compounds. Dehydrogenation (ethanol/acetaldehyde/H
2
)
was rst considered, then dehydration (ethanol/ethylene/water) and nally
the two reactions together. The results are shown in Fig. 9. Dehydroge-
nation (Fig. 9A) is favored at higher temperatures than is dehydration
(Fig. 9B): while total conversion of ethanol can be reached by dehydration
at less than 200 1C, dehydrogenation requires almost 400 1C. It should be
noted that acetaldehyde and hydrogen, on one hand and ethylene and water
on the other hand are produced in same amount: the mole percentage of
each product is 50% at full conversion of ethanol (Fig. 9A and 9B). When
the two reactions are possible, dehydration is strongly favored with a
maximal production of ethylene around 200 1C while that of acetaldehyde
increases only slowly with temperature (Fig. 9C).
As this will be discussed later, dehydration occurs mainly on acid sites
while dehydrogenation is catalyzed preferably on basic or metal sites. To
counterbalance the thermodynamic trend, it should be necessary to elim-
inate virtually all the acid sites of the catalyst if one wants avoiding ethylene
formation for kinetic or mechanistic reasons.
Ethanol may also give rise to many other products: diethyl ether,
acetic acid, acetone, n-butanol.
132,133
The richness of possibility of
ethanol decomposition over acid, basic and metal sites makes that numer-
ous surface species can be detected according to the nature of metal and
supports.
Catalysis, 2010, 22, 155 | 27
3.2 Noble metals
3.2.1 Rhodium catalysts. Rhodium catalysts were early recognized as
very active in ethanol steam reforming.
134,135
Cavallaro, Freni and the
Group of Messina were among the rst authors to investigate ethanol steam
reforming over Rh/Al
2
O
3
catalysts.
136139
The reaction was carried out at
temperatures between 50 and 650 1C with a standard H
2
O/EtOH ratio
of 4.28.4
136,137
with or without O
2
addition for autothermal process.
138,139
These Authors concluded that the mechanism starts with ethanol de-
hydrogenation and/or dehydration followed by the gasication of
acetaldehyde or ethylene intermediates. Ethylene would be formed
on acidic sites of alumina while all other steps (including dehydro-
genation and gasication) would be catalyzed by the metal. Catalyst
coking seems linked to ethylene formation and can be largely sup-
pressed by O
2
addition.
138,139
Interestingly, it was proved that methane
is a primary product whose selectivity decreases with contact time
(Table 17).
A comparison of Rh with other metal catalysts was performed by
Aupretre et al.,
140
Breen et al.
141
and Liguras et al.
142
The catalysts and the
conditions used in these studies are reported in Table 18. Catalysts per-
formances are given in the table as H
2
yield or ethanol conversion. The total
conversion of ethanol being very high in their conditions, Breen et al.
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 200
(A) (B)
(C)
400 600 800
M
o
l

%
T (C)
Ethanol
Acetaldehyde/H
2
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 200 400 600 800
M
o
l

%
T (C)
Ethanol
Ethylene/H
2
O
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
0 200 400 600 800
M
o
l

%
T (C)
Ethanol
Ethylene
Acetaldehyde
Fig. 9 Equilibrium composition in ethanol dehydrogenation (A), in ethanol dehydration (B)
and in both reactions (C).
28 | Catalysis, 2010, 22, 155
dened a useful conversion C
COX
in steam reforming corresponding
to the partial conversion of ethanol in H
2
via equations 50, 51:
C
COX
%
1
2
CO CO
2

out
Ethanol
in
100 61
The performances of the alumina-supported metals can be ranked as
follows:
NiWRh cPdWPtWCuWRu, according to Aupretre et al.
140
Rh cPdWNiEPt, according to Breen et al.
141
Rh cPtWPdWRu, according to Liguras et al.
142
As a rule, Rh appears as the most active metal but interesting
performance can be achieve over highly loaded Ni
140
or Ru
142
catalysts. The
product distribution and the stability of Rh catalysts can also depend on the
metal precursor used for the catalyst preparation.
143,144
A comparison of MgO-supported metals was also carried out by Frusteri
et al. at 650 1C.
145
The results reported in Table 19 conrm the very good
Table 18 Comparison of metal catalyst performances in ethanol steam reforming. Unless
otherwise indicated, all metals are deposited over alumina supports
Aupretre et al.
140
Breen et al.
141
Liguras et al.
142
700 1C, R=3
No dilution
400750 1C, R=3.
Dilution in N
2
.
H
2
O/EtOH/N
2
=3/1/7.6
600850 1C, R=3
No dilution
Catalyst
H
2
yield
(g h
1
g
1
cat
) Catalyst
C
COX
(Useful
conversion)
at 700 1C (%)
Catalyst
(% dispersion
in parenthese)
Conversion
at 750 1C (%)
1%Rh 2.3 1%Rh 90 0.5%Rh (62) 52
1%Pt 0.6 5%Ni 15 1%Rh (45) 79
0.75%Pd 1.1 0.5%Pd 30 2%Rh (50) 91
0.67%Ru 0.3 1%Pt 15 1%Ru (14) 18
9.7%Ni 3.1 3%Ru (22) 69
9.1%Cu 0.4 5%Ru (21) 70
1% Rh/CeZrOx 5.1 1%Pd (39) 25
9.7%Ni/CeZrOx 4.4 1%Pt (98) 32
Table 17 Ethanol conversion, C1-product selectivity and hydrogen yield Y
H
in ethanol steam
reforming at 650 1C (R=4.2 with 9.6% EtOH, 80.4% H
2
O and 10% N
2
). Catalyst: 5%-wt Rh/
Al
2
O
3
(Rh crystallite size: 8-9 nm). From ref.
138
Contact time (s)
Ethanol
conversion %
C1-selectivity (%)
Y
H
(mol H
2
/mol
EtOH) CO
2
CO CH
4
0.120 100.00 69.26 27.41 3.33 5.17
0.048 100.00 55.60 32.00 12.40 4.34
0.033 80.59 49.35 33.69 14.00 3.43
0.020 55.59 47.04 35.37 17.59 2.30
Catalysis, 2010, 22, 155 | 29
performance of Rh on this support. On the basis of 100 for Rh, the fol-
lowing ranking was obtained:
Rh,100 WPd,45 WCo,27 WNi,17, not so far from the relative activity of
these metals in toluene steam dealkylation (See Table 7).
Aupretre et al.
140
also showed that CeZrOx mixed oxides could be
excellent supports for Rh and Ni, increasing signicantly the H
2
yield.
Diagne et al. investigated the hydrogen production by ethanol reforming
over Rh catalysts supported on CeO
2
, ZrO
2
and various CeZrOx oxides
(Ce/Zr=4, 2 or 1).
146,147
The reaction was carried out between 300 and
500 1C with a high H
2
O/EtOH ratio and a large dilution in Ar (H
2
O/EtOH/
Ar=8/1/35). These conditions strongly favor H
2
yields and are not repre-
sentative of real conditions. At 450 1C, Y
H
is close to 5.7 mol H
2
/mol
EtOH for pure zirconia and CeZrOx support at 50% Ce. Beyond 50%
Ce, Y
H
slightly decreases with %Ce to slow down to 5.0 for pure ceria.
Interestingly, the oxide basicity was characterized by CO
2
chemisorption
and the determination of the adsorption constant K
CO2
at 0 1C. It was
shown that ceria was the most basic oxide (K
CO2
=0.7 kPa
1
) and that
K
CO2
decreased linearly with the Zr/Ce ratio down to 0.25 kPa
1
for pure
zirconia. Diagne et al. concluded that the hydrogen yield is not favored by a
high basicity of support. Rh/CeZrOx catalysts were also studied by De
Rogatis et al.
148
and the group of Wang at Richland.
149151
In spite of
dierent experimental conditions (R=5 and dilution in Ar for De Rogatis
et al.; R=4, no dilution for Wang et al.), the conclusions of these studies
were rather similar:

While alumina or Al-spinel supports favor ethanol dehydration to

ethylene,
149,151
CeZrOx supports strongly favor the acetaldehyde route to
COx and H
2
.
148,149
It is not clear, however, if the CeZrOx support promotes
ethanol dehydrogenation or inhibits ethanol dehydration.

Once acetaldehyde is formed, CeZrOx favors its gasication into COx

and H
2
instead of its decomposition into methane and CO.
149
Oxygen
storage capacity (and mobility) on CeZrOx would play a crucial role in the
reaction mechanism, O species promoting the fast oxidation of the CH
3
group of acetaldehyde, thus hindering methane formation.

CeZrOx also promotes the water-gas shift reaction and favors the nal
conversion of CO to CO
2
.
148

Owing to its redox properties, CeZrOx would also favor the direct
decomposition of water into hydrogen (and not only into OH groups).
148,151
Table 19 Comparison of MgO-supported Rh, Ni, Pd and Co catalysts in ethanol steam
reforming. T=650 1C, R=4.2 (H
2
O/EtOH/N
2
=4.2/1/3), GHSV: 300000 h
1
. EtOH con-
versions are between 7 and 20%
Catalyst
BET area
(m
2
g
1
)
Metal
dispersion %
C-product distribution (vol-%)
TOF (s
1
) CO CO
2
CH
4
CH
3
CHO
3%Rh 2.1 16.0 19.5 67.1 8.1 5.3 12.1
3%Pd 2.0 12.8 31.8 32.8 21.7 14.5 5.5
21%Ni 6.3 14.0 16.5 58.2 5.7 19.6 2.1
21%Co 7.6 15.6 18.8 44.4 5.6 31.2 3.3
30 | Catalysis, 2010, 22, 155
This is in line with direct evidence of water dissociation into hydrogen over
reduced Rh/CeO
2
.
45

CeZrOx gives more stable catalysts by reinforcing their resistance

to coking.
150
This is linked to the inhibition of the dehydration route to
ethylene which is a strong coke precursor and to the oxygen storage capacity
promoting CHx oxidation and surface cleaning along the steam reforming
process.
Aupretre et al. have studied the ethanol steam reforming at 700 1C under
1 or 11bar and R=4 over 0.2%Rh/Mg
x
Ni
1 x
Al
2
O
4
catalysts.
152
Metal
accessibility were close to 40% for all the catalysts. Tests under 11 bar were
performed in view of a coupling of the reformer with a separation mem-
brane for H
2
purication. The acid-base properties of the supports were
carefully characterized by CO
2
chemisorption and dimethyl-3,3-but-1-ene
isomerization as well as FTIR of lutidine and DRIFT. The morphology of
the support, with a Mg-decient spinel layer (thickness of about 89 nm)
intimately covering all of the alumina grains (around 40 nm in size), can
explain the neutralization of most acidic sites. Some of them are created
during the metal precursor impregnation. The highest H
2
yield at 1 bar was
obtained with the Rh/Mg
0.75
Ni
0.25
A
2
O
4
catalyst (4.68 mol H
2
/mol EtOH
and 5.58 mol/mol with WGS) while the best performances under 11 bar
were obtained with the nickel-free catalyst (2.74 mol H
2
/mol EtOH and 3.25
with WGS). Acid-base properties of alumina can be tailored by adding
some oxide promoters. Recently, Can et al. have investigated the eect of
Sc, Y, La, Er and Gd addition to a Rh/Al
2
O
3
in ethanol steam reforming
(675 1C, 2 bar, R=4).
153
The best performances were observed with the
most basic catalysts presenting a new type of acid site less able to form coke
precursor.
Most of the previous studies report that ethanol conversion in gas phase
is far to be negligible and it seems that several products of gas phase con-
version are coke precursors. For instance, Aupretre et al. showed that a
signicant amount of ethylene was produced when the reactor was loaded
with SiC only (the inert material used as diluant of the catalyst).
152
At
700 1C, 1 bar, ethanol conversion was 71% while it increased with the
pressure to reach 98% at 11 bar (residence time eect). The formation of
undesirable by-products in gas phase can be avoided by performing the
reaction of steam reforming or autothermal reforming in ultra-short resi-
dence time reactors (o10 ms). Deluga et al. reported very interesting results
on this type of reactor with a catayst consisting in a Rh/CeO
2
layer de-
posited on a ceramic foam.
154
Surface species and gas phase products in the steam reforming of ethanol
on TiO
2
and Rh/TiO
2
were studied by Rasko et al. by coupling FTIR and
TPD-MS.
155
Ethanol dissociation forms ethoxides C
2
H
5
O

at ambient
temperature. Dehydrogenation leads to acetaldehyde whose formation is
accelerated in the presence of rhodium and steam. The same study was
extended to other metals and to other supports (alumina, ceria, . . .).
156
At
low temperature, ethanol is molecularly adsorbed on oxides while it forms
ethoxides and proton on supported noble metals. Heating these adsorbed
species above 150 1C progressively leads to acetate species (on the support)
or to their decomposition into hydrogen and carbon oxides (at metal/
Catalysis, 2010, 22, 155 | 31
support interface). Certain acetate species are so strongly adsorbed that they
may deactivate the catalyst. Dehydration to ethylene is observed only on
alumina and virtually not on ceria. Surface species issued from ethanol
adsorption at room temperature and their decomposition by HT-treatment
were investigated by Idriss over ceria-supported Rh, Pd, Pt and Au
monometallics as well as over Pt-Rh, Rh-Au, Rh-Pd and Pt-Pd bime-
tallics.
157
OH bond dissociation leading to ethoxy species can be observed
on Rh, Pt and Pd. In the meanwhile, and only on Rh, a CH bond dis-
sociation of the CH
3
group leading to oxometallate species is also observed.
As a result, Pd and Pt may produce signicant amounts of acetaldehyde
while the CC bond dissociation, leading to CO and methane, is favored
on Rh.
From all the studies carried out over Rh catalysts, a global picture of the
reaction mechanism as illustrated in Fig. 10 can be proposed.
In this mechanism, methane is formed by acetaldehyde (or ethanol)
cracking and is then steam reformed in a further step. It would be a primary
product of ESR. To support this mechanism, it may be remarked that
the actual methane concentration in gas phase is sometimes higher than
the equilibrium concentration. Another route to methane, not evoked in
equations 5058 is the hydrogenation of CO or CO
2
. This way of methane
formation was investigated by Birot et al.
158
over Rh/CeZrOx ESR cata-
lysts. They showed that methane can be produced by CO hydrogenation but
not by CO
2
hydrogenation whose rate is negligible in ESR conditions.
3.2.2 Other metals. Though group 10 noble metals were compared to
rhodium in many studies (y 3.2.1), they were sometimes investigated alone,
generally with the objective to prove their eciency when deposited on
adequate supports.
Platinum. One of the rst study on ethanol steam reforming was reported
by Rampe et al.
159
Catalysts were Pt, Ru, Pd and Ni or bimetallics Ni-Pt
and Ni-Pd on alumina. Their performances were evaluated at R=2, 3 or 4,
P=2, 5 or 9 bar and T=600, 700 or 800 1C. The main objective of this
study was to demonstrate the feasibility of an ethanol reformer of 3kW.
CH
3
CH
2
OH
Metal
Support
H
2
O
OH OH
Basic site
Acid site
CH
3
CHO H
2
, CO, CO
2
, CH
4
CH
3
CH
2
OH
C
2
H
4
Fig. 10 Mechanism of ethanol steam reforming. Ethanol is either dehydrogenated into acet-
aldehyde over basic (or metal site) or dehydrated into ethylene over acid sites. Acetaldehyde is
then decomposed in COCH
4
CO
2
. Methane can be reformed at elevated temperature while
the CO/CO
2
mixture is shifted to more or less CO
2
according to the temperature and the R
ratio. Ethylene can be directly reformed into syngas or hydrogenolyzed into methane. This is
also a coke precursor whose formation is preferably to be avoided.
32 | Catalysis, 2010, 22, 155
Jacobs et al. have investigated the Pt/CeO
2
system in ethanol steam
reforming at 200550 1C in diluted medium (H
2
O/EtOH/N
2
H
2
/=
33/1/29).
160
Adding hydrogen to the inlet feedstream allows to maintain
ceria in a reduced state. Jacobs et al. showed that ceria played a signicant
role in the reaction mechanism: ethanol would be adsorbed on defect sites of
ceria forming ethoxy species which, in turn, are transformed into acetate
species. One of the role of the metal would be to hydrogenate surface species
into carbon dioxide and methane. In this mechanism, CO
2
is the primary
COx product. Unfortunately, as Pt/CeO
2
is a good WGS/RWGS catalyst,
a part of the CO
2
is shifted to CO with a loss of hydrogen. Other studies
were performed by the Group of Davis at Lexington and the Group of
Noronha at Rio de Janeiro over Pt/CeZrOx catalysts.
161,162
A wide range of
by-products were identied. The catalyst is mainly deactivated by carbon
which creates a barrier at the metal/support interface, thus inhibiting
acetate decomposition and hydrogenation. Co-feeding oxygen with water
strongly reduces coke formation and increases catalyst stability at the
expenses of H
2
yield.
162
Platinum was also used to improve Ni stability by
decreasing coke formation in Ni-Pt bimetallic catalysts.
163
Ruthenium. Ru/alumina catalysts (in the form of pellets or wash-coated
on cordierite monolith or on ceramic foams) were investigated by Liguras
et al.
164
On such structured catalysts, the control of temperature along
the bed (or monolith) axis is fair (T may vary from 900 to 600 1C). However,
Ru appears to be a good candidate for the steam reforming or even auto-
thermal reforming of ethanol. Contrary to the conclusions of the previous
studies on Pt, CO would be a primary product of the reaction and sub-
sequently transformed into CO
2
and H
2
by WGS. As Ru is a very good
catalyst for this reaction, CO and CO
2
concentration would be close to
equilibrium.
Palladium. Ethanol steam reforming on Pd catalysts was studied by
Goula et al. over Pd/Al
2
O
3
165
and by Casanovas et al. over Pd/ZnO.
166
At
low temperature, Goula et al.
165
observe an important formation of CO and
methane corresponding to ethanol (or acetaldehyde) decomposition. In-
creasing the temperature favors the formation of CO
2
and H
2
. Above
500 1C, the formation of CO increases again in accordance with the WGS
equilibrium. Casanovas et al. have tested their 5%Pd/ZnO catalyst between
250 and 4501C with a H
2
O/EtOH ratio of 13.
166
They report very good
activity at medium temperature (300400 1C) with, however, a signicant
formation of acetaldehyde. The major problem they encountered was the
formation of PdZn alloy at the highest temperature. A two-layer xed bed
reactor was proposed by Galvita et al.
167
for ethanol reforming. Ethanol is
rst transformed by dehydrogenation and cracking on a Pd/C catalyst in a
gas mixture composed of methane, COx and hydrogen (see equations 54
56, section 3.1). Methane is then reformed at high temperature to carbon
oxides and hydrogen on a conventional Ni catalyst.
Iridium. Ethanol steam reforming was investigated over Ir/CeO
2
by
Zhang et al.
168
Cai et al.
169,170
In spite of a very low H
2
O/EtOH ratio
(R=1.8), these authors showed that their catalyst was stable over 60 h
in ESR or autothermal ESR. It seems that the combination of Ir metal
and ceria can prevent coke formation even at low steam concentration.
Catalysis, 2010, 22, 155 | 33
Zhang, Cai et al. explained this result by the high oxygen storage properties
of the Ir/CeO
2
system and the exceptional stability of Ir in these
conditions. These results are coherent with the OSC and
18
O/
16
O exchange
properties measured on similar Ir/CeO
2
catalysts by Bedrane et al.
55
As on
most ceria-supported catalysts, Ir/CeO
2
produces a signicant amount of
acetaldehyde at low temperature (below 450 1C). In addition, acetone was
also observed up to 500 1C by secondary reaction of acetaldehyde with
water (62):
2CH
3
CHO H
2
O ! CH
3
COCH
3
CO
2
2H
2
62
Ethanol conversion is total above 4501C and the product distribution is
close to equilibrium above 550 1C except for methane and CO
2
(15% CO,
20% CO
2
, 7% CH
4
and 58% H
2
at 600 1C, to be compared to equilibrium
values: 15% CO, 14% CO
2
, 16% CH
4
and 55% H
2
).
3.3 Non-noble metal catalysts
3.3.1 Nickel catalysts. Nickel-based catalysts are widely used in in-
dustry for many chemical reactions. Because of its high performances and
its low cost, nickel is also one of the most studied metals for ethanol steam
reforming. Nickel-containing catalysts are reported to have a high activity
for ethanol steam reforming. Fatsikostas and Verykios
171
studied the
ethanol steam reforming over nickel catalysts supported on g-Al
2
O
3
, La
2
O
3
,
and La
2
O
3
/g-Al
2
O
3
. They demonstrated that Ni promoted reforming of
ethanol and acetaldehyde as well as the watergas shift and methanation
reactions. At temperature below 300 1C, pure nickel causes bond breaking
of ethanol in the following order: OH, CH
2
, CCand CH
3
, the
key reaction being ethanol dehydrogenation. At elevated temperature, the
overall reaction network of ethanol steam reforming results in the for-
mation of H
2
, CO, CO
2
, and traces of CH
4
. Nickel is also known to present
a high hydrogenation activity and it may help to combine hydrogen atoms
on the catalyst surface to form molecular hydrogen.
135,172
However, nickel
presents a limited WGS activity, limiting the selectivity towards H
2
and
CO
2
. Consequently, the support will also play a role in the catalytic per-
formances. The ethanol conversion as well as the selectivity to hydrogen of
nickel catalysts on various support reported in the literature for tempera-
tures higher than 550 1C are given in Table 20. The results presented in
Table 20 show that whatever the experimental conditions and the nickel
content, the majority of the supports lead to high selectivity to hydrogen.
In fact, one of the major problem to overcome with nickel catalysts is to
avoid the catalyst deactivation due to metal particle sintering as well as to
coke deposition. To improve the stability of the nickel catalyst, several ways
were investigated by modifying either the nature of the support or the
metallic phase. Thus, various supports were studied, such as Al
2
O
3
, SiO
2
,
MgO, MgAl
2
O
4
, La
2
O
3
, ZnO, CeO
2
, CeO
2
ZrO
2
, Ce
x
Ti
1 x
O
2
or per-
ovskite-type oxides (LaAlO
3
, SrTiO
3
and BaTiO
3
).
135,140,173180,188,189
The
better performances were obtained with the most basic supports favoring
the ethanol dehydrogenation and inhibiting ethanol dehydration leading to
ethylene, which is coke precursor. The addition of dopants to the support
34 | Catalysis, 2010, 22, 155
can also improve the activity, the selectivity and the stability of the catalysts.
For example, alkali are very often added to the support to neutralize
the acid sites, inhibiting in this way the dehydration reaction leading to the
formation of olens responsible for coke production.
181184
It was also
shown that the addition of potassium to the support improves the stability
of Ni/MgO catalysts by limiting the sintering of nickel particles without any
eect on coke formation rate.
181
Ce, Co, Cu, Mg, Zn, Fe, Cr
190193
were also added to a Ni/g-Al
2
O
3
catalysts for auto-thermal steam reforming. Iron is known to be an active
metal for the water-gas-shift reaction thus increasing the hydrogen yield,
and to relieve the carbon deposition. Moreover, iron has electronic prop-
erties and a ion radius similar to that of nickel and then it can easily replace
nickel in nickel-containing phase. The iron-promoted nickel-based catalysts
showed high selectivity to hydrogen as well as high resitance to both sin-
tering and oxidation in oxidative atmosphere. The improved durability,
compared to the iron-free nickel catalyst was attributed to the presence of
NiAl
2
O
4
-FeAl
2
O
4
mixed crystals.
193
Copper-based catalysts are known to favor the ethanol dehydrogenation
route and copper is also more active in methane steam reforming. Associ-
ated to nickel, copper increases the water-gas shift activity as well as the
stability of nickel particles.
194,195
Biswas and Kunzru evidenced
178
that
the addition of copper to Ni/CeO
2
-ZrO
2
catalyst not only increased the
steam reforming and WGS activities but also enhanced acetaldehyde
decomposition and reforming. Klouz et al.
190
and Fierro et al.
191
also shown
that the addition of Cu to Ni-based catalysts enhanced the selectivity
Table 20 Initial ethanol conversion and initial selectivity to hydrogen obtained on various
Ni supported catalysts and dierent reactions conditions (temperature, water to ethanol ratio
R, in the presence or not of inert gas), at atmospheric pressure
Ni content
(wt.%) Support R Inert gas T
Ethanol
conversion (%)
Selectivity
to H
2
(%) Ref.
10 g-Al
2
O
3
4 600 1C 100 75 185
15 g-Al
2
O
3
6 600 1C 100 87 186
17 g-Al
2
O
3
3 He, 62.5
vol.%
750 1C 100 93 187
17 La
2
O
3
3 600 1C 93 87 188
17 La
2
O
3
3 700 1C 100 95 188
17 La
2
O
3
3 He, 62.5
vol.%
750 1C 100 90 187
15 La
2
O
3
-Al
2
O
3
6 600 1C 100 87 186
10 TiO
2
4 600 1C 100 86 185
10 Ce
0.5
Ti
0.5
O
2
3 N
2
, 80
vol.%
600 1C 100 58 189
30 Ce
0.74
Zr
0.26
O
2
8 N
2
600 1C 98 88 178
30 Ce
0.74
Zr
0.26
O
2
8 N
2
650 1C 100 93 178
10 ZnO 4 600 1C 95 80 185
17 MgO 3 He, 62.5
vol.%
750 1C 100 79 187
17 YSZ 3 He, 62.5
vol.%
750 1C 100 92 187
Catalysis, 2010, 22, 155 | 35
towards hydrogen and improved its stability. This was related to the ability
of copper of modifying the anity of nickel particles for carbon, thus in-
hibiting coke formation. The interaction between the CuNi phase and the
support plays also an important role in the complex reaction network taking
place during the ethanol steam reforming. Calles et al.,
196
prepared Cu-Ni
bimetallic catalysts on Ce and La modied SBA15 support. They observed
that on the Ce-modied support, the formation of large CeO
2
particles
decreased the metal-support interaction thus increasing the metal particle
size, leading to a low hydrogen selectivity. On the contrary, a high metal-
support interaction, as observed with high contents of La
2
O
3
in the modi-
ed support, leads to a better metallic dispersion as well as a lower coke
formation.
Another way of improving the stability of Ni-based catalysts consists
of adding small amount of noble metals such as platinum
197,198
or pal-
ladium
198
The addition of promoters caused a decrease in the NiO reduction
temperature. Moreover, the bimetallic catalysts showed a higher ethanol
conversion and higher hydrogen yield than the monometallic one, whatever
the nature and concentration of the noble metal. Rhodium was also added
to to Ni/CeZr.
199
In that case, the presence of rhodium had a negative eect,
the presence of rhodium favoring the rejection of nickel oxide from the
support. The reduction of the RhNi/CeZr mixed oxide during the catalytic
test decreased the nickel-support interaction, thus favoring the carbon
lament production and diminishing the oxidizing properties of the
support.
3.3.2 Cobalt-based catalysts. Cobalt has also been the object of many
papers on ethanol steam reforming.
179,200209
It was demonstrated that the
support is of major importance for the catalytic performances in ethanol
steam reforming in the presence of Co-supported catalysts. Among the
supports studied, the alumina support was reported to yield the highest
selectivity towards hydrogen
200,207
but the basic supports, such as MgO lead
to more stable catalyst, resistant to coke formation.
207
The metal-oxide
interaction appeared to be also essential for the stability.
201
Thus, to favor
Co-support interactions, uorite-type Ce-Zr-Co oxide was prepared and
evaluated in real bioethanol steam reforming at 540 1C. At this temperature,
the catalyst deactivated, due to the formation of carbonaceous products at
the oxide surface and also of laments. This result was explained by the
reduction of cobalt cations of the mixed oxide, weakening the metal support
interaction, thus favoring carbon deposition.
210
The addition of Rh to this
CeZrCo catalyst increased the catalyst stability by avoiding the accumu-
lation of carbon species on the surface.
211
As recently developped by Urasaki et al.,
179
the Co catalysts supported on
perovskites such as SrTiO
3
and LaAlO
3
showed higher catalytic activities
and much longerterm stabilities compared to conventional Co/MgO and
Co/gAl
2
O
3
catalysts. It was inferred that the lattice oxygen in perovskites
played a positive role in inhibiting the coke.
3.3.3 Copper-based catalysts. Copper is a good dehydrogenation cata-
lyst
212
and is known to present a high WGS activity. A copper-based catalyst,
Cu/ZnO/Al
2
O
3
is used for industrial hydrogen production by methanol steam
36 | Catalysis, 2010, 22, 155
reforming. It was demonstated that this catalyst is also active for ethanol
steam reforming, yielding CO, CO
2
and H
2
as the main products at low
temperature, above 360 1C.
213
Recently,
214
nickel, cobalt and/or manganese
were added to a commercial Cu/ZnO/Al
2
O
3
and the resulting catalysts were
tested in ethanol steam reforming. It was demonstrated that, below 480 1C,
the presence of modiers leads to a decrease in the methane formation and an
increase in the hydrogen yield and selectivity. At this temperature, the for-
mation of organic by-products, excepted methane is strongly decreased.
4. Utilisation of crude bioethanol
Ethanol has been used as an automotive biofuel ever since the introduction
of the combustion engine. From 1935 to 1945, ethanol was used pure, or
mixed with petrol before to be replaced by gasoline or diesel with the de-
velopment of the petrochemical industry. The crisis in the 1970s revived the
interest of ethanol with the running of the Brazilian National Alcohol
Production Progam (PROALCOOL), in 1975. However except for this
decade the price of the oil remained low making the use of other alternative
energy resource hardly acceptable. It was necessary to wait for the begin-
ning of the 21st century with the realization of two simultaneous concerns,
the decreasing of the resources of the fossil fuels and the global warming to
really consider that an alternative energy became essential. One way of
reducing environmental eects and the dependance on fossil fuels is to use
renewable bioethanol as direct fuel for transportation. Another way is to
use hydrogen as an energy carrier to support sustainable energy develop-
ment. Hydrogen can be used in a fuel cell to generate electricity with high
eciency. It is extremely clean as the only by-product is water. In order to
support sustainable hydrogen economy, it is crucial to produce ethanol and
hydrogen cleanly and renewably.
4.1 Bioethanol production and composition
Bioethanol is an ethanol produced renewably by fermentation by yeast of
biomass materials, such as sugar cane, sugar beet, wheat, potatoes, corns,
and other sugar- and starch-rich plants.
215
Such crops which have a food
use are often referred as rst generation biomass crops. Sugar and starch
crops have been utilized for bioethanol production due to the relative ease
at which their constituent reducing sugar unit can be separated in water
(hydrolysis) and subsequently fermented. It should be noted that that fer-
mentation is not a green process since one C6 unit of sugar gives only two
moles of ethanol, two carbons being lost as CO
2
. Brazil and United States
produce large quantities of bioethanol from sugar cane and corn respect-
ively. In the European Union, where France and Spain are the largest
producers, the ethanol production is more modest and comes from the
fermentation of sugar beet or wheat in a large part. As ethanol is produced
from biomass, its environmental performances in terms of greenhouse gas
(GHG) emissions and energy saving are strongly related to the raw material.
As an example, depending on the crop, the ethanol yield could vary dras-
tically. Table 21 gives a comparison of the performances obtained in terms
of ethanol yields from main rst generation feedstocks.
Catalysis, 2010, 22, 155 | 37
These data corresponding to the cultivation eciency have a direct im-
pact on the climate benets. Other factors inuence the GHG emissions : (i)
the fuel and fertilizer used in the ethanol plant; (ii) the eciency with which
by-product are dealt with; (iii) the type of land for cultivation.
218
According
to the raw material, to the agricultural yield and to the transformation
process eciency, the energy balance (energy used/energy produced) has
been shown to vary from 0.3 to 1.6 when bioethanol is used as biofuel.
217
Because of the existence of the high diversity of ways to produce ethanol,
the divergences about the method to be used for calculating the level of
GHG saving cannot be avoided. Dierent studies can bring to entirely
opposite conclusions. For Searchinger et al. who assume that a production
of biofuel requires new cultivation of cropland by displacement eect, the
production of bioethanol is considered as a threat for the environment.
219
From other authors it seems clear that, under most production scenari, the
net greenhouse gas eect of bioethanol is positive.
220
This last conclusion is
usually accepted even if the data calculted in term of reduction of GHG
emissions vary. ADEME reported a detailed comparison of the two rst
works reported in the Table 22 in order to analyse the reasons of the
divergences. One of the conclusions was that as far as normalized results are
concerned the values become comparable.
An other vehement debate is caused by the use of rst generation
biomass: the ethical issues of using food for fuels.
225
For instance, corn and
sugarcane, are used to produce food and sugar as consumer goods. The
recent rise in the price of various crops such as the wheat has been attributed
sometimes to the greatly increased demand for biofuels in recent years by
many developed nations. The use of second-generation lignocellulosic
biomass, emerged to be the best option available currently. This second-
generation bioethanol only requires inexpensive cellulosic biomass as
Table 21 Some examples of ethanol yields from
various crops (from 216 and 217)
Crop Ethanol yield (hl/ha)
Sugar cane 70
Sugar beet 21.747.4
Wheat 11.620.1
Corn 18.232.8
Table 22 Reduction of GHG emissions for bioethanol from dierent European feedstock as
compared with fossil fuel emissions. From ref. 221
Source
Bioethanol from sugar
crops (%)
Bioethanol from
grain (%) Ref.
Concawe/Eucar/JRC 3744 6 to 43 222
ADEME 75 75 223
PWC 4060 4070 224
38 | Catalysis, 2010, 22, 155
feedstock, which is plentiful and easily obtainable throughout the world
(wood, grasses or the non-edible parts of plants). However because of its
more complex molecular structures, the production of ethanol from lig-
nocellulosics is more dicult than from sugar cane or stach-rich materials.
Lignocellulose consists of three main components: cellulose, hemicellulose
and lignin, the rst two being composed of chains of sugar molecules. The
percentage of each component dier with the nature of the feedstock
(Table 23). The dierence between rst- and second-generation bioethanol
production is that, in the latter case, an extra step is required to hydrolyse
lignocellulose biomass.
226,227
The nal step, the distillation process, remains the same for both gener-
ations of bioethanol. Important factors to consider when evaluating the use
of bioethanol are fuel or feedstock is the overall economy of processes in-
volved as well as the energy-ecency from biomass to wheel. Fuel grade
bioethanol needs to be water-free, thus the production requires distillation
beyond the azeotrope point, and this is one of the major production costs of
fuel-ethanol.
229
On the contrary, ESR process requires, as mentioned pre-
viously, a signicant amount of water (50, 51), which makes the expensive
distillation superuous. Only a simple ash distillation to some 5070% is
necessary thereby considerably lowering the production costs of bioethanol.
However the use of the diverse feedstocks as well as the ash distillation can
pose dierent challenges in a subsequent ESR catalyst, due to the variety of
contaminants present in the dierent bioethanol fractions. The composition
of two qualities of bioethanol produced in France from sugar beet is pre-
sented in Table 24. In the crude bioethanol fraction, the main impurities are
alcohols accounting for 87% of the impurities contained in crude ethanol,
the most important being propan-1-ol (27%) and methyl-3 butanol-1
(27%). One can also note the presence of esters, aldehydes, acetic acid and
nitrogen-containing bases. The following paragraph of this review will re-
port a study of the eect of impurities present in raw bioethanol, such as
esters, aldehydes, higher alcohols or acetic acid, on the stability of the
several catalysts during bioethanol steam reforming.
As far as rst generation bioethanol is concerned, the major part of the
contaminants will be always heavy alcohols with a variation in the com-
position that depends on the crop (Table 25).
To our knowledge, only one group reported the composition of diverse
fractions (Table 26) obtained from a second generation bioethanol and
investigated the eect of its utilization as a feedstock in the ESR process.
231
The biomass used is the wheat straw which was mixed with enzymes and
Table 23 Composition of the lignocellulosic biomass from dierent feedstock. From ref. 228
Biomass Lignin (%) Cellulose (%) Hemicellulose (%)
Soft wood 2730 3542 2030
Hard wood 2025 4050 2025
Wheat straw 1520 3043 2027
Catalysis, 2010, 22, 155 | 39
yeast and fermented for 5 days which resulted in an ethanol concentration
of around 56% (fraction 1 in Table 26). Fraction 2 and 3 were obtained
from dierent parts of the distillation Inbicon Process.
232
Because the
fraction 1 caramelized when evaporized, this fraction was not directly used
and the authors needed to further distill in order to remove the dierent
sugars. Looking at the major contaminants of the fractions 2 and 3 we nd
again similarities with the composition of the raw bioethanol obtained from
sugar beet. The consequences of these feedstocks on the catalytic activity in
ESR is reported hereafter.
4.2 Crude bioethanol steam reforming
Until now crude bioethanol has been very rarely used as ethanol source for
ESR reaction, whereas it is a solution to produce hydrogen in a cost-
eective manner. The majority of the studies reported in the literature on
the production of hydrogen by ethanol steam reforming were performed
Table 25 Constituents met in dierent bioethanol charges from several type of crops (% vol.).
From ref. 230
Constituents
Crops
Sugar beet Cereal Potatoes
Methanol 5.1
n-propan-1-ol 31.7 9.1 16.4
Sec-butan-1-ol
Isobutan-1-ol 16.6 19.2 15.9
n-butan-1-ol 0.2 1.2
2-methylbutan-1-ol 14.9 19.0 13.6
3-methylbutan-1-ol 31.7 52.4 52.9
Table 24 Composition of rectied and crude bioethanol produced from sugar beet. Analysis
performed by the alcohol distillers union (n.d. : non detected)
Crop Units Rectied Alcohol Raw Alcohol
Alcohol percentage %vol. (@ 20 1C) 96.3 92.9
Total acidity (Acetic acid) g m
3
0.8 0.4
Dry extract g m
3
20 39
Esters g m
3
o1 123
Aldehydes g m
3
o1 108
Methanol g m
3
42.5 94
Butan-2-ol g m
3
o0.5 o10
Propan-1-ol g m
3
o0.5 581
Methyl-2 Propanol-1 g m
3
o1 304
Propen-2 ol-1 g m
3
n.d. o10
Butan-1-ol g m
3
o0.5 o10
Methyl-2 butanol-1 g m
3
n.d. 273
Total higher alcohols g m
3
n.d. 582
Total sulphur g m
3
o0.5 855
Volatile nitrogenated bases g m
3
o1 1746
40 | Catalysis, 2010, 22, 155
using pure ethanol. The steam reforming of crude ethanol diers from that
of pure ethanol by the fact that the impurities present in the crude ethanol
feed may inuence the hydrogen yield and the catalyst stability. Two types
of studies on the eect of the use of crude bioethanol have been performed
by either using model ethanol and water mixtures containing one impurity
as identied in crude bioethanol or using directly a real crude bioethanol
feed.
Very few studies report the use of crude ethanol for hydrogen production
by steam reforming. Akande et al.
233
used directly the mixture provided by
Pound Maker Agventures (Canada) and obtained by fermentation of high
starch feed wheat. This crude bioethanol contained, for a most part, water
(86 vol.%) and ethanol (12 vol.%), and impurities such as lactic acid
(1 vol.%), glycerol (1 vol.%) and traces of maltose. Crude bioethanol steam
reforming was directly performed on the crude ethanol sample at atmos-
pheric pressure and 400 1C, at a rather low weight hourly space velocity
(WHSV) of 1.68 h
1
. Ni/Al
2
O
3
catalysts containing 10 to 25 wt.% of
Ni and prepared by various techniques (coprecipitation, precipitation and
impregnation) were used for the experiments. Whatever the nickel content
and the preparation method, the initial ethanol conversion was high, be-
tween roughly 55 and 95%, and then decreased with time on stream (TOS)
to stabilize at about 200 min. The same catalyst behaviour was obtained
during the steam reforming of crude bioethanol from sugar beet, in the
presence of a Rh/MgAl
2
O
4
catalyst.
234
In both cases, the deactivation ob-
served at the onset of the reaction was attributed to coking.
In another study, Vargas et al.
235
observed also a deactivation, but only
after 11h of time-on-stream. They used a real bioethanol obtained by sugar
cane molasses fermentation followed a simple distillation at 60 1C.
Table 26 Constituents met in dierent fractions of bioethanol from wheat straw fermentation.
From ref. 231
Fraction 1 Vol% Fraction 2 Mol% Fraction 3 Mol%
Major
constituents
Ethanol 5.7 Ethanol 18 Ethanol 44
Xylose 1.2 3-Methyl-1-
butanol
0.7 Ethyl acetate 0.5
Glucose 1.1 2-Methyl-1-
propanol
0.3 1,1-Diethoxyethane 0.2
Lactate 0.5 2-Methyl-1-
butanol
0.3
Acetate 0.5 Propanol 0.1
Glycerol 0.4 Cyclopentanone 0.05
Other
constituents
(traces)
Ethyl acetate Furfural Propanol
Acetic acid 4-Hexen-1-ol 2-Methyl-1-
propanol
1,1-Diethoxyethane 3-Methyl-1-
butanol
2-Methyl-1-
butanol
Cyclopentanone
Catalysis, 2010, 22, 155 | 41
The solution was mainly made of water and ethanol (ethanol/water=
1/5.95 mol/mol) and contained only traces of methanol, n-propanol,
n-butanol and 3-methylbutanol (isoamylic alcohol) as impurities. The re-
action was also performed at atmospheric pressure, 540 1C and the real
bioethanol mixture was diluted in a Ar/N
2
gas mixture. The catalyst was a
Ce-Zr-Co uorite-type oxide. The results obtained showed that the catalytic
behavior is similar when using a water/pure ethanol mixture or a real
bioethanol feed. The only dierence concerned the slightly higher hydrogen
yields obtained from bioethanol due to the steam reforming of the higher
alcohols. Nevertheless, whatever the origin of the ethanol used for the
reaction, the ethanol conversion was 100% at the onset of the reaction,
remained stable during the rst 11h of TOS and then declined continuously
to reach roughly 4550% after 25 h TOS. Consequently, the hydrogen yield,
which was higher than 0.3 g H
2
h
1
g
cat
1
at the beginning of the reaction,
falled down 0.1 H
2
h
1
g
cat
1
after 25 h. The apparent stability observed
during the rst hours of TOS may be explained by the large amount of
catalyst used for this reaction, in excess compared to the one needed to
reach the complete ethanol conversion. Possibly during the rst hours of
TOS a part of the catalyst did not work. In this study, the deactivation was
also explained by the authors by the formation of carbon during the
reaction.
More recently, Rass-Hansen et al.
231
used a technical bioethanol pro-
duced from wheat straw. Two fractions of technical alcohol were tested
in ethanol steam reforming. These fractions were obtained from dierent
parts of the distillation process. They contained contaminants such as
ethyl acetate , 1,1-diethoxyethane, higher alcohols and cyclopentanone, the
percentage of each type of impurity depending on the fraction considered.
The catalysts used for this study were Ni and Ru catalysts supported on
MgAl
2
O
4
spinel. The authors observed that whatever the reaction tem-
perature and the catalyst, the rate of carbon formation is generally slightly
higher for the technical bioethanol than for a pure ethanol/water mixture.
The rate of carbon formation is also the highest at the onset of the reaction.
They also noticed that the presence of higher alcohols is likely to contribute
to the fast deactivation of catalyst.
In conclusion, whatever the origin of the bioethanol, a deactivation of the
catalyst was observed during the steam reforming reaction that was at-
tributed to the formation of carbon deposit.
4.3 Ethanol steam reforming in the presence of various impurities
As previously detailed, the main impurities present in crude raw bioethanol
(92.9 vol.%) obtained from sugar beet are higher alcohols accounting for
87% of the impurities, the most important being propan-1-ol (27%) and
methyl-3 butanol-1 (27%), and also esters, aldehydes, acetic acid and
nitrogen-containing bases.
236
In order to determine which type of impurity
is responsible for the deactivation observed during the steam reforming of
crude bioethanol, the impact of various impurities on this reaction was
studied. For that purpose, model raw ethanol feeds were prepared by
addition of 1 mol% of one impurity in ethanol. Three series of impurities
42 | Catalysis, 2010, 22, 155
have been studied, namely (i) molecules with four carbon atoms and dif-
ferent functions (butanal, diethylether, butanol, ethylacetate) (ii) molecules
with acidic and basic properties (acetic acid and diethylamine) and (iii)
linear or branched alcohols (methanol, propan-1-ol, butan-1-ol, pentan-1-
ol, isopropanol, 2-methylpropan-1-ol, 3-methylbutan-1-ol). The results
obtained in the presence or not of various impurities after 8h of time on
stream on a 1 wt.%Rh/MgAl
2
O
4
catalyst with a molar water to ethanol
ratio R of 4, a weight hourly space velocity of 19.5 h
1
are summarized in
Table 27. These reaction conditions were chosen in order to have less than
100% of ethanol conversion (X
EtOH
%) to discriminate the possible eects
of the compounds present in bioethanol on the catalyst stability.
4.3.1 Acid and basic impurities. Table 27 shows that the presence of
diethylamine favors the ethanol conversion, and slightly increases the
hydrogen yield. This promoting eect of diethylamine has been explained
by a competition of this basic molecule with the alcohol molecules for the
acidic sites.
236
Diethylamine being adsorbed preferentially on the acidic sites
of the support, the dehydration of ethanol on these sites is thus inhibited.
The promoting eect of diethylamine on ethanol conversion was explained
by a modication of the metal electronic properties resulting from an
electron transfer of the free nitrogen doublet toward the metal.
236
Contrary to what is observed with diethylamine, the presence of acetic
acid leads to a decrease of both ethanol conversion and hydrogen yield
compared to what is obtained without impurity. Acetic acid may promote
ethylene formation by increasing the acidity of the support surface and then
favors the catalyst deactivation by coke deposition. The yield in ethylene
observed in the presence of acetic acid is similar to that obtained in the
absence of this impurity, but it is at a lower ethanol conversion, which
Table 27 Performances in steam reforming of ethanol with or without 1% of impurity using
Rh(1%)/MgAl
2
O
4
/Al
2
O
3
catalyst after 8 h of time on stream (T=675 1C, P=2 bar, R=4)
Impurity
Distribution of products (mol mol
EtOH
1
)
X
EtOH
Coke
a
H
2
CO CO
2
CH
4
C
2
H
4
C
2
H
6
CH
3
CHO H
2
O (%)
2.35 0.57 0.34 0.3 0.07 0.04 0.03 3.5 78 29.5
Diethylamine 2.53 0.67 0.37 0.38 0.06 0.04 0.02 3.45 88 64.0
Acetic acid 2.08 0.49 0.31 0.26 0.07 0.04 0.04 3.6 72 68.0
Butanal 2.6 0.67 0.39 0.35 0.06 0.04 0.02 3.41 86 93.3
Butanol 1.42 0.35 0.19 0.26 0.09 0.04 0.04 3.95 64 77.4
Ethyl acetate 0.97 0.31 0.09 0.29 0.13 0.04 0.05 4.06 57 67.0
MeOH 2.48 0.57 0.37 0.25 0.06 0.04 0.03 3.06 78 74.0
n-C
3
H
7
OH 1.52 0.47 0.19 0.38 0.12 0.05 0.04 3.47 74 80.0
n-C
4
H
9
OH 1.42 0.35 0.19 0.26 0.09 0.04 0.04 3.63 65 77.4
n-C
5
H
11
OH 1.23 0.33 0.14 0.29 0.11 0.04 0.05 3.46 57 62.0
i-C
3
H
7
OH 1.22 0.38 0.13 0.33 0.13 0.04 0.04 3.76 70 101.0
i-C
4
H
9
OH 1.05 0.31 0.10 0.29 0.11 0.04 0.05 3.61 56 62.5
i-C
5
H
11
OH 0.89 0.28 0.09 0.25 0.10 0.04 0.05 3.78 53 75.0
a
In mgC.g
cat
1
obtained from TPO experiments on spent catalyst after reaction.
Catalysis, 2010, 22, 155 | 43
means that the selectivity in ethylene is higher in the presence of acetic acid.
The catalyst deactivation observed in the presence of acetic acid may also be
explained by the formation of intermediate acetate species that decompose
into H
2
, CO
2
and adsorbed carbon on the surface. Then, whatever
the intermediate species invoked (ethylene or acetate) the deactivation of the
catalyst observed in the presence of acetic acid was explained by the for-
mation of coke, favored in the presence of this acidic molecule.
236
4.3.2 Various types of impurities with four carbon atoms. Various type
of impurities identied in raw bioethanol were studied (aldehyde, higher
alcohol and ester) with the same amount of carbon atoms, i.e. butan-1-al,
butan-1-ol and ethyl acetate were also studied. Table 27 shows that in the
presence of butanal, the ethanol conversion and the hydrogen yield are
increased compared to the reference test (without impurity), as it was ob-
served in the presence of diethylamine. On the contrary, the presence of
butanol and ethylacetate strongly deactivates the catalyst, but the most
deactivating impurity is diethylether since the ethanol conversion is of 64
and 57% in the presence of the alcohol and the ester, respectively. In the
presence of these impurities, the yields of nal products (H
2
, CO, CO
2
, CH
4
)
are strongly decreased, whereas the yields of intermediate products, espe-
cially ethylene and acetaldehyde are higher than that of the reference test.
Then, it can be inferred that intermediate products are rapidly produced by
ethanol dehydration or dehydrogenation on the catalyst but they are more
slowly transformed. The presence of high amounts of ethylene may explain
the catalyst deactivation by formation of carbonaceous products. The
deactivation observed in the presence of butanol may also be linked to the
production of butene, which is also a coke precursor, by butanol de-
hydration. The deactivation by the ester may be due to the hydrolysis of
ethylacetate on the acidic sites of the support, yielding ethanol and acetic
acid, and then to the presence of acetic acid. But, the deactivation observed
is much more important than that observed in the presence of acetic acid.
The deactivation may be also explained by a competitive adsorption, since
it has been reported in the literature that ethylacetate is more strongly
adsorbed on alumina than ethanol.
237
4.3.3 Eect of the alcohols. In the presence of methanol (Table 27), the
ethanol conversion is not modied but the hydrogen yield is slightly in-
creased, compared to the reference test. Methanol is easily converted by
steam reforming, thus producing also hydrogen, and then its presence does
not aect the ethanol conversion. In the presence of the higher alcohols
(more than three carbon atoms), linear or branched, the ethanol conversion
and the hydrogen yield decrease when the amount of carbon atoms in the
molecule is increased. This eect is more pronounced in the presence
of branched alcohols compared to the linear ones. It can be seen from
the value presented in Table 27 that the yield in ethylene is much more
important in the presence of these alcohols than with ethanol alone, thus
leading to a more important amount of coke. It has been also demonstrated
by studying the steam reforming of these higher alcohols
234
that they are
dehydrated to the corresponding olen. The olens may be then polymer-
ized to yield coke, the coke extent increasing with the amount of carbon
44 | Catalysis, 2010, 22, 155
atoms in the olen. The more important deactivating eect of the branched
alcohols may be explained by the formation of more stable carbocations
thus facilitating the olen production.
210
In conclusion, except methanol, diethylamine and butanal, all the im-
purities identied in crude bioethanol from sugar beet lead to the de-
activation of the Rh/MgAl
2
O
4
catalyst, mainly by coke deposition.
4.4 Catalysts for crude bioethanol steam reforming
As, whatever the experimental conditions and the catalysts, the catalyst
deactivation observed during the steam reforming of crude bioethanol is
due to coke formation,
233235
it is of major importance to reconsider the
catalyst formulation, by modifying the support and then metallic phase, in
order to nd a stable catalyst able to convert crude bioethanol by steam
reforming.
In order to improve the catalyst stability in the presence of crude bioe-
thanol, various rare earth elements (Sc, Y, La, Er and Gd) were added to an
alumina support. Indeed, these species are known to improve the catalytic
performance in steam reforming and the stability of the catalysts, by de-
creasing the support acidity, thus disfavoring the olen formation, and by
increasing its basicity, necessary to activate water. These supports were used
for depositing 1wt.% of rhodium. The characterization of this catalyst series
has been described in detail by Can et al.
153
Table 28 reports the results
obtained during the pure ethanol steam reforming in the presence of these
catalysts, compared to that of a Rh/MgAl
2
O
4
one. All modied samples
clearly show higher ethanol conversions (X
EtOH
), hydrogen yields and
lower intermediate product yields, especially ethylene, compared to the
Rh/MgAl
2
O
4
catalyst. The highest performances were obtained with the
Rh/Y
2
O
3
-Al
2
O
3
(Table 28).
Nevertheless, whatever the catalyst, the methane yield is much higher
than the value at the thermodynamic equilibrium. This result may be ex-
plained if methane is considered as an intermediate product. Then, a way
to improve the yield in hydrogen would be to decrease the yield in methane.
For that purpose, the metallic phase was also modied by adding a second
metal.
236
Pd, Pt (1 wt.%) and Ni (6 wt.%) precursor salts were thus
Table 28 Performances in steam reforming of pure ethanol, using Rh(1%) catalyst supported
on MgAl
2
O
4
or on alumina modied by addition of rare earth elements, after 8 h of time on
stream (T=675 1C, P=2 bar, R=4)
Catalyst Impurity
Yield (mol mol
1
)
X
EtOH
(%) H
2
CO CO
2
CH
4
C
2
H
4
C
2
H
6
CH
3
CHO H
2
O
Thermodynamic
equilibrium
3.77 0.54 0.71 0.10 0.00 0.00 0.00 3.03
Rh/MgAl
2
O
4
2.35 0.57 0.34 0.3 0.07 0.04 0.03 3.50 78.0
Rh/Sc
2
O
3
-Al
2
O
3
3.30 0.71 0.63 0.53 0.01 0.02 0.01 2.56 99.4
Rh/Y
2
O
3
-Al
2
O
3
3.43 0.67 0.65 0.50 0.01 0.01 0.01 2.50 98.7
Rh/La
2
O
3
-Al
2
O
3
3.34 0.62 0.69 0.54 0.01 0.01 0.01 2.50 98.6
Rh/Er
2
O
3
-Al
2
O
3
3.09 0.69 0.59 0.57 0.02 0.02 0.01 2.64 98.7
Rh/Gd
2
O
3
-Al
2
O
3
3.29 0.67 0.66 0.54 0.01 0.02 0.00 2.54 98.7
Catalysis, 2010, 22, 155 | 45
coimpregnated with the Rh precursor onto the Y
2
O
3
-Al
2
O
3
support.
The results presented in Table 29 show that the presence of nickel or pal-
ladium allows one to increase the hydrogen yield, whereas platinum has no
benecial eect. Nevertheless, the promoting eect of Ni is more pro-
nounced than that of palladium. The better performances of the Rh-Ni
catalysts may be explained either by a better water-gas shift activity or by
a better methane steam reforming activity, both reactions leading to the
formation of hydrogen. The yield in CO is slightly increased in the presence
of Rh-Pd and Rh-Ni catalysts compared to that obtained in the presence of
Rh (from 0.7 to 0.79 and 0.75 respectively), but the methane yield is much
more decreased (from 0.55 to 0.49 and 0.46 respectively). It can be inferred
from these results that the presence of Pd or Ni decreases slightly the
activity of the catalysts for the water gas shift reaction but increases in a
major extent the activity in methane steam reforming. As this reaction
yields 3 molecules of hydrogen per molecule of methane converted, the
highest hydrogen yield obtained with the Rh-Ni catalyst may be explained
by its higher activity in methane steam reforming compared to the Rh
catalysts.
The Rh-Ni/Y
2
O
3
-Al
2
O
3
was tested in the presence of crude bioethanol
from sugar beet and its stability was compared to that of the Rh/MgAl
2
O
4
catalyst in the same conditions. Fig. 11 presents the hydrogen yield vs.
time on stream for these two catalysts. After 24 h of time-on-stream, the
hydrogen yield is very high (3.49 mol/mol
ethanol
) with the Rh-Ni/ Y
2
O
3
-
Al
2
O
3
catalyst, and the conversion is only slightly decreased from 100% at
the onset of the reaction to 97% after 24 h of time-on-stream (97% of
conversion compared to 100% at the beginning of the reaction). On the
contrary, in the same reaction conditions, the Rh/MgAl
2
O
4
catalyst is
strongly deactivated by coke deposition, especially during the rst 2 h of
reaction.
5. Conclusions and recommendations
Although catalytic steam reforming (SR) is widely used for hydrogen
production, it is not a green process since all the carbon contained
in the feedstock is transformed into CO
2
. Replacing fossil fuels (mainly
natural gas today) by biofuels may circumvent this drawback. Bio-
ethanol is an excellent candidate in the perspective of a hydrogen-based
economy.
Table 29 Performances in steam reforming of ethanol with 1% of 2-methylpropan-1-ol as
impurity, using Rh(1%)-X catalysts (X=Pt, Pd or Ni) catalysts supported on Y
2
O
3
-Al
2
O
3
,
after 8 h of time on stream (T=675 1C, P=2 bar, R=4)
Metal phase
Yield (mol mol
1
)
X
EtOH
(%) H
2
CO CO
2
CH
4
C
2
H
4
C
2
H
6
CH
3
CHO H
2
O
Rh 3.43 0.67 0.65 0.50 0.01 0.01 0.01 2.50 98.7
Rh-Pt 3.53 0.69 0.77 0.57 0.02 0.02 0.01 2.04 93.4
Rh-Pd 3.64 0.79 0.69 0.49 0.01 0.02 0.01 2.24 98.6
Rh-Ni 3.84 0.75 0.76 0.46 0.01 0.01 0.01 2.10 98.2
46 | Catalysis, 2010, 22, 155
On a kinetics and catalysis point of view, there are some similarities
between the steam reforming of hydrocarbons and that of alcohols:

Rhodium is the most active metal for the reaction. However, the steam
reforming being not very sensitive to the nature of metal, other metals (Ni,
Co, . . .) can also be used.

Thermodynamically, the steam reforming requires relatively high

temperatures and low pressures.

When the reaction is carried out at moderate temperatures (400

500 1C; case of aromatic steam dealkylation), the support may play a
dominant role, specially on Rh. At higher temperatures (550 1C and above),
and specially for methane steam reforming, hydrocarbon activation is the
determining step of reaction.
But there are also some remarkable dierences between hydrocarbons
and alcohols.

Alcohols currently lead to complex kinetic schemes including

dehydration, dehydrogenation, cracking,. These reactions may be much
more rapid than the steam reforming itself, which makes that alcohol
conversion is not fully representative of the SR rate and of the rate of H
2
production.

Alcohols are more reactive than the corresponding hydrocarbons

in steam reforming but the maximal H
2
yield is lower (for instance,
it is of 6 moles H
2
per mole of ethanol and 7 moles H
2
per mole of
ethane).
Several grades of bioethanol can be processed to produce hydrogen but
high purication costs should be avoided. Most studies were devoted to the
steam reforming of pure ethanol. The present tendency is to produce bio-
fuels of second generation from lignocellulosic biomass or even from lig-
nine. It is recommended to pay more attention to the use of raw bioethanol
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
0 4 8 12
Rh/MgAl
2
O
4
Rh-Ni/Y
2
O
3
-Al
2
O
3
16 20 24
Time (h)
H
y
d
r
o
g
e
n

y
i
e
l
d

(
m
o
l
/
m
o
l
)
Fig. 11 Hydrogen yield as a function of time-on-stream during the steam reforming of crude
bioethanol in the presence of the Rh/MgAl
2
O
4
and Rh-Ni/Y
2
O
3
-Al
2
O
3
Rh-Ni/Y-Al
2
O
3
catalysts.
Catalysis, 2010, 22, 155 | 47
that could be produced by such processes and to develop catalysts more
resistant to deactivation.
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Catalysis, 2010, 22, 155 | 55
Catalytic reforming of liquid hydrocarbons
for on-board solid oxide fuel cell auxiliary
power units
Johannes W. Schwank
a
and Andrew R. Tadd
a
DOI: 10.1039/9781847559630-00056
Catalytic reforming of liquid transportation fuels and their hydrocarbon
components via steam reforming, catalytic partial oxidation, and auto-
thermal reforming is reviewed. The review focuses on fuel reforming to
generate hydrogen-rich syngas for on-board applications, with emphasis on
solid-oxide fuel cell (SOFC) based auxiliary power units (APU). After a
brief overview of fuel properties of gasoline, diesel and kerosene-based jet-
fuels such as JP-8, reforming methods including steam reforming, catalytic
partial oxidation and autothermal reforming are discussed. Strategies to
deal with catalyst deactivation caused by carbon deposition and sulfur
poisoning are delineated. The review also addresses the special engineering
challenges associated with the development of compact, on-board fuel re-
formers for gasoline, diesel, and jet fuels.
1. Introduction
Motivated by requirements for better fuel economy and lower emissions,
the automobile industry has been working on various concepts for electri-
cation of drive trains. While the immediate future may see the large-scale
deployment of hybrid and plug-in hybrid electric vehicles, the development
of hydrogen-powered proton exchange membrane (PEM) fuel cell vehicles
is being pursued as an alternative option for eventually replacing the
internal combustion engine.
With growing interest in fuel cells as primary propulsion systems for
automobiles,
1
a concerted research and development eort was mounted
towards on-board reforming of gasoline.
2
PEM fuel cells require high-purity
H
2
. Given the challenges of limited on-board hydrogen storage capacity and
the lack of hydrogen refueling infrastructure, on-board processing of gas-
oline into pure H
2
has been considered as a possible solution.
3
Most of the
research projects focused on partial oxidation or autothermal reforming
processes, as on-board applications required fast start-up and good transient
response.
4
Large-scale conventional steam reforming technology developed
for stationary applications cannot easily be transferred to automotive ap-
plications, due to size and weight limitations, and the limited availability of
steamon board a vehicle. To generate the amount of hydrogen required for a
PEMfuel cell vehicle would have taken a reformer systemtoo large to t into
a typical passenger car. Therefore, major eorts had to be directed towards
downsizing of fuel reformer systems and the development of novel catalytic
reactor congurations, including microstructured and plate reformers.
515
a
Transportation Energy Center, Department of Chemical Engineering, University of Michigan,
3014 H.H. Dow Building, 2300 Hayward Road, Ann Arbor MI 48109-2136
56 | Catalysis, 2010, 22, 5693
c
The Royal Society of Chemistry 2010
The technical challenges in developing compact on-board fuel processors are
quite formidable, especially for applications requiring the fuel processing of
logistic fuels such as JP-8 and diesel.
Catalytic fuel reforming generates a hydrogen-rich gas stream from
hydrocarbons.
16,17
Catalysts for onboard fuel reforming must meet a large
number of requirements. First, they should be able to catalyze reforming
reactions of hydrocarbons and their thermal decomposition products, and
be able to function under transient conditions, permitting multiple startups
and shutdowns without requiring elaborate regeneration schemes. Catalysts
should be resistant to coking, and they must be thermally stable without
sintering at the high temperatures encountered under typical fuel processing
conditions. Furthermore, they must be mechanically strong and withstand
the vibrations on moving vehicles. Ideally, they should also be tolerant to
sulfur, even if low-sulfur fuels are being used. Finally, catalysts must be able
to cope with the variability in the chemical composition of fuels and fuel
additives.
Despite considerable progress towards technical targets set by the U.S.
Department of Energy, the complexity and technical diculty of generating
pure H
2
from gasoline on-board of vehicles prompted the U.S. Department
of Energy in 2004 to make a no-go decision, and funding of research eorts
for on-board fuel reforming of gasoline into PEM-fuel cell grade H
2
dried
up.
18
Instead, the research and development eort was redirected towards
centralized hydrogen generation and on-board storage of H
2
.
There is, however, another fuel cell application that could greatly benet
from on-board reforming of liquid transportation fuels, namely auxiliary
power units (APU) containing solid oxide fuel cells. Heavy-duty trucks,
military vehicles, and recreational vehicles have signicant needs for electric
power even when the vehicle is not moving.
1923
For example, heavy-duty
trucks tend to idle their diesel engines for many hours at a time, burning fuel
at very low eciency, to provide heating and cooling and generate power
for sleeper compartment accessories such as televisions, microwave ovens,
and refrigerators. According to recent studies, idling diesel engines burn
nearly a billion gallons of diesel fuel every year in the United States alone,
and shifting to SOFC-APU systems could result in signicant fuel savings
and lower emissions.
24,25
Depending on the degree of thermal integration,
on-board SOFC APUs can be more ecient than conventional combustion-
engine based electricity generators and provide the additional benets of
lower emissions and lower noise levels. The major impediment to the
commercial deployment of SOFC-based APU systems is the challenge to
convert liquid transportation fuels such as diesel and JP-8 military fuels on-
board into hydrogen-rich syngas suitable for SOFCs.
Several books on the subject of fuel cell technology contain chapters
providing an introduction into the basic principles of fuel processing.
2629
There have also been several review papers published on the subject of fuel
processing for transportation and other portable power applications.
3034
Song provided an overview of the fuel processing options for low-
temperature and high-temperature fuel cells.
35
Qi et al. reviewed the techno-
logical progress in the development of integrated fuel processors, with focus
on process optimization and process intensication technologies such as
Catalysis, 2010, 22, 5693 | 57
engineered catalysts, heat integration, and in situ product purication.
36
Recently, two German reviews were published, dealing with the reforming
of liquid fuels with special regard to the properties of diesel fuel and light
fuel oil.
37,38
Semelsberger et al. analyzed various reforming processes from a
thermodynamic point of view.
39
An extensive review of catalytic reforming
of liquid hydrocarbon fuels for fuel cell applications appeared in 2006,
40
focusing on reforming of diesel, gasoline, and representative model com-
pounds. This earlier review
40
provided an excellent treatment of the relevant
thermodynamics, especially with regard to formation of carbon and coke,
and also summarized kinetics and rate laws.
Studies of heavy liquid hydrocarbon reforming started to appear during
the 1980s,
41
and there has been considerable interest in smaller scale
fuel reforming using monolithic structures for distributed power generation
in both stationary and mobile applications.
42
Considerable progress has
been made towards reforming of C8

hydrocarbons that are typically

encountered in gasoline, diesel, or jet fuel.
4352
However, there are still
many open questions as to how specic types of molecules aect the
reforming behavior of commercial fuels. Research publications on the
subject of fuel processing of liquid fuels fall into two general categories:
the rst category includes fundamental studies of catalytic conversion of
individual molecular components of a fuel or mixtures of model compounds
serving as surrogates for fuels. The second category contains papers that
demonstrate a catalysts ability to reform gasoline, diesel, or jet fuel
at laboratory scales to demonstrate the feasibility of various fuel proces-
sing strategies. Here, we are focusing exclusively on reviewing on-board
catalytic fuel processing of hydrocarbon-based liquid transportation
fuels with emphasis on SOFC-based APU applications. This review
will not deal with other reforming methods such as plasma-assisted
reforming,
53
or supercritical reforming that have been covered in earlier
reviews.
40
This review also does not cover the extensive literature on
reforming of methane, propane, butane,
54,55
or alcohols such as methanol
56
and bioethanol.
57
2. Fuel properties and SOFC fuel requirements
PEM fuel cells function only with very pure H
2
that contains at most ppm
levels of CO. Consequently, on-board fuel processing of gasoline or diesel
for a PEM fuel cell requires an elaborate set of catalytic reactors operating
in series, including a desulfurizer, a reformer, high and low temperature
water gas shift reactors, and a selective oxidation reactor, methanation
reactor, or palladium membrane to remove the remaining traces of CO.
This poses a major challenge to operate all these reactors in a synchronized,
load-following mode. SOFCs do not require such an elaborate fuel-
processing scheme. The only requirement is to convert the liquid hydro-
carbons into hydrogen-rich syngas and to protect the fuel cell from sulfur
contamination. This, for all practical purposes, requires only a reformer and
desulfurizer. Furthermore, APUs for heavy duty vehicles tend to operate
under more or less steady-state load for long periods of time, and there is
less demand for dynamic load following.
58 | Catalysis, 2010, 22, 5693
To gain a better understanding of the challenges involved in converting
gasoline, diesel, or jet fuels into H
2
-rich syngas, a brief overview of prop-
erties and compositions of these fuels may be helpful. Gasoline, diesel, and
commercial jet fuels consist of hundreds of compounds. The exact fuel
compositions may be adjusted depending on the season and geography.
Gasoline is a complex fuel and contains many impurities that can create
problems in catalytic fuel processing. Its catalytic conversion to syngas re-
quires high temperatures in excess of 930 K. Commercial jet fuels JET-A
and JET-A1 that are primarily used in the US are kerosene-based fuels. The
military uses specially formulated kerosene jet fuels, JP-4, JP-5, JP-8, and
JP-100. These fuels have been hydrotreated and contain several additives.
Jet fuels are considered kerosene-type fuels because fuel vaporization takes
place mainly within a temperature range of 473623 K. This range is much
narrower compared to diesel, to meet the specications for turbine engines.
The high temperature boiling ranges of diesel and jet fuels make laboratory-
scale fuel reforming studies quite dicult.
Diesel and jet fuels contain three major types of hydrocarbons: linear and
branched parans, cycloalkanes, and aromatics. The ring structures in
cycloalkanes and aromatics are generally believed to be more dicult to
reform than parans. Diesel has typical carbon numbers of 1016, while
JP-8 can be represented by an average carbon number of 11, excluding
sulfur compounds and heteroatom containing additives, and gasoline by a
carbon number of 8. Often, studies of fuel reforming of complex fuels are
carried out using simpler surrogate model compounds and their mixtures.
58
A good fuel surrogate should capture the major characteristics of the fuel,
but make the analysis simpler. For example, JP-8 can be modeled with
mixtures of n-dodecane, methylcyclohexane, and butylbenzene. For diesel,
hexadecane could be used as surrogate as it provides a match of the C
16
carbon number, but it turns out that the combustion properties of diesel are
closer to dodecane, which is therefore often used as a surrogate. Inci-
dentally, dodecane is also a suitable surrogate for parans in JP-8. Violi et
al. developed a surrogate blend of six pure hydrocarbons to simulate the
distillation and compositional characteristics of JP-8.
59
Although heteroatoms such as sulfur and copper are present in only small
concentrations, they can have a signicant eect on a fuels reforming
chemistry and on the performance of reforming catalysts. Jet fuels such
as JP-8 can contain 300 ppm to 5000 ppm of sulfur and 100 ppb copper.
Nitrogen containing compounds in the fuels seem to have less inuence on
reforming catalysts.
Jet fuels contain a number of additives, and the type and concentration of
additives represents the main dierence between Jet-A and JP-8.
60
For ex-
ample, the military specication MIL-DTL-83133 for JP-8 requires the
addition of compounds that can act as static electricity dissipators, cor-
rosion inhibitors, lubricity enhancers, fuel system icing inhibitors, and
antioxidants.
Jet fuels tend to be quite susceptible to oxidation, since they may
have undergone hydrotreating to remove mercaptans. The role of anti-
oxidants is to prevent reactions of dissolved oxygen with fuel molecules that
could lead to the formation of peroxides, gums, and particulates. Typical
Catalysis, 2010, 22, 5693 | 59
antioxidants are sterically hindered phenols, for example 2,6-ditertiary
butyl-4-methylphenol.
The purpose of adding static dissipators is to increase the electrical con-
ductivity of the fuel, thereby preventing the build-up of hazardous static
charges. The currently used Statdis 450, manufactured by Octel, contains
dinonylnaphthalene sulfonic acid along with other organic solvents and two
additional ingredients consisting of sulfur and nitrogen-containing polymers.
61
Corrosion inhibiting and lubricity improving additives protect the fuel
distribution system from corrosion and lubricate metal surfaces in the tur-
bine engine. These are compounds that strongly interact with metal surfaces,
and are added at typically 20 mg/L concentrations. There are many dierent
trade names for these additives, for example QPL-25017-7 shown below.
Fuel system icing inhibitors consist of di-ethyleneglycol monomethylether
(di-EGME).
CH
3
OCH
2
CH
2
OCH
2
CH
2
OH
This additive, present at 0.10.15 vol%, prevents water that is dissolved in
the fuel from freezing at low temperatures. The handling of fuels containing
di-EGME in a fuel processor is dicult because di-EGME can precipitate
out and form a gelatinous phase when water and fuel are co-fed in liquid
form. Therefore, it is of critical importance to completely vaporize both the
water and the fuel prior to feeding them into the fuel processor.
The purpose of the metal deactivating additive N,N
0
-disalicylidene-1,2-
propane diamine, added typically at 10 mg/L is to improve the thermal
stability of fuels by deactivating trace contaminations of metals.
60 | Catalysis, 2010, 22, 5693
One of the major issues in fuel processing of liquid fuels is the require-
ment to vaporize the fuel prior to feeding it into the reformer. Heavy
hydrocarbons typically present in diesel have boiling points higher than
620670 K, and at these temperatures, some fuels begin to pyrolyze. Some
reforming methods, as we will see later, require the co-feeding of steam, and
this can cause complications with miscibility and gelation of some of the fuel
components.
3. Catalysts for reforming of liquid hydrocarbons
The catalysts used for reforming of liquid hydrocarbons are usually pre-
cious metal such as rhodium or nickel supported on oxide supports. There
seems to be a consensus that the reforming of hydrocarbons in liquid
transportation fuels is possible, but dicult because of problems associated
with carbon formation and sulfur poisoning. Consequently, the literature
shows a strong interest in catalytic supports with oxygen storage capacity,
particularly mixed ceria-oxides, as a means to reduce coke formation.
Mobile oxygen in the support might play an important role in the reforming
of the liquid hydrocarbons, possibly by making the catalyst more resistant
to coking by facilitating the oxidation of surface carbon species.
62,63
In
addition to typical supported metal catalysts, doped or substituted metal-
oxide catalysts have also been applied to liquid fuel reforming. Of note are
pyrochlore catalysts and hexaaluminate catalysts.
67
The majority of reforming catalysts reported in the literature have been
prepared by conventional techniques. General descriptions of catalyst syn-
thesis may be found in two recent books.
68,69
Typically, a catalyst support is
chosen and the active metal component is added as a solution. Removal of
the solvent by drying leads to crystals of the metal precursor distributed
through the pore structure of the support. These precursor crystals are
converted to metal or metal oxide particles usually by heating under
hydrogen or air. The usual goal is to distribute the metal as widely as pos-
sible, achieving very small average metal particle sizes so that the greatest
possible portion of metal atoms are in the surface of the particles, available
for reaction. A number of variables can aect the metal dispersion, including
but not limited to the precursor, solvent, support, and drying method.
Catalyst supports may be obtained from suppliers or prepared using
various techniques. Many mixed oxide supports are prepared by co-pre-
cipitation or a sol-gel approach. Both approaches begin with solutions of
the desired metals. In co-precipitation a base or other precipitating agent is
added or evolved in solution to cause precipitation of the metal hydroxides
or other insoluble forms, such as carbonates. After recovery by ltration
and washing, the solids are calcined to convert to the desired oxides. Sup-
ports such as Al
2
O
3
and SiO
2
are easily obtained from major suppliers and
are less often prepared by investigators.
Most often catalysts are tested in packed beds of small particles, but
ultimately for mobile applications they must be prepared in some structured
form. A washcoat on planar surfaces, honeycomb-type monoliths, or other
support is usually required to provide low pressure drop and prevent
catalyst attrition.
Catalysis, 2010, 22, 5693 | 61
There are a large number of catalyst characterization techniques avail-
able.
7072
Among the most important physical characteristics of reforming
catalysts are the total surface area and the metal dispersion. High specic
surface areas provide space to widely distribute metal particles, and high
metal dispersions yield ecient use of the active component, particularly
important when using noble metals. Often dispersions as high as 2550%
may be obtained when using noble metals.
7375
Nickel-based catalysts are
most often reported to have lower dispersions.
74,101,126,127
Some investi-
gators, however, have reported obtaining high dispersions when working
with nickel.
76
Catalyst surface areas are usually measured by N
2
physisorption at
cryogenic temperatures following the BET method. Metal particle sizes are
often estimated by titrating the metal with a chemisorbing species such as
H
2
or CO, which adsorb selectively on the metal. Metal particle sizes may
also be estimated using SEM or XRD, provided that the particles are large
enough to yield suciently well dened peaks.
Operation under reforming conditions often leads to decreases in the
catalyst surface area.
73,7779,138,141
Surface area losses can be caused by high
operating temperatures or phase transitions in unstable support materials.
Blocking of pores by coke can also lead to lower measured surface areas if
the carbonaceous species are not removed prior to characterization.
The metal dispersion often decreases during reforming.
73,141
High tem-
peratures tend to cause sintering of the metal particles, leading to lowered
dispersions. Components of the feed can also lead to reduction in available
metal surface area; for example operation with S-containing feeds may lead
to lower measured metal dispersions. It is important to note that surface
bound species may block chemisorption sites without changing the actual
metal particle sizes.
4. Fuel reforming methods
In the next section, three methods for fuel processing are reviewed, namely
steam reforming (SR), catalytic partial oxidation (CPOX), and autothermal
reforming (ATR).
4.1 Steam reforming
Steam reforming dates back to the late 1800s and early 1900s where Mond
and Langer pioneered the use of nickel or cobalt on pumice as catalysts,
80
and Mittasch and Schneider demonstrated methane steam reforming over
magnesia supported nickel.
81
Today, steam reforming is practiced on a large
industrial scale for generating hydrogen-rich syngas from natural gas.
Typical steam reforming catalysts contain anywhere from 430 wt%
nickel supported on refractory oxides. More expensive cobalt and noble
metal catalyst have also been used. An extensive review of catalytic steam
reforming was written by Rostrup-Nielsen.
82
Steam reforming is typically
conducted at operating temperatures of 950 to 1200 K under 1012500 kPa
of pressure and steam to carbon ratios of 2/1 to 3/1. Excess steam is
benecial, as it drives the reaction to completion, and it also decreases the
deposition of carbonaceous species, coke, on the catalyst surface. The
62 | Catalysis, 2010, 22, 5693
endothermic nature of the steam reforming reaction requires high operation
temperatures to achieve good conversion. Since steam reforming reactors
require indirect heating, the process does not lend itself well to applications
where rapid startup and response to transients is necessary. Steam re-
forming of hydrocarbons involves a number of consecutive and parallel
reactions.
83
The most important reactions can be described by the following
overall equations:
C
n
H
m
nH
2
O !nCOn 1=2mH
2
1
C
n
H
m
2nH
2
O !nCO
2
2n 1=2mH
2
2
The latter overall equation includes the formation of CO
2
, which is
formed in the exothermic water gas shift reaction:
COH
2
O ,CO
2
H
2
3
In addition to water gas shift, CO and hydrogen can also undergo
methanation:
CO3H
2
,CH
4
H
2
O 4
Furthermore, carbon deposition on the catalyst can occur by the fol-
lowing reactions:
2CO ,C CO
2
5
C
n
H
m
,nC m=2H
2
6
Carbon deposition via reactions (5) and (6) and dehydrogenation of
larger hydrocarbons would be detrimental to the maintenance of catalyst
activity, but these reactions can in principle be avoided by feeding water in
excess to operate under high steam/carbon ratios. There have been many
studies aimed at minimizing the deposition of carbon during steam re-
forming.
8489
The need for high steam/carbon ratios makes on-board steam
reforming impractical, because of the limited supply of water on board of a
vehicle.
While many contributions to the steam reforming literature focus on
steam reforming of methane or natural gas, there is some literature dealing
with the steam reforming of heavier hydrocarbons. For example, Gorte and
coworkers have investigated steam reforming of benzene, toluene, cyclo-
hexane and n-octane, molecules that are relevant as surrogates for gasoline
reforming.
90
This study, conducted on ceria-supported Pd catalysts, dem-
onstrated that parans are more amenable to steam reforming than aro-
matic compounds. Benzene in particular had a much higher activation
barrier than paranic molecules. An extensive review of steam reforming of
aromatic compounds over Al
2
O
3
and SiO
2
supported group VIII metals,
published by Duprez, delineated trends that can provide guidance for fuel
processing of kerosene-based liquid fuels.
91
As a normalized measure of
catalytic activity, Duprez compared the turnover frequencies for benzene,
alkylbenzenes, alkylnaphthalenes, and heteroatom-containing aromatics.
Rh proved to be four to ve times more active than Pt or Ni for overall
Catalysis, 2010, 22, 5693 | 63
steam reforming, encompassing the summation of dealkylation, de-
hydrogenation, and total gasication reactions. For fuel processing aimed
at generating hydrogen-rich gas for fuel cells, total gasication is the most
important reaction. In terms of total gasication activity, Rh proved to be
the most active catalyst, closely followed by Ni. Pt, however, was less active
by an order of magnitude. The activity of Rh appeared to be strongly af-
fected by the nature of the support, while Pt and Ni seemed to be less
sensitive. Rh/Al
2
O
3
had much higher activity than Rh/SiO
2
.
There has been some work on Ru-based steam reforming catalysts. For
example, Suzuki et al. demonstrated that hydrodesulfurized kerosene could
be reformed over a Ru/CeO
2
Al
2
O
3
catalyst at 1073 K and a steam to
carbon ratio of 3.5, and 100% conversion of hydrodesulfurized kerosene
with high H
2
yield could be maintained for 8000 h on stream.
92
However,
under their reaction conditions, signicant amounts of methane, approxi-
mately 5%, were formed. Hu et al. used a proprietary Pd/ZnO catalyst for
steam reforming of iso-octane, synthetic diesel, desulfurized JP-8, and JP-8.
9
However, it turned out that not only the unmodied sulfur containing JP-8
fuel, but also desulfurized JP-8 deactivated the catalyst within a few hours
on stream.
In summary, it can be stated that steam reforming of hydrocarbons
typical for kerosene-type fuels is possible under relatively high steam/car-
bon ratios and at high temperatures as long as catalyst poisons, especially
sulfur, are removed. In general, aromatic hydrocarbons are more dicult to
reform than parans. It needs to be noted that steam reforming, due to its
slow dynamic response and large water supply requirements, is not a very
attractive option for on-board fuel processing systems.
4.2 Catalytic partial oxidation (CPOX)
Partial oxidation of hydrocarbons in presence of substoichiometric amounts
of oxygen is an ecient method for generating CO and H
2
.
93
Partial oxi-
dation of hydrocarbons is a highly exothermic process and raises the un-
converted reactants and products to very high temperatures. The
noncatalytic, homogeneous partial oxidation occurs at temperatures of
about 16001700 K, but in presence of suitable catalysts, the temperature
can be signicantly lowered to about 1150 K. The incomplete combustion of
hydrocarbons leading to formation of CO and H
2
is attractive for on-board
reforming because it does not require water to reform the fuel, and the
reaction has rapid light-o, providing fast start-up and good transient re-
sponse. The overall reaction is depicted below:
C
n
H
m
1=2nO
2
1:88nN
2
!nCO1=2mH
2
1:88nN
2
7
CPOX reactions are highly exothermic with fast kinetics, and may
become mass transfer limited. Nevertheless, the high reaction rates and the
concomitant rapid release of heat facilitate rapid start-up of the fuel pro-
cessor, an important issue for on-board applications. A major concern is the
susceptibility of catalysts to coking, as the feed to the reactor does not
64 | Catalysis, 2010, 22, 5693
contain any steam, which is known to inhibit coke formation. The absence
of steam in the feed leads to lower H
2
yield compared to steam reforming. It
is very important to carefully control the oxygen to carbon ratio (O/C), as
even small variations in the O/C ratio can lead to signicant changes in
catalyst bed temperature, product yields, and coking. The sensitivity to O/C
ratios and the highly exothermic nature of the process pose a major chal-
lenge for controlling CPOX reactors, and there has been major emphasis on
developing coke resistant CPOX catalysts.
94
There is an extensive body of literature dealing with partial oxidation of
methane, but there have also been many studies regarding CPOX of liquid
hydrocarbons and transportation fuels.
95
Early developments of POX re-
actors focused on the use of methanol, which thanks to its lower heat of
reaction permits a relatively simple reactor design.
96
An example of this is
the HotSpot
TM
reactor for methanol fuel processing developed by Johnson
Matthey.
97
POX technology for gasoline or diesel reforming is very chal-
lenging, mainly in terms of temperature control.
On the fundamental research side, the Schmidt group at the University of
Minnesota has investigated the partial oxidation of C
1
C
16
hydrocarbons
and low sulfur diesel into syngas with Rh catalysts on monoliths at high
space velocities under very short contact times.
50,98,99
They also explored
the contributions of homogeneous and heterogeneous reactions in the
catalytic partial oxidation of n-octane, iso-octane, and their mixtures on
Rh-coated a-alumina foams.
100
They found that the syngas product selec-
tivities were independent of the structure of the reacting fuel, but not the
olen product distribution. Iso-octane produced mostly propylene and iso-
butylene, while n-octane gave mostly ethylene and propylene.
Pengpanich et al. studied the partial oxidation of iso-octane over NiSn/
Ce
0.75
Zr
0.25
O
2
catalysts.
101
It was found that the addition of small amounts
of Sn (o0.5 wt%) lowered the activity for iso-octane POX only slightly,
while causing a signicant decrease in the extent of carbon deposition.
These results were interpreted in terms of Sn species partially covering the
Ni surface, thereby limiting the number of Ni atom surface ensembles
available for CC bond formation and coke build-up, while leaving the
active sites for partial oxidation more or less intact. Since the reaction en-
vironment in a CPOX reactor is rather complex, involving highly exo-
thermic combustion and partial combustion reactions, followed by
endothermic steam reforming using H
2
O generated in the combustion zone
and slightly exothermic water gas shift that becomes signicant in the cooler
regions of the reformer, it would be important to experimentally measure
products, intermediates, and temperatures as a function of time and pos-
ition in the reformer. The boundaries between the dierent reaction zones in
the reformer are most likely dynamic, and signicant temperature and
concentration gradients will be present due to variations in the steam/C and
O/C ratio. To probe these spatial variations in reforming reactors and to
gain insight into the complex interplay of reactions and intermediates,
analytical techniques such as Spatially Resolved Capillary Inlet Mass
Spectrometry (SpaciMS) have been used by Galen Fisher at Delphi
Research Labs in collaboration with a group at ORNL led by William
Partridge and Jae-Soon Choi.
102
This approach permits mapping of
Catalysis, 2010, 22, 5693 | 65
composition and temperature proles within the working reactor, in both
axial as well as radial directions. The SpaciMS method utilizes capillaries
inserted into monolith channels, and the gas collected at various positions in
the monolith is fed to a mass spectrometer for analysis. Temperatures are
measured by thermocouples. A schematic of the experimental setup is
shown in Fig. 1.
This method was originally pioneered for time-resolved measurements of
emission transients
103
and in situ measurement of reactions occurring in
lean-NO
x
trap catalysts.
104107
While diesel lean NO
x
traps operate at lower
temperatures in the range of 473773 K, reformers reach much higher
temperatures creating a challenge for the thermal and mechanical stability
of the capillary probes. At ORNL, temporal resolutions of 71 Hz have
been obtained for capillaries with lengths of 0.4 and 2.5 m, respectively. The
capillaries can be moved via a translation device within the monolith
channels, thereby probing gas compositions as function of position. To map
temperature proles, either thermocouples or phosphor-tipped non-con-
ductive optical bers can be used, with dierent types of phosphors oering
the ability to monitor dierent temperature regimes.
108
The SpaciMS analysis has been used to investigate the CPOX reaction of
light hydrocarbons, methane, and propane. Fig. 2 shows typical results
obtained for propane reforming under O/C of about 1 and at space velocity
of 30 000 h
1
.
109
In the oxidation zone, which is about 0.6 mm wide, syngas
is generated and both combustion and then reforming appear to occur, and
CO
2
, H
2
O, and temperature peaks are observed.
This zone is followed by a 0.6 mm wide C
3
H
8
depletion zone, where steam
and dry reforming occurs, and CH
4
generation is observed. Steam and dry
reforming dominate the downstream section of the monolith, and water gas
shift equilibrium is established. A similar approach was taken by the
Schmidt group
110
to obtain species and temperature proles for cata-
lytic partial oxidation of methane on Rh-coated a-Al
2
O
3
foams.
111,112
Their experimental set-up included a moveable thin quartz capillary for
sampling of gases via mass spectrometry and a thermocouple. Applying
such spatially resolved analysis methods to liquid fuel reforming would be
very useful.
Fig. 1 Experimental setup for spatially resolved analysis (SpaciMS) of compositions and
temperatures in a catalytic fuel reformer (reproduced with permission of Galen B. Fisher).
102
66 | Catalysis, 2010, 22, 5693
4.3 Autothermal reforming (ATR)
Autothermal reforming, a combination of steam reforming and partial
oxidation, may be more suitable for on-board reforming than steam re-
forming because of its better response to transient operation. In auto-
thermal reforming, a portion of the fuel is oxidized by air, and the heat
released in the process is used to drive the endothermic steam reforming
reactions in the downstream sections of the reactor. The overall heat duty of
the reactor can be adjusted by using varying O/C and steam/C ratios. The
introduction of superheated steam leads to the onset of steam reforming and
water gas shift reactions, causing the downstream section of the catalyst bed
to cool. The overall stoichiometry of the autothermal reforming process can
be described by equation (8):
C
n
H
m
O
y
xO
2
3:76N
2
2n 2x yH
2
O
nCO
2
2n 2x y m=2H
2
3:76xN
2
8
Since the autothermal reforming process uses both water and oxygen in
the feed stream and produces CO
2
and H
2
, it might intuitively appear to be
a poor choice for a fuel processor because of CO
2
dilution of the SOFC
anode feed stream. However, in reality the reaction does not proceed to
completion and there is a signicant concentration of CO present in the
reactor euent, according to the water gas shift equilibrium equation (3).
There is a large body of literature on autothermal reforming of methane
and light hydrocarbons.
113
However, for heavier liquid hydrocarbons, it has
proven dicult to establish reaction mechanisms and determine rate laws.
One of the major challenges is that the reaction is highly non-isothermal,
with fast partial oxidation reactions rapidly raising the temperature at the
catalyst bed entrance, followed by gradual decrease in temperature in the
Fig. 2 Reaction zones in propane reforming measured by SpaciMS (reproduced with per-
mission of Galen B. Fisher).
109
Catalysis, 2010, 22, 5693 | 67
downstream sections of the catalyst bed. In addition, there is the possibility
of homogeneous and heterogeneous thermal cracking reactions of hydro-
carbons. A schematic of these reaction zones in shown in Fig. 3. The
photograph of a nickel-containing monolith shows clearly the demarcation
between the partial oxidation and steam reforming zones.
The generation of hydrogen through autothermal reforming of iso-octane
with lowering of CO concentrations through water-gas shift and preferen-
tial oxidation was studied by several research groups, for example Moon
et al.
114
and Thompson and coworkers.
115
A comparison of the iso-octane
reforming performance of Ni/CeZrO
2
catalysts in packed beds versus
microreactors showed the importance of properly managing heat transfer
eects, an issue that is very critical in microchannel reactors.
116
A group at Argonne National Laboratories has worked on reforming
liquid hydrocarbons with a Pt catalyst supported on cerium oxide and
gadolinium oxide.
117
A temperature of 1123 K was required to achieve
satisfactory hydrogen yields and bring the methane concentration to low
levels. To describe the reaction kinetics relevant for autothermal reforming
of iso-octane, Pacheco et al.
118
developed a mathematical model using the
Aspen Plus process simulator, and using the experimental results obtained
by the Argonne team. Palm et al. reformed a mixture of C
13
C
19
hydro-
carbons in presence of precious metal based catalyst, and they achieved high
hydrogen and low methane yields.
119
To capture the characteristics of
naphthenes, aromatics, and sulfur in diesel fuel, which are thought to be
responsible for coking and catalyst poisoning, the eect of model com-
pounds 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene and 1-ben-
zothiophene on ATR conversion was also investigated. It was found that
decahydronaphthalene did not have a detrimental eect on conversion, but
1,2,3,4-tetrahydronaphthalene gave a decrease in conversion. It was hy-
pothesized that the aromatic character of the 1,2,3,4-tetrahydronaphthalene
made it more dicult to reform, thus lowering the conversion. The addition
of 1-benzothiophene, at 30 ppm sulfur, sharply decreased the conversion
and also altered the temperature prole of the reactor. The changes in
temperature prole suggest that the sulfur poisons primarily the endo-
thermic steam reforming sites of the catalyst.
Fig. 4 shows a schematic autothermal reforming reaction network for
dodecane over ceria-zirconia supported Ni catalysts, taking into account
homogeneous and heterogeneous reaction pathways.
120
These proposed
routes do not explicitly show the contributions of water gas shift, but the
contribution of water gas shift is implied by the product distribution. The
primary route to syngas is CPOX of dodecane, with steam reforming acting
Fig. 3 Reaction zones in autothermal reforming reactor.
68 | Catalysis, 2010, 22, 5693
primarily on conversion of C
1
C
4
hydrocarbons produced in various
homogeneous and heterogeneous cracking reactions.
A recent study reported the use of perovskite oxides containing rare earth
elements for autothermal reforming of isooctane in a xed bed micro-
reactor.
121
It turned out that the binary oxides LaNiO
3
and LaCoO
3
were
active and gave high yields of H
2
, but suered from structural stability
problems, as the oxides decomposed under the reducing conditions of the
reformer. Other binary oxides such as LaCrO
3
, LaFeO
3
, and LaMnO
3
were
stable but less active.
Similar to steam reforming, aromatic compounds are more dicult to
process by ATR than ring and chain compounds. The eect of fuel additives
on catalyst activity and durability remain largely unknown. The review of
the literature on the processing of JP-8 into syngas suggests that sulfur
poisoning is the dominant challenge with coking being the second most
important concern.
5. Deactivation of reforming catalysts
5.1 Carbon deposition
A major technical obstacle to reforming of liquid hydrocarbon fuels is
carbon deposition and coking on the catalyst. During reforming, hydro-
carbons are broken down on catalytic surfaces, their constituent fragments
react with steam or oxygen, and CO, CO
2
, and H
2
are released from the
catalyst surface. Accumulation of carbon can lead to catalyst deactivation,
reactor fouling and pressure drop problems, and in some cases even
structural failure of catalysts. However, the detailed mechanisms for carbon
Fig. 4 Schematic of autothermal reforming reaction network for dodecane, taking into ac-
count homogeneous and heterogeneous reaction pathways (adapted from
120
).
Catalysis, 2010, 22, 5693 | 69
deposition and coke formation remain open to debate, and a clear under-
standing does not currently exist how the chemical structure of fuels in-
uences coking behavior. One school of thought is that coke forms by the
polymerization of large hydrocarbons into arrays of polycyclics. It is be-
lieved that aromatics are detrimental to reforming because the compounds
act as precursors for the formation of the polycyclic networks. On nickel
catalysts, an additional route for carbon deposition needs to be considered,
namely the growth of carbon laments.
In general, nickel-based catalysts are more susceptible to carbon accu-
mulation than are those based on precious metals. In his general review,
Sehested has summarized the development of dierent types of carbon
structures formed from higher hydrocarbons during steam reforming on
nickel catalysts.
122
Of signicant importance is the mechanism of carbon
lament formation, which can lead to macroscopic catalyst failure beyond
simple deactivation. It has been proposed that the formation of lamentous
carbon involves the diusion of carbon atoms formed via decomposition of
adsorbed hydrocarbons through Ni particles, forming a nickel carbide
intermediate phase.
123
One approach to increase the coking resistance of Ni catalysts is the use
of supports with mobile oxygen, for example mixed oxides of ceria and
zirconia, but even with this support, some carbon deposition mainly in form
of laments was observed.
124,125
Cordierite monoliths loaded with Ni used in the reforming of dodecane
showed signicant carbon deposition following reaction.
126
At high nickel
loadings (W7 wt%) the carbon deposition was so severe that the monoliths
disintegrated during the reaction. TPO of the recovered monoliths showed
that carbon deposited during POX, SR, and ATR had dierent oxidation
temperatures, indicating dierences in composition or morphology. When
Ni/Ce
0.75
Zr
0.25
O
2
was loaded on the monoliths, carbon deposition was
greatly reduced.
Carbon deposition was also observed during ATR of isooctane over
Ni/Ce
0.75
Zr
0.25
O
2
catalysts of varying nickel loadings.
127
Here the amount
of carbon was found to increase with increasing nickel loading, which
was associated with increasing average nickel particle size. SEM analysis of
the spent catalysts showed carbon laments of various sizes, as well as what
appeared to be amorphous carbon coating the particles.
Chen et al. carried out a detailed spatially-resolved analysis of carbon
deposition in monoliths coated with Ni/ceria-zirconia or just Ni alone under
ATR, CPOX, and SR conditions.
128
They mapped the amount and types of
carbon deposited in dierent sections of the monoliths with a combination
of scanning electron microscopy, energy-dispersive X-ray spectroscopy
(EDS), and temperature-programmed oxidation. They found signicant
dierences in the amounts and location of carbon, depending on the type of
reforming reaction, reecting axial variations in temperature and oxygen
concentration. Fig. 5 shows a typical SEM image of lamentous carbon
deposited in the downstream sections of a monolith catalyst.
An alternative approach to impart better resistance to carbon deposition
and coking is to modify the nickel surface. Sn has been successfully used to
decrease carbon deposition in several catalytic processes, for example
70 | Catalysis, 2010, 22, 5693
aromatization and dehydrogenation of parans. Motivated by the bene-
cial eect of Sn in these reactions, the eect of Sn was explored for Ni-
catalyzed steam reforming, partial oxidation,
129,130
and dry reforming.
131
The benecial eect of adding small amounts of tin to nickel was also ob-
served on reducible oxides, such as ceria-zirconia.
124,125
Nikolla et al. showed by combined DFT and experimental studies that
the carbon surface chemistry of nickel catalysts can be very eectively
controlled by alloying the nickel surface with tin.
132
Long-term activity
maintenance of a nickel catalyst is governed by the prevention of carbon-
carbon bond formation leading to coke while selectively facilitating the
formation of CO bonds. On Ni surfaces, there is no dierentiation in the
activation barriers for CC versus CO bond formation, while introducing
Sn into the Ni surface leads to a situation where the overall rate of carbon
oxidation is much greater than the rate of CC bond formation. It is for-
tunate that in the limit of small Sn concentrations, the formation of Sn/Ni
surface alloys is favored over Sn/Ni bulk alloys or pure Sn and Ni phases.
133
The electronic structures of monometallic Ni and Sn/Ni surface alloy
catalysts supported on yttria stabilized zirconia, a ceramic used in solid
oxide fuel cell anodes were measured using a variety of experimental probes,
and the results supported theoretical models indicating a relationship be-
tween catalytic activity and the position of the center of the electronic d
band.
134
Contrary to the common belief that the change in the electronic
structure of metals in an alloy is caused by charge transfer among the alloy
components, this work showed that the interaction of Sn and Ni leads to
shared electronic states. Consequently, the lling of the Ni d band remains
unchanged (Fig. 6). This has important consequences for the catalytic
performance of Sn/Ni alloy catalysts. The Sn-induced decrease of the
average energy of d electrons decreases the binding strength of carbon
species. This lowers the surface concentration of carbon-containing reaction
Fig. 5 Scanning electron micrograph of carbon laments formed in pores of the downstream
section of a Ni/CZO monolith catalyst after steam reforming of dodecane.
128
Catalysis, 2010, 22, 5693 | 71
intermediates during reforming. The result is a signicant decrease in the
driving force for coke deposition.
While more resistant to carbon deposition than nickel, precious metal
catalysts do exhibit varying levels of carbon accumulation during re-
forming. Shekhawat et al. investigated POX of tetradecane over Pt/Al
2
O
3
,
Pt/ZrCeO
2
, and Pd/ZrCeO
2
catalysts and found 0.85, 0.69, and 0.21 gC/g
catalyst after reaction, respectively.
48
Carbon deposition levels appeared
to be correlated with the presence of unsaturated intermediates. Addition of
5% 1-methylnaphthalene to the feed increased carbon deposition for
all the catalysts. Although signicant carbon was found in the spent cata-
lysts, no signicant impact on performance was reported. As with several
nickel-based investigations, TPO of the spent catalysts revealed very dif-
ferent oxidation temperatures for the carbon species deposited on the
catalyst.
Dreyer et al. observed carbon deposition during POX and ATR of decane
and hexadecane.
135
Although the carbon was not strictly quantied, carbon
burn-o temperature proles indicated there was more carbon deposited
under pure POX conditions than ATR. No eect on the catalytic per-
formance due to carbon was noted.
The presence of heavy polyaromatic compounds in Diesel creates a ten-
dency for deposition of large amounts of carbon. This can become a serious
issue especially under autothermal conditions where the downstream sec-
tions of the catalyst bed may experience a decrease in temperature due to
endothermic steam reforming reactions. To prevent carbon formation, the
reactor temperature must be kept at temperatures above 1070 K. One
strategy to decrease carbon formation has been to introduce additives such
as tin, to use rare earth oxide supports,
136
and to avoid conditions that
would lead to the formation of carbides.
88
After reviewing carbon deposition data across many investigations it may
be concluded that carbon deposition remains a concern for both nickel- and
precious-metal based catalysts. It is important to note, however, that the
mere presence of carbon on a spent catalyst is not necessarily indicative of
carbon poisoning. Surface carbon is a necessary intermediate of reforming
and may be expected to be present on all reforming catalysts; it is the
quantity and form of carbon that lead to performance issues.
Fig. 6 Illustration of the interactions between an adsorbate and the d bands of Ni on a
monometallic Ni surface and on a Sn/Ni surface alloy.
134
72 | Catalysis, 2010, 22, 5693
5.2 Deactivation by sulfur
There are various strategies that can be pursued to prevent deactivation of
catalysts during reforming of sulfur-containing fuels. The rst strategy aims
at development of catalysts that can tolerate signicant levels of sulfur
without experiencing long-term deterioration of performance.
35,137
This is
challenging, as sulfur strongly binds to the active sites on the catalyst and
prevents access by other reactants. In addition to simple site blocking, sulfur
atoms can have detrimental electronic eects on active metals, which can
eectively poison surrounding sites. Mitigation of sulfur poisoning requires
operation of the catalysts at high temperatures, and may still require the
removal of sulfur compounds from the fuel reformer euent to protect the
SOFC anode catalyst from sulfur poisoning. Signicant research eorts,
however, have been directed towards developing hydrocarbon-reforming
catalysts capable of tolerating moderate to high concentrations of sulfur.
Several factors in catalyst formulation and operation can be used to en-
hance sulfur tolerance. The most straightforward is the use of a noble metal
such as Pt, Pd, or Rh as the active component. Noble metals exhibit lower
susceptibility to poisoning by sulfur than other transition metals. Within the
noble metals, some appear better than others. Azads group at the Uni-
versity of Toledo has reported that 1 wt% Rh or Rh-Pd supported on
Gd
0.1
Ce
0.9
O
1.9
or Zr
0.25
Ce
0.75
O
2
was stable for steam reforming toluene in
presence of 50 ppm thiophene.
138
Catalysts of the same formulation where
Pd was substituted for Rh showed greater deactivation.
139
Schmidts group
has reported partial oxidation of methane with 28 ppm CH
3
SH (0.5 wt%
Rh/CeO
2
/Al
2
O
3
)
140
and JP-8 (5 wt% Rh/Al
2
O
3
).
135
Catalytic performance
was lowered but stable after addition of sulfur to the feed, with a decrease in
hydrogen yield observed.
Shekhawat et al. directly compared Rh/ZrO
2
CeO
2
, Pt/ZrO
2
CeO
2
, and
Pt/Al
2
O
3
.
48
The Rh/ ZrO
2
CeO
2
catalyst was the only one to show stable
operation under 1000 ppmw S content in the fuel. They also demonstrated
that the Rh catalyst can substantially recover activity when sulfur is re-
moved from the feed. While Rh appears to be superior, Pt has also been
shown to act as a stable reforming component under some conditions. Lu
et al. have reported that 1.5 wt% Pt/ Gd
0.1
Ce
0.9
O
1.9
was stable for steam
reforming of isooctane with a sulfur level of 300 ppmw.
75
Some deactivation
was observed at sulfur loadings of 500 ppmw, but hydrocarbon conversion
was maintained above 90% for 100 hours.
The use of reducible metal oxide supports has been shown to be superior
to conventional supports such as Al
2
O
3
. Cheekatamarla and Lane have
compared various bimetallic catalysts supported on both Al
2
O
3
and CeO
2
for reforming of JP-8.
141
They found that the catalyst activity was higher for
all metal combinations when using CeO
2
as a support. Mixed oxides in-
cluding TiO
2
and CeO
2
are a central claim in BASFs patent application for
a sulfur tolerant natural gas steam reforming catalyst.
142
A group at NETL, in conjunction with Spivey, has studied pyrochlores as
catalysts for liquid fuel processing. Catalytically active metals may be sub-
stituted into the pyrochlore structure, which has excellent thermal properties
of interest for high temperature catalytic reactions. La
1.5
Sr
0.5
Ru
0.05
Zr
1.95
O
7y
Catalysis, 2010, 22, 5693 | 73
(LSRuZ) was compared to Ru/gAl
2
O
3
for the catalytic partial oxidation of
n-tetradecane and n-tetradecane/1-methylnaphthalene/dibenzothiophene
mixtures (50 ppmw).
64
Both catalysts showed reduction features assignable to
Ru during temperature programmed reduction, although the reduction in the
pyrochlore took place at higher temperature. The Ru dispersion was 2.3% for
the pyrochlore and 27% for the Ru/gAl
2
O
3
catalyst. The pryochlore catalyst
was signicantly more resistant to deactivation during S-feeding, maintaing
H
2
and CO yields in excess of 70% with only small increases in CO
2
and
CH
4
production. The Ru/gAl
2
O
3
catalyst showed catastrophic loss of H
2
and CO yields with larger increases in CO
2
and CH
4
production. The sup-
ported Ru catalyst also gave a much higher olen yield during S-feeding than
the pyrochlore. Upon removal of S from the feed, neither catalyst completely
recovered its prior activity, but the pyrchlore recovered to a much higher
H
2
and CO yield than the alumina-supported Ru catalyst. The alumina-
supported Ru catalyst also showed much higher C deposition.
Rh-substituted La-Zr pyrochlores also showed better S tolerance than
comparable supported Rh catalyst.
65
During catalytic partial oxidation of
n-tetradecane with addition of 1000 ppmw dibenzothiophene, the pyro-
chlore (La
1.50
Sr
0.50
Rh
0.10
Zr
1.90
O
6.70
) showed a drop in H
2
and CO yield
from 90% to 7075% on S addition. The original H
2
and CO yields were
almost totally recovered 200 minutes after removing S from the feed.
In contrast, the supported Rh catalyst showed a drop in H
2
and CO from
7580% to less than 40%, with continuing deactivation. Neither H
2
nor
CO yield recovered to above 50% upon removing S from the feed stream.
Olen production during S-feeding was lower on the pyrochlore than
on the supported Rh catalyst. The level of activity recovery was nega-
tively correlated to the amount of C found deposited on the catalyst
following reaction. The amounts of C deposited on the catalysts were higher
following reaction with S than during partial oxidation with n-tetradecane
only.
66
Hexaaluminates are oxide materials with a spinel structure and refractory
properties. The cations may be chosen from among the transition metals.
Some oxygen sites within the framework are more accessible than others,
and this has led to their study for oxidation reactions. Hexaaluminates of
the formula ANi
0.4
Al
11.6
O
19 d
(A=La, Sr, Ba) have been studied for the
catalytic partial oxidation of n-tetradecane.
67
The Ba and Sr substituted
catalysts showed a b-alumina structure, while the La substituted material
exhibited a magnetoplumbite structure. Catalyst surface areas ranged from
14 to 22 m
2
/g, and nickel dispersions (as measured by H
2
chemisorption)
were quite low, as expected since Ni is incorporated in the bulk structure.
Partial oxidation of n-tetradecane was tested at an O/C ratio of 1.2, 850 1C,
and a GHSV of 50 Lg
1
h
1
. The La-substitued catalyst showed a peak in
H
2
and CO production, followed by slight decreases then steady perform-
ance. This was attributed to carbon deposition deactivating the most active
nickel sites. Both the Ba and Sr-substituted catalysts showed no loss in H
2
and CO production. All catalysts produced some CO
2
and some light
hydrocarbons. The tolerance of the catalysts to S was tested by introduction
of 50 ppmw dibenzothiophene to the fuel stream during reaction. The
La-substituted catalyst showed greater loss of H
2
and CO production than
74 | Catalysis, 2010, 22, 5693
the Sr-substituted catalyst, although it did recover some activity after
dibenzothiophene was removed whereas the Sr-substituted catalyst did not.
Additives such as promoters or sacricial components have also been
used to improve sulfur tolerance. Azad et al. examined the eect of adding
Y
2
O
3
and CuO to Rh-based steam reforming catalysts. Y
2
O
3
had a bene-
cial eect on performance, apparently by increasing or stabilizing the Rh
dispersion.
139
CuO was added as a sacricial component to react with
sulfur, thereby removing sulfur from the active metal sites.
138
While this
improved the hydrogen yield obtained during reforming with sulfur, in the
absence of sulfur more coking was observed as compared to the catalyst
without CuO. Similarly, BASFs methane steam reforming catalyst also
includes a transition metal component to capture sulfur during reforming,
which is released during a subsequent regeneration step.
143
Dinka has re-
ported that addition of 2 wt%K to a La
0.6
Ce
0.4
Fe
0.8
Ni
0.2
O
3
perovskite
catalyst increased sulfur tolerance, allowing an increase from 50 to 225 ppm
S in autothermal reforming of JP-8 with no change in performance.
144
The
eect of 2 wt%K addition was similar to the eect of 1 wt% Ru. Mawdsley
and Krause reported that introducing Cr as stabilizing element into LaNiO
3
improved the sulfur tolerance.
121
Modication of Ni/Sr/ZrO
2
catalysts with
Re or La was also found to improve the sulfur tolerance of the catalyst
during autothermal reforming of hydrocarbon fuels.
145
Molybdenum car-
bide catalysts have also shown some tolerance to sulfur poisoning in a study
of steam reforming of tri-methylpentane.
146
Many sulfur tolerant catalysts have been studied at modest space vel-
ocities, allowing for greater contact time with the catalyst region and op-
portunity for reaction. Reactions can be carried to high conversion in very
short contact times when no sulfur is present in the feed. Schmidts group
has published extensively on successful CPOX using precious metal cata-
lysts of hydrocarbons from methane to tetradecane at contact times of a few
milliseconds.
98,147
Schwanks group at the University of Michigan has
demonstrated ATR of isooctane, dodecane, and isooctane at gas hourly
space velocities of 200 000 hr
1
.
148,149
Of the sulfur tolerant catalysts sur-
veyed here, the space velocities range from 8000 hr
1
to 62 000 hr
1
. These
lower space velocities allow catalysts with lower activities, a result of partial
sulfur poisoning, to achieve the required hydrocarbon conversion.
The organic sulfur compounds present in liquid fuels can react with
catalytic surface sites to form stable metal suldes, thus causing severe
deactivation. One possible solution is to remove sulfur compounds from
fuels via selective adsorption on adsorbents such as zeolites that can be
regenerated.
150,151
Yang and co-workers developed a p-complexation
method for selective sorption of sulfur compounds by copper and palladium
halide sorbents and CuY zeolites.
152156
They also investigated the use of
carbon-based sorbents.
157
For on-board applications, the need for re-
generation of the sorbents introduces an additional degree of complexity,
and in some cases there may also be some issues with eective removal of
sterically hindered sulfur compounds in presence of aromatic hydrocarbons.
Given the diculties in fuel processing of heavy hydrocarbon fuels, a
third strategy may be pursued, namely catalytic hydrodesulfurization of the
fuel prior to sending it into the reformer. The heavier organosulfur
Catalysis, 2010, 22, 5693 | 75
compounds in the fuel can be converted into H
2
S in presence of a suitable
catalyst, and the H
2
S is then absorbed in a sulfur absorption bed, for ex-
ample zinc oxide. This method is widely used on an industrial scale,
158
but
since hydrodesulfurization reactors require high pressure H
2
, it may not be
practical for on-board deployment. A group from PNNL has recently de-
scribed a very interesting alternative.
159
Their process uses an integrated
steam reformer to generate hydrogen for hydrodesulfurization and a
microchannel distillation unit upstream of the hydrodesulfurizer. This ap-
proach makes it possible to process a lighter feed fraction instead of the
unmodied JP-8 fuel. The light fraction from the microchannel distillation
unit contains smaller concentrations of refractory sulfur compounds,
thereby facilitating the hydrodesulfurization. The U.S. Navy has also pur-
sued a fuel processing system capable of handling JP-8 type fuels that
utilizes a sulfur-tolerant autothermal reformer (ATR).
160
6. On-board reforming of fuels for SOFC APU applications
Conceptually, three dierent strategies can be used in fuel reforming for
SOFC APUs. The rst strategy is external reforming, where the catalytic
conversion of liquid fuels into syngas takes place in a separate catalytic
reactor. The H
2
-rich syngas product is then fed to the anode compartments
of the fuel cell stack. From a reaction engineering perspective, external re-
forming is the simplest method for reforming of complex liquid transpor-
tation fuels such as diesel and gasoline, but suers from low overall
eciency and high system cost.
The second strategy is indirect internal reforming. This method is very
similar to external reforming, but in this case the catalytic reformer is de-
signed in such a way that it is in direct thermal contact with the anode
compartment of the solid oxide fuel cell. This method was initially applied
to molten carbonate fuel cells.
161
Having the reforming reactor in thermal
contact with the high-temperature fuel cell facilitates better thermal inte-
gration of the heat released during the electrochemical reactions on the
anode with the heat requirements for vaporizing steam and fuel, and can be
utilized to provide additional heat for endothermic steam reforming re-
actions in the fuel reformer. The practical implementation of this concept
has to deal with the problem of thermal mismatch between the relatively fast
endothermic steam reforming reactions and the much slower exothermic
electrochemical reactions in the fuel cell. This thermal mismatch can lead to
cold spots in sections of the reformer, and in a worst case scenario could
cause fractures of the system.
162
The third possible strategy is direct internal reforming, which is perhaps
the ideal heat integration strategy. Due to high SOFC operating tempera-
tures, internal reforming of methane or light hydrocarbons such as propane
is possible. Internal reforming is attractive because of the SOFCs ability to
utilize CO along with H
2
. Carrying the reforming reaction out directly in the
anode compartment of the fuel cell provides the most ecient way to
transfer heat from the electrochemical reactions to the catalytic sites where
the reforming reactions take place. The direct reforming of liquid fuels is
very challenging, but there have been some reports of successful direct
76 | Catalysis, 2010, 22, 5693
reforming of iso-octane on carbon-resistant Sn/Ni alloy anodes that were
designed with guidance from DFT calculations.
163
Barnett and Zhan car-
ried out internal partial oxidation of iso-octane on SOFC anodes, but had
to place an additional Ru-CeO
2
layer between the fuel stream and the anode
to obtain stable operation without anode coking.
164
6.1 Gasoline
In view of the extensive infrastructure for gasoline distribution, there have
been substantial eorts towards the development of gasoline reformers in
industry, involving companies such as Hydrogen Burner Technology and
Arthur D. Little,
165
which later partnered with the Italian company De
Nora to start Nuvera. A. D. Little developed a system that included a POX
reactor as primary fuel processor and water gas shift and preferential partial
oxidation (PROX) reactors to generate PEM-fuel cell grade pure H
2
.
Gasoline fuel processor development also was carried out at ExxonMobil in
collaboration with General Motors. Shell worked on the development of
gasoline CPOX reactors for Daimler Chrysler in partnership with Ballard
and UTC.
Delphi Corporation has been one of the leading developers of on-board
SOFC APU technology with integrated fuel processor and SOFC stack,
166
in partnership with BMW, Battelle, Global Thermal Electric of Canada,
TotalFinaElf, and Los Alamos National Laboratory. In 2001, a proof
of concept gasoline powered SOFC APU was demonstrated on a BMW
7-series sedan.
167
The fuel processor for this system involved a catalytic
partial oxidation (CPOX) reformer containing alumina or zirconia based
catalyst formulations.
168
This fuel processor shown in Fig. 7 does not include provisions for re-
moval of sulfur, requiring that the catalysts must have adequate sulfur
tolerance. As strategy for decreasing the size of the reformer, planar
Fig. 7 Delphi Corporations gasoline catalytic partial oxidation reformer.
168
Catalysis, 2010, 22, 5693 | 77
geometries have been considered that facilitate heat integration with an
energy recovery unit.
On a more fundamental basis, researchers at Argonne National La-
boratory investigated the eect of the major constituents of gasoline, fuel
additives, and impurities on fuel processor performance.
169
They found that
at high space velocities and/or low reforming temperatures antioxidant
additives in gasoline decreased the hydrogen yield in the reformate.
6.2 Diesel
Diesel fuel has a relatively high hydrogen content, making it an attractive
fuel for on-board reforming.
170
H
2
-rich reformate gas can be generated
from diesel fuel not only through reforming, but also though direct
hydrocarbon decomposition. A group at Argonne National Lab has utilized
simplied mixtures of fuel components to understand how factors such as
H
2
O:C and O
2
:C ratios, temperature, and fuel composition aect the re-
actions in diesel reforming.
171
They indentied intermediates in the oxi-
dation and coke-forming reactions.
While steam reforming provides in principle the highest H
2
yield, the
endothermic nature of the process and the need to supply large amounts of
steam makes this process unfavorable for on-board, transient operation.
The exothermic catalytic partial oxidation (CPOX) lends itself much better
to transient operation. Diesel CPOX reactors can be operated without
catalyst, and after start-up in air, the reactors operate at very high tem-
peratures in excess of 1500 K. By adding catalysts, the reactor temperature
can be signicantly lowered, making such systems attractive for on-board
vehicle applications. The major components of diesel fuel, n-decane and n-
hexadecane, can be converted to syngas with high selectivity.
172
CPOX,
thanks to its exothermic nature, requires only very short contact times in the
order of milliseconds.
173
However, catalytic diesel reforming is quite challenging due to the pro-
pensity of diesel to pyrolyze, and coke formation and sulfur deactivation of
the catalysts are major issues that need to be carefully managed. Due to the
large number of hydrocarbon components in the fuel, a multitude of re-
actions are involved, making it very dicult to unravel mechanistic de-
tails.
88,174
For diesel reformers, typical catalysts contain either precious
metals (Pt, Rh, Ru) or less expensive base metals (Ni) that are supported on
carefully engineered oxide supports. For example, Pt/ceria and bimetallic
Pt-Pd ceria catalysts
175,176
and Pt catalysts supported on Al
2
O
3
CeO
2
or
Al
2
O
3
La
2
O
3
177
have been used for autothermal reforming of synthetic
diesel. As Spivey has pointed out in a recent ACS meeting, the tendency of
reforming catalysts to deactivate by coke deposition and sulfur poisoning
calls for innovative approaches to novel catalytic materials and reactor
designs, guided by computational catalysis methods.
178
In a study of
autothermal diesel fuel reforming over Ru-doped lanthanum chromite and
aluminite catalysts, adequate fuel mixing prior to feeding diesel, steam and
air into the autothermal reformer was identied as a critical issue.
179
There has been recent patent activity regarding thermoneutral reforming
processes for conversion of fuels including light naphtha, heavy naphtha,
78 | Catalysis, 2010, 22, 5693
kerosene, or diesel in absence of any external heat source.
180
These patents
claim the use of multicomponent catalysts containing Ni, Ce
2
O
3
La
2
O
3
, Pt,
ZrO
2
, Pt, Rh, and Re for reforming of feedstocks containing o200 pm
sulfur without coke formation.
Alternate strategies to circumvent carbon formation have been employed.
Low and intermediate temperatures can favor the formation of C, as can
low local O/C ratios. Mundschau and coworkers have reported the use of a
membrane reactor comprising YSZ walls.
181
Fuel is fed inside the mem-
brane and air passes through the membrane walls to mix with the fuel above
the catalyst bed. The air passing through the walls increases the local O/C
ratio in the cool regions of the reactor, suppressing the driving force for C
formation. The catalyst employed inside the reactor is a La
0.5
Sr
0.5
CoO
3d
perovskite, operated at 1223 K to suppress carbon formation in the catalyst
region. The perovskites catalyzed both total and partial oxidation of com-
mercial diesel, depending on the O/C ratio employed.
6.3 Jet fuel
As already discussed above, the reforming of kerosene-based jet fuels such
as JP-8 is dicult due to the presence of heavy hydrocarbons in these fuels.
Among heavy hydrocarbons, parans and cycloalkanes are relatively easy
to convert while the aromatics are known to be the most dicult ones to
process. The challenges in reforming heavy aromatics stem both from their
lower reactivities as well as from their higher propensities to form coke
under typical reforming conditions.
Sung and Ibaretta developed a model for reforming of a kerosene sur-
rogate over a wide range of conditions with varying feed temperatures,
operating pressures, steam/carbon ratio and O/C ratio.
182
Based on calcu-
lations using nite gas-phase chemistry, the concluded that short residence
times and partial oxidation with minimal water addition gave the most ef-
cient reforming performance.
Gould et al. examined the performance of a nickel-ceria-zirconia catalyst
for autothermal reforming of n-dodecane, tetralin, and their mixture, as
representative compounds for alkanes and bicyclic compounds in jet fuel.
149
It was found that the mixture of tetralin and n-dodecane did not react as
expected for a linear combination of the two types of molecules. Instead, the
reforming behavior was dominated by reforming characteristics of pure
tetralin. This observation appeared to be counterintuitive, as one would
expect that the aromatic character of tetralin would make it more dicult to
reform. It is well documented that compared to alkanes, aromatic molecules
have higher activation energies for steam reforming.
183
The simple ex-
planation for the tetralin-dominated reforming behavior of the mixture was
that the tetralin-containing mixture led to higher temperature proles in the
reactor compared to n-dodecane, due to the higher adiabatic equilibrium
temperature obtained with tetralin.
As potential low-cost coking-resistant catalysts for reforming of JP-8 fuel
surrogate, Ce- and Ni-substituted LaFeO
3
perovskites have been used.
184
The improved coking resistance was attributed to improved oxygen ion
Catalysis, 2010, 22, 5693 | 79
mobility imparting higher activity for carbon oxidation on the catalyst
surface.
An alternative strategy for avoiding the coking problem is to remove the
heavy hydrocarbons, especially the heavy aromatics from the feedstocks
before reforming. In reneries, aromatics can easily be separated from
petroleum fractions through solvent extraction or adsorption. Clearly, such
strategies are not applicable for compact, on-board fuel processors. The
unit operations required for the regeneration of solvent or adsorbent would
introduce far too much complexity. Unfortunately, the boiling points of the
various hydrocarbon species in these types of fuels are too close to each
other for eective separation via distillation. Therefore, alternative ap-
proaches have been considered for selective removal of heavy polynuclear
aromatics prior to reforming. One such approach involves the catalytic
cracking of JP-8, followed by separation of light cracked gases from heavies
before reforming, thereby eliminating non-volatile aromatic species.
186
Catalytic cracking can convert heavier hydrocarbons to C
1
C
3
compounds.
Since cracking reactions are generally associated with carbon deposition
and catalyst deactivation, pre-reforming strategies relying on cracking
might require frequent catalyst regeneration. As an alternative, reactive
separation of heavy aromatics appears possible, taking advantage of the
dierences in the relative reactivities of various hydrocarbons. Prereforming
has been practiced widely in industry as a preliminary step to convert
distillate fuels for the production of synthesis gas.
185
Naphtha feed is pro-
cessed rst in a prereformer to produce an equilibrium mixture of methane,
hydrogen, CO and CO
2
that is then subsequently sent to the main reformer
where the conversion to synthesis gas takes place. In this approach, reactive
hydrocarbons would be converted into lighter components such as methane,
hydrogen and oxides of carbon, while keeping the less reactive heavy
aromatics intact. The product mixture will then be cooled down to a
temperature where the unconverted heavy aromatics condense as liquid.
The methane-rich gaseous stream would be fed into the reformer to
produce synthesis gas, while the condensed heavy aromatics would be
used as fuel to generate heat. To deal with non-volatile residues that
can constitute up to 1.5 vol% in jet fuels, and to decrease the danger of
coking due to heavy hydrocarbons, catalytic cracking of the fuel with
zeolite catalysts and manganese/alumina catalysts and subsequent
separation of the light cracked gas from the non-volatile aromatic species
has been investigated.
186
The Air Force Research Laboratory (AFRL) has developed a JP-8 fuel
processor capable of generating 3kWe of SOFC grade feed reformate.
187
Their fuel processor uses a combination of partial fuel vaporization and
catalytic cracking to pre-reform the fuel. Their strategy for JP-8 processing
is twofold. First, the fuel is partially vaporized so that the bulk of the sulfur
containing species remain in the liquid phase, which can be fed to a com-
bustor that heats a steam reformer. Second, the remaining organosulfur
compounds are converted into H
2
S by catalytic cracking, which can sub-
sequently be adsorbed on ZnO. Additionally, the cracking unit converts the
larger hydrocarbons, which have a propensity to coke, into smaller non-
coking species.
80 | Catalysis, 2010, 22, 5693
McDermott Technology Inc has developed a fuel processor for Navy ship
service capable of converting military logistic fuel (NATO F-76) into a H
2
rich gas.
188
In conjunction with Siemens Westinghouse and Phillips Pet-
roleum they developed a 250 kWe low-sulfur diesel powered SOFC.
189
Their
design incorporates an ATR with a sulfur removal unit operation down-
stream of the ATR to protect the SOFC. They have operated a pilot scale
processor at 1030 kWe on low sulfur diesel (7 ppm) for 110 hours with 99%
conversion.
A recent study of autothermal reforming of kerosene in a microreformer
system used Pt supported on Gd-doped CeO
2
, but this system was designed
for stationary, residential applications, rather than for on-board deploy-
ment.
190
The reformer was coupled with a downstream ZnO bed to remove
sulfur, to protect the SOFC.
7. Systems engineering aspects of on-board fuel processing
No discussion of on-board fuel reforming can be complete without ad-
dressing system and engineering considerations. Issues of reactant delivery,
heat integration, and others must be dealt with to achieve on-board re-
forming of liquid fuels. This balance of plant introduces parasitic losses on
the system, reducing the amount of power that can be eectively extracted
from the fuel. High operating pressures or long processing trains, which
introduce signicant pressure drops across the system, will lead to increased
energy costs for reactant delivery. Separate heat exchange steps will increase
the system weight and volume, adversely aecting power density of the full
system.
The primary driver for system-related considerations is the choice of re-
forming scheme. While SR oers high hydrogen yields without nitrogen
dilution, it requires a supply of water, a high-duty vaporization step, and
high rates of heat transfer into the reforming reactor from a separate heat
source. ATR also requires water, but the feed ratio to the fuel will be much
lower than SR. POX operation requires only air as a co-reactant for the
fuel, but may be prone to carbon deposition and higher operating tem-
peratures than SR and ATR. For mobile applications, POX or ATR are
likely the most practical reactions schemes.
The literature regarding design of reformers and systems integration is
relatively sparse. Studies of reforming trains for PEM fuel cells, which in-
clude water gas shift and preferential oxidation reactors, are available.
191
There has also been an appreciable research eort directed towards mem-
brane reactors, particularly for hydrogen separation using Pd-based mem-
branes, which can accommodate the PEMs requirement for high-purity
hydrogen.
192194
As SOFCs are able to utilize CO as well as hydrogen, the
membrane approach is unnecessary.
In contrast to large-scale stationary reformer operation,
195
on-board
systems have to deal with several additional major technical challenges,
including frequent transient operation during start-up and shutdown, op-
eration under high space velocities, and ability to function under harsh
thermal conditions and mechanical vibrations. Conventional packed-bed
reactor technology does not meet these constraints, motivating the move
Catalysis, 2010, 22, 5693 | 81
towards wash-coated monoliths containing either noble or base metals.
Such monolith designs have the advantage of lower pressure drops, and they
are more responsive to fast transients.
196198
Delphi Corporation teamed up with PACCAR Incorporated and Volvo
Trucks North America to dene what system level requirements must be
met for diesel fuelled SOFC based auxiliary power units on commercial
trucks.
199
Battery power was used to bring the SOFC up to operating
temperature. Once the reformer was operating in partial oxidation mode
and supplied hydrogen-rich syngas to the SOFC, it became possible to re-
cycle anode tail gas, providing additional steam thereby moving from
CPOX mode towards autothermal reforming. A potential hazard en-
countered during warm-up was that at temperatures below 773 K, H
2
leaking from the reformer or fuel cell stack could collect in the system and
ignite as the temperature increases. To deal with this challenge, sensors had
to be added to detect leakage of H
2
and CO, and the sensor signal would as
necessary trigger appropriate control action to shut the system down. As
additional safety precaution, special eorts were made to tightly seal the
components to minimize leakage and maximize containment.
In principle, water required for ATR can be recovered from the SOFC
anode exhaust or tail gas burner, as schematically shown in Fig. 8. If
condensation is used as a recovery step, re-vaporization will be required. If
water is kept in the gas phase by recycling uncondensed SOFC exhaust,
there will be a practical limit to the steam/C ratio that may be obtained as
CO
2
and N
2
will be recycled along with the steam (Fig. 9).
200
A group from Los Alamos National Laboratory found that changing the
recycle rate from 20% to 30% resulted in a much slower temperature rise in
the autothermal catalyst bed and required operation under higher O/C
ratios to compensate for the dierences in the catalyst bed temperature
Fig. 8 Schematic of APU with SOFC anode tail gas recycle.
82 | Catalysis, 2010, 22, 5693
proles.
201
An ASPEN simulation showed how the condensed exhaust gases
could dramatically alter the anode feed.
202
The patent literature covering low and high temperature fuel cells,
reformers, and combinations of fuel cells and reformers is rich. Over the
past decade signicant eorts have been made to advance fuel cells
closer to commercialization. A great portion of the eort, however, has been
directed at PEM fuel cells and reforming systems designed to support
them. General Motors has disclosed work on heat management in a
PEM-supporting reformer system wherein water vaporization is used to
control the PrOX reactor temperature and fuel cell exhaust is combusted
to increase heat recovery, integration with a water-cooled high-temperature
PEM stack, and heat-exchange networks to enable rapid startup.
203205
They have worked on design considerations for decreasing the volume
and mass of the reformer train, and managing steam within the fuel
processor/fuel cell.
206,207
Volvo has also published some work on fuel cell
systems, but as with GM it is aimed at motive power and low temperature
fuel cells.
208
Ford Motor Company made a signicant number of patent applications
regarding fuel cells, but apparently only one that is inclusive of an on-board
reformer.
209
The companys focus appeared to be on the fuel cell stack,
hydrogen separation membranes, and the use of metal-hydrides as a load
leveling and startup reservoir of hydrogen.
Delphi has perhaps the strongest patent literature record of fuel cell
system integration development. Their work has been geared towards
SOFCs as the electrical generation device. Work has covered the range of
process considerations including but not limited to startup strategies,
210,211
SOFC tail gas recycling,
212,213
heat transfer,
214
waste heat recovery,
215
and
temperature control.
216
In work which is more applicable to SOFC-APUs, General Motors has
investigated solutions to reformer startup using electrical preheat to initiate
light-o.
217
This pre-heated reformer is nominally intended for use within
Fig. 9 Steam/carbon ratio as function of anode tail gas recycle ratio.
200
Catalysis, 2010, 22, 5693 | 83
the PEM-supporting fuel processor train disclosed in other General Motors
patents.
Besides supplying hydrogen rich gas for fuel cell applications, on-board
reformers can also be used for hydrogen-assisted engine operation, en-
hanced rapid 3-way catalyst light-o in emission control systems, and for
providing reductant for enhanced diesel aftertreatment and selective cata-
lytic reduction (SCR) of NO
x
. In SCR systems, NO
x
is converted into N
2
with reducing agents like ammonia, urea, or hydrocarbons, for example:
3NO
2
4NH
3
!3:5N
2
6H
2
O 9
2NO2NH
3
1=2O
2
!2N
2
3H
2
O 10
10NOC
3
H
8
!5N
2
3CO
2
4H
2
O 11
2NOCH
4
O
2
!N
2
2H
2
OCO
2
12
While ammonia and urea, which can be thermally decomposed into
ammonia, are very eective for selective catalytic reduction of NO
x
, they are
cumbersome to use, as they require separate tanks to be installed on the
vehicle. Furthermore, there is the danger that unconverted ammonia slips
through the catalytic converter. An alternative strategy is to rely on
hydrocarbons from the fuel as reducing agents.
218
Compared to ammonia,
hydrocarbons are less eective NO
x
reducing agents, but adding small
amounts of hydrogen can drastically improve the rates of reduction.
219
An
on-board fuel reformer could provide not only hydrogen, but also CO and
light hydrocarbons to facilitate NO
x
reduction to N
2
. Not surprisingly,
supported Pt catalysts are among the most active catalysts for NO
x
re-
duction with H
2
, but their N
2
selectivity is not very good.
220
Other group
VIII noble metals, such as Pd, are also active and selective at moderate
temperatures.
221
While CO by itself can be used as a reductant under oxi-
dizing conditions, it appears to be less eective compared to hydrocarbons
or hydrogen, but on a Pd/Al
2
O
3
catalyst good NO
x
conversion and se-
lectivity was achieved with a syngas mixture of CO and H
2
.
222
Another
promising catalyst system is Ag/Al
2
O
3
.
223228
On Ag catalysts, hydrogen
addition to ammonia
229
or hydrocarbons
230,231
has proven to be very
benecial for NO
x
conversion and N
2
selectivity, and it signicantly lowers
the light-o temperature of the catalyst.
219,232,233
8. Conclusions
While there has been considerable eort devoted to the development of
compact fuel processors for liquid fuels, there are still many challenges re-
maining that need to be addressed. From a fundamental science standpoint,
more detailed reaction kinetics and rate laws need to be determined, not
only for pure hydrocarbons, but also for mixtures of hydrocarbons where
synergistic eects might be at work, and ultimately for actual fuels. The
extension of spatially resolved analysis of axial and radial composition and
temperature proles in monolith reactors from light gases to liquid
84 | Catalysis, 2010, 22, 5693
hydrocarbons and actual fuels appears promising. Guided by density-
functional theory, the design and synthesis of advanced carbon- and sulfur
tolerant catalyst formulations comes within reach. From a reaction-engin-
eering standpoint, major issues that remain to be addressed are adequate
performance under transient operation, ability to mitigate coking and sulfur
poisoning of catalysts, thermal integration and eciency, and overall sys-
tem integration within the weight and space constraints of vehicles. There is
also a need to demonstrate long term maintenance of catalytic activity
under typical on-board conditions with repeated start-up and shutdown
cycles. Start-up sequences for auxiliary power units appear to be closely
guarded secrets in the industrial community.
There is a need for more extensive system level auxiliary power unit re-
search to gain a better understanding of how fuel processors can be best
integrated with the fuel cell stacks and the balance of plant. Focusing on
optimization of individual components is unlikely to lead to optimized
overall system performance.
Acknowledgments
The authors would like to acknowledge the nancial support provided by
the U.S. Army Tank-Automotive Research, Development & Engineering
Center under Cooperative Agreement Number W56HZV-05-2-0001, and
details on the SpaciMS method provided by Galen B. Fisher.
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Catalysis, 2010, 22, 5693 | 93
Coupling kinetic and spectroscopic methods
for the investigation of environmentally
important reactions
F. C. Meunier
a
DOI: 10.1039/9781847559630-00094
1. Introduction
The improvement of the activity and selectivity of catalysts is a perpetual
objective for researchers in catalysis and can rely on a number of approaches.
While high-throughput combinatorial methods are raising a lot interest and
nding some success in heterogeneous catalysis,
1
the understanding of re-
action mechanism through detailed kinetic and spectroscopic studies is an-
other proven approach to support catalyst development. The purpose of this
report is to present some examples as to how insights into catalyst struc-
ture and/or reaction mechanisms can be obtained from combining in situ/
operando spectroscopic data and kinetics (i.e. spectrokinetics).
The examples treated here are (mostly taken from the previous work of
the author) related to the production of hydrogen via the water-gas shift
reaction (WGSR) and the selective reduction of NOx, which are both of
current interest with respect to environmental issues. The most recent work
put the emphasis on using so-called operando conditions, in which the
spectroscopic data were recorded while the reaction rate was simultaneously
measured over the catalyst using a single bed reactor. One of the aims of this
report was to highlight some of the benets of combining kinetic and
spectroscopic analyses, but also some of the shortcomings.
The rst example discusses the seminal work of Tamaru and co-workers
2
dating back to the 1960s. The decomposition rate of surface formates were
compared to the rate of CO
2
production during WGSR obtained over the
same sample in a dierent experiment. The second example describes how a
combination of kinetic and spectroscopic data (here recorded on two sep-
arate apparatuses) helped understanding, in parts, a very complex reaction,
which is the selective catalytic reduction of NO with propene. The subtle
role of NO oxidation on the reaction pathway of NO reduction over Ag-
Al
2
O
3
-based catalysts is discussed. The dierent mechanisms taking place
depending on the Ag loading are highlighted. The formation of oxidised
NOx(ads) species, important reaction intermediates, was evidenced by
in situ DRIFTS and thermogravimetric measurements. The isocyanates
observed by DRIFTS were also proposed as a crucial surface intermediate.
The third and nal example documents the use of operando DRIFTS
with steady-state isotopic kinetic analysis (SSITKA), using a mass spectro-
meter (MS) to follow mass transients, to investigate catalytic reactions. The
water-gas shift (WGS) reaction over noble metals supported on cerium-
containing oxides is presented in details. The DRIFTS-MS-SSITKA tech-
nique proved invaluable in determining the true role of formates seen by
a
Laboratoire Catalyse et Spectrochimie, ENSICAEN, Universite de Caen, CNRS, 6 Bd
Marechal Juin, 14050, Caen, France
94 | Catalysis, 2010, 22, 94118
_c
The Royal Society of Chemistry 2010
IR, which turned out to be minor reaction intermediates (i.e. essentially
spectators). Many advantages of coupling kinetic and spectroscopic meas-
urements are discussed, e.g. cell validation as a kinetic reactor, role of the
observed surface species, oxidation state of the working catalyst, spectator
versus potential reaction intermediate.
2. The bases of spectrokinetic analyses
Tamaru and co-workers reported investigative work in heterogeneous cata-
lysis combining spectroscopic and kinetic data dating back to the 1960s.
25
The corresponding studies represented some of the rst attempts to relate the
concentration and reactivity of surface species to the rate of the reaction
measured over the same catalyst. The water-gas shift reaction, COH
2
O-
CO
2
H
2
, over base metal oxides was one of the reaction investigated. The
type of experiments was highly challenging at the time, bearing in mind the
technological limitation of the equipment (e.g. dispersive IR, since FTIR
only become widespread much later)
6
and supply of high purity gases (e.g.
CO was sometimes obtained from the decomposition of sodium formate by
sulphuric acid and using a liquid nitrogen trap).
4
Custom-made cells were
designed and used for the spectroscopic and kinetic measurements.
It must be stressed that the system used was actually made of a dual cell,
each of those containing a catalytic bed. The rst bed was used for the
transmission IR analysis of a single wafer (e.g. with a mass of 300 mg) and
the second bed contained a much larger mass of catalyst (e.g. 11 g) to ensure
a measurable conversion.
4
The utilisation of a dual bed implies a non-
negligible risk that each bed experienced dierent experimental such as
temperature and concentration gradients.
The decomposition rate of surface formates were compared to the rate of
CO
2
production during the water-gas shift reaction (WGSR) obtained over a
MgO sample at 280 1C. The WGSR was measured under a feed of CO and
water in a recirculation mode. In a dierent experiment, the rate of formate
decomposition was obtained by following the decay of the formate bands for
various initial surface coverages. The quantitative relation between IR band
intensity and formate concentration was obtained via calibration curve
realised using reference samples derived from adsorption of know amounts of
formic acid on the catalyst. The values of WGSR rate and formate de-
composition were suciently similar (Table 1) so that the formates seen by
IR could be conclusively proposed as the main reaction intermediate.
Table 1 Comparison of the rate of formate decomposition to CO
2
H
2
over MgO
at 280 1C and the corresponding WGSR rate. Both set of data were obtained for the
same surface coverage of formate [reproduced from reference 4, copyright RSC]
Formate fractional
surface coverage
Rate of formate
decomposition to
CO
2
H
2
(mm
3
g
1
h
1
)
Rate of the water-gas
shift reaction
(mm
3
g
1
h
1
)
0.06 17 11
0.07 25 23
0.08 37 31
Catalysis, 2010, 22, 94118 | 95
This type of study, based on a transient involving a change in the
chemical potential of one or more of the chemical elements present,
assumes that the reactivity of the surface species is the same under reaction
condition and under concentration changes. This is clearly not always the
case
7
and will be discussed in more details in section four of the present
report.
A large number of spectrokinetic studies were also carried out in the
1970s in the former USSR by Mathyshak and co-workers.
8
A recent review
gathering many examples of this work has been published in Catalysis
Today.
9
In essence, these authors varied many experimental parameters (in
particular reactants concentrations) for the reaction of interest and meas-
ured the consumption rate of the reactant(s), formation rates of the prod-
uct(s) and the surface coverage of adsorbates observable by IR. A
microkinetic model was then developed and the experimental and simulated
variations of rates and surface coverages were compared to ascertain the
model.
9
The procedure, leading to a possible reaction mechanism, appears
to be experiment and time-intensive. Unfortunately, the methods used to
carry out spectral decomposition are often unclear, while this point is often
the bottle neck when complex spectra are considered. Other diculties
associated with the techniques regard the determination of molar
absorption coecients and, sometimes, the use of chemical transients.
In summary, the full microkinetic analysis combined with spectroscopy is an
elegant method but clearly requires a signicant amount of work and still
some assumptions.
Many teams around the World have since used spectrokinetic methods
derived from these seminal investigations, in particular by using isotopic
transients (e.g. for studying syn-gas conversion,
1014
CO
2
-reforming of
methane
15,16
and nitrogen oxides decomposition,
17,18
) but it is not the scope
of the present article to provide an exhaustive review of this eld.
3. Investigation of the selective reduction of NOx with propene
over Ag/Al
2
O
3
The example treated in this section regards a combination of kinetic,
thermodynamic, spectroscopic and gravimetric data that was very useful in
our investigation of the selective catalytic reduction of NOx with hydro-
carbons, a highly complex reaction. The data corresponding to dierent
experimental techniques were recorded on separate apparatuses, each hav-
ing its own reactor. Therefore, the experimental parameters (e.g. tempera-
ture prole, gas ow pattern, catalyst bed geometry and dead-volume,
impurities) were possibly not strictly identical for each type of measurement.
Nonetheless, the trends observed between the results obtained from the
various techniques were consistent and worthwhile qualitative conclusions
could be drawn.
A commercial cell from Spectra-Tech
s
was used to carry out the diuse
reectance FTIR (DRIFTS) measurements. The bottom part of the
catalyst bed, which was not probed by the IR beam, was possibly by-passed
by the reaction mixture, due to the high pressure drop of the original
reactor frit holding the sample.
19
The catalytic data were obtained
96 | Catalysis, 2010, 22, 94118
using a tubular quartz plug ow reactor, as the amount of catalyst that
could be placed in the DRIFTS cell (typically 20 mg) was not sucient
to induce a signicant conversion. The thermogravimetric data were
recorded on an IGA microbalance. More experimental details can be found
elsewhere.
20,21
3.1 Selective catalytic reduction (SCR) over alumina and silver-based
catalysts
Many base oxides/metals (e.g., Al
2
O
3
, TiO
2
, ZrO
2
, and these oxides pro-
moted by, e.g., Co, Ni, Cu, Fe, Sn, Ga, In, Ag) are active catalysts for the
selective reduction of NOx (NO and NO
2
) with hydrocarbons (HC-SCR).
22
Note that under typical lean-burn conditions, the promoting metals are
almost exclusively in an oxidised state. Catalysts based on Ag supported on
g-alumina received a particular attention, as these materials are among the
most active and selective for this reaction.
The activity of alumina and that of the same support promoted by a low
(i.e. 1.2 wt.%) and high (i.e. 10 wt.%) loading of silver are shown in Fig. 1.
The alumina was active and selective for the formation of N
2
at higher
temperatures (W400 1C), under these experimental conditions. It is inter-
esting to note that some N
2
O and especially high concentrations of NO
2
were observed over the alumina after complete propene conversion, i.e.
above 565 1C. On the contrary, some NH
3
could be observed but only be-
fore complete propene conversion. The 1.2% Ag/g-Al
2
O
3
yielded similar
conversions to N
2
as those obtained over the alumina but at lower tem-
peratures. Low concentrations of N
2
O, NO
2
and NH
3
were also obtained in
this case.
The activity of the high loading silver catalyst was signicantly dierent
from that of the g-Al
2
O
3
and the 1.2% Ag/g-Al
2
O
3
. Complete combustion
of the reductant was achieved at 350 1C over the 10% Ag/g-Al
2
O
3
, in
contrast to the temperatures of 100% combustion of the reductant over
1.2% Ag/g-Al
2
O
3
and g-Al
2
O
3
of 500 1C and 565 1C, respectively. In add-
ition, the N
2
yield remained signicantly lower than that of N
2
O (obtained
at the lower temperatures) and NO
2
(obtained at the higher temperatures).
Over the 10% Ag/g-Al
2
O
3
and at the higher temperatures, the conversion to
NO
2
was limited by the thermodynamics of the reaction (see dotted line in
Fig. 1, NO
2
yield):
NO
1
2
O
2
=NO
2
(1)
One of the striking features of the catalytic data reported in Fig. 1 was the
sharp increase in the NO
2
yield obtained over the alumina as soon as
complete conversion of propene was achieved, at ca. 565 1C. The values of
NO
2
yield obtained at these temperatures were signicantly higher than that
allowed by the thermodynamics of the reaction represented by equation (1).
It has to be stressed that identical plots were obtained independently of
using increasing or decreasing temperature proles and no change in the
yield of NO
2
was observed after several hours on stream. A NO
2
yield in
slight excess of the thermodynamic limit was also observed over the 1.2%
Ag/g-Al
2
O
3
. This surprising observation was not due to any quantication
Catalysis, 2010, 22, 94118 | 97
error, as indicated by the fact that the NO
2
yield value measured in the case
of the 10% Ag/g-Al
2
O
3
was exactly equal to that expected by the thermo-
dynamics (Fig. 1).
Such high NO
2
(g)/NO(g) ratios largely exceeding the value expected from
thermodynamics were also observed during the course of the SCR reaction
over other excellent SCR catalysts based on cobalt/alumina.
23
These obser-
vations clearly indicates that the main route to NO
2
(g) over these catalysts is
not the direct oxidation of NO by O
2
as described by the equation (1),
contrary to what had been suggested by many authors.
24
Hamada et al. had
proposed that NO
2
was an intermediate, based on the facts (i) that the re-
action starting from this molecule was much faster than that starting from
NO and (ii) that the activity measured in the presence of NO
2
did not require
the presence of the promoter.
0
20
40
60
80
100
150 350 550
C
3
H
6

c
o
n
v
e
r
s
i
o
n

/
%
0
20
40
60
80
100
150 350 550
N
O

c
o
n
v
e
r
s
i
o
n

/
%
0
10
20
30
150 350 550
N
O
2

Y
i
e
l
d

/
%
0
20
40
60
150 350 550
N
2

Y
i
e
l
d

/
%
0
2
4
6
150 350 550
Temperature /C Temperature /C
N
H
3

Y
i
e
l
d

/
%
0
10
20
30
150 350 550
N
2
O

Y
i
e
l
d

/
%
Fig. 1 C
3
H
6
-SCR of NO over g-Al
2
O
3
(), 1.2% Ag/ g -Al
2
O
3
() and 10% Ag/g -Al
2
O
3
(v)
catalysts as a function of temperature. Feed: 500 ppm NO500 ppm C
3
H
6
2.5% O
2
/He,
W/F=0.06 g s cm
3
(GHSVB50 000 h
1
). The dotted line in the plot giving the NO
2
yield
represents the thermodynamic limit associated with the reaction NO1/2O
2
3NO
2
.
(Reprinted from reference 20.)
98 | Catalysis, 2010, 22, 94118
3.2 Oxidation of NO(g) to NO
2
(g) and to NOx(ads)
The NO(g) to NO
2
(g) oxidation ability of our samples was measured
and the best SCR catalysts (i.e. those leading to N
2
, alumina and 1.2%
Ag-promoted alumina) displayed a very poor activity at the optimum
temperatures for the SCR reaction (Fig. 2). The activity of the 1.2% Ag-
alumina was essentially identical to that of the support, while the high
loading sample (10 wt.% Ag) was very active for NO
2
formation.
IR and thermogravimetric data were also collected in order to unravel the
role of the Ag promoter. The in situ DRIFTS spectra reported in Fig. 3
qualitatively describe the growth of various surface nitrate species (bands
at ca. 1560, 1305 and 1255 cm
1
) when the samples were exposed to a
NOO
2
stream. Both silver-promoted materials appeared to exhibit a
faster uptake rate of NOx(ads) than that observed over the plain alumina.
This trend was conrmed quantitatively using the mass uptake measured
with the microbalance (Fig. 3). It is clear that at least one of the main role of
the 1.2% silver promoter was to favour the oxidation of NO(g) to strongly
bound NOx(ads) species (and not to NO
2
(g), as shown above).
3.3 Proposed reaction mechanisms of the SCR over Ag/Al
2
O
3
The marked dierences between the activity of, on the one hand, the 10
wt.% Ag sample and, on the other hand, the 1.2% Ag and plain alumina
(see Figs. 1, 2 and 3) suggests that dierent reaction mechanisms may occur
on these catalysts. A NO decomposition-type mechanism was suggested to
occur on the high loading material, which probably consisted of large me-
tallic silver particles deposited on the alumina (Fig. 4). To this respect, the
activity pattern of this sample resembles that of platinum group metals. In
the case of the low loading Ag/Al
2
O
3
, dispersed Ag

cations and/or small

0
5
10
15
20
150 250 350 450
Temperature /C
550 650
N
O
2

Y
i
e
l
d

/
%
Thermal Equilibrium
10% Ag/Al
2
O
3
Al
2
O
3
1.2% Ag/Al
2
O
3
Fig. 2 Conversion of NO to NO
2
over g-Al
2
O
3
( ), 1.2% Ag/g-Al
2
O
3
(

) and 10%
Ag/g-Al
2
O
3
(
v
) catalysts as a function of temperature. Feed: 0.05% NO5% O
2
in Ar,
W/F=0.06 g s cm
3
. (Reprinted from reference 20.)
Catalysis, 2010, 22, 94118 | 99
1200 1300 1400 1500 1600 1700
1200 1300 1400 1500 1600 1700
1200 1300
Wavenumber /cm
-1
Time under the NO/O
2
/He stream /min
1400 1500 1600 1700
1255
1305
1550
1550
1300 1560
Absorbance
0.3
a
b
c
1235
0
2
4
6
0 1 2 3 4 5
R
e
l
a
t
i
v
e

w
e
i
g
h
t

u
p
t
a
k
e

/

1
0

3
Al
2
O
3
1.2% Ag/Al
2
O
3
10% Ag/Al
2
O
3
Fig. 3 Right: in situ DRIFTS analysis of the formation of ad-NOx species at 4001C over
(a) g-Al
2
O
3
, (b) 1.2% Ag/g-Al
2
O
3
and (c) 10% Ag/g-Al
2
O
3
. For each catalyst, time on stream
was 15 min (lower spectrum), 60 min (middle spectrum) and 180 min (upper spectrum). Left.
Thermogravimetric analysis of the formation of ad-NOx species at 400 1C over g-Al
2
O
3
(x),
1.2% Ag/g-Al
2
O
3
(

) and 10% Ag/g-Al

2
O
3
(
v
) as a function of time. Feed: 0.05%
NO2.5%O
2
/He. (Reprinted from reference 20.)
R-NO
2
R-ONO
NOx
-
N
2
O + N
2
alumina
Ag
Ag
+
O
N O O
C
3
H
6
NO / O
2
H
2
O
CO
x
CxHy
NO + O
2
C
3
H
6
N
2
NO
2
R-NH
2
R-NCO
NH
3
O
2
O
N
Fig. 4 Schematic representation of the two main reaction pathways taking place on
Ag/g-Al
2
O
3
. (Reprinted from reference 20.)
100 | Catalysis, 2010, 22, 94118
electropositive silver clusters in strong interaction with the alumina pre-
vailed. The exact nature of the reaction mechanism(s) occurring over alu-
mina and low loading Ag/Al
2
O
3
is not yet fully understood, but N
2
is
probably formed via a series of parallel and consecutive reactions involving
numerous intermediates over both the silver and alumina phases.
Oxidised species of nitrogen (e.g., inorganic nitrates) are thought to react
with reduced forms of this element (e.g., isocyanate, ammonia, formed via
organo-nitrogen compounds) to produce N
2
(Fig. 4). The typical volcano-
shape of the N
2
yields plots is ascribed to the competitive reactions between
NO and O
2
for the reductant. The unselective combustion of the reducing
agent with O
2
becomes much faster than the SCR at higher temperatures
and diminishes the number of reductant molecules available for the
SCR. The temperature of maximum N
2
yield often corresponds to ca. 90%
conversion of the reductant.
The reaction scheme proposed for the low loading sample is supported by
the evidence described thereafter. The formation of organonitrogen com-
pounds was observed over some SCR catalysts.
25
The formation and de-
composition of such compounds would rationalise the high concentrations of
NO
2
observed. The example given below equations (24) is arbitrarily based
on nitromethane, simply because thermodynamic data are readily available for
this molecule. The organonitrogen compound would be formed along with CO
(or CO
2
) from the reaction of propene, O
2
and NO equation (2). The sub-
sequent oxidation of this organo-NOx species would yield NO
2
equation (3):
C
3
H
6

3
2
O
2
2NO 2CH
3
NO
2
CO (2)
2CH
3
NO
2

7
2
O
2
2NO
2
2CO
2
3H
2
O (3)
Overall, the equations above combine to give:
C
3
H
6
5O
2
2NO 2NO
2
2CO
2
CO3H
2
O (4)
While it is likely that the actual mechanism occurring on the low loading
Ag materials involves more than one organonitrogen species according to a
more complex reaction scheme, these equations are important in the
sense that the reactions are strongly exergonic over the temperature range
investigated here. The standard Gibbs free energy of reaction at 813 K
associated with eqn. 4.3.2 and 4.3.3, are D
r
G1 = 298 kJ mol
1
and
734 kJ mol
1
, respectively. The global reaction equation (4) is therefore
also strongly favoured and provides a rational explanation for the high
NO
2
/NO ratio observed during the experiments (Fig. 1).
3.4 Reactivity of organonitrogen species over Ag/Al
2
O
3
Organonitrogen species can be readily formed non-catalytically by reaction
of hydrocarbon, dioxygen and nitric oxide in the liquid or gas phase.
26
The
decomposition products of organo-nitrogen species yield similar products
to those observed during the SCR reactions (e.g., cyanide, isocyanates),
supporting their role as intermediates. NH
3
can be obtained from nitro-
methane through the tautomerisation to the corresponding oxime followed
by dehydration to a nitrile N-oxide equation (5) which isomerise to an
Catalysis, 2010, 22, 94118 | 101
isocyanate before yielding a primary amine and NH
3
by hydrolysis equation
(6, H
2
O/CO
2
are not reported). Over alumina, the possibility of forming NH
3
from reaction of organo-nitrile N-oxides species was conrmed;
27
the organo-
nitrile N-oxide were formed from organo-nitroso compounds, via enol and
cyanide formation (eqn. 7, only the N-containing fragment is shown).
CH
2
NO
2
CHQNO(OH) CQNQOH
2
O (5)
CQNQO NQCQO NH
2
NH
3
(6)
CH
2
NO CHQN(OH) CRN CQNQO (7)
We have shown that the nature of the organonitrogen compounds greatly
inuenced the nature of the products formed, as two main reactivity
1258
1306
1554
1376
1393
1447
1598
2094
2228
2902
3003 3390
1200 1600 2000 2400 2800 3200 3600 4000
/ cm
1
(a)
(b)
0.1
Abs
Fig. 5 DRIFT spectra at 573 K in argon of Al
2
O
3
following pre-adsorption of (a) nitro-
methane and (b) tert-butyl nitrite at room temperature. (Reprinted from reference 28, RSC.)
102 | Catalysis, 2010, 22, 94118
patterns were observed during the oxidation over the 1.2% Ag/alumina.
28,29
Nitro-type molecules led to the formation of reduced nitrogen products,
including ammonia and hydrogen cyanide, with isocyanates being a main
surface species (Fig. 5). In contrast, nitrito-type compounds led to NO
2
and
surface nitrates and nitrites. The latter type of compounds is therefore an
obvious candidate for the source of the NO
2
formed under SCR conditions.
3.5 Proposed SCR reaction mechanisms over oxide-based catalysts
The global reaction scheme proposed in the case of our 1.2% Ag/Al
2
O
3
can
probably be extended to other oxide-based SCR catalysts (Fig. 6).
22,23
The
role of dioxygen is intricate and paradoxal, as this oxidiser strongly favours
the reduction of NO over most catalytic formulations. Most authors ac-
knowledge that the two main functions of O
2
are the oxidation of NO and
of the reductant to form the various reaction intermediates.
As far as the hydrocarbon is concerned, one of the important initial steps
proposed is its oxidation to strongly bound oxidised species such as acet-
ates. The acetate species or other adsorbed oxidised hydrocarbon species
(e.g. acrylates)
30
are then believed to react with the surface nitrates (or
possibly with gas-phase NOx) to yield organo-nitrogen species, the exact
nature of these species remaining unclear. The formation of the organoni-
trogen species is likely to be the rate-determining step of the reaction, as
NO (g) + O
2
(g) + C
x
H
y
(g)
Inorganic NOx (ads)
(several species, in
particular, monodentate
nitrate)
CxHyOz (ads)
(several species, in
particular acetate)
Organo-nitrogen,
e.g., R-NO
2
(g or ads)
R-ONO (g or ads)
R-CN
R-NCO
R-NH
2
NH
3
NO
2
(g)
N
2
(g)
adNO
x
Minor route
Fig. 6 Schematic representation of the two main reaction pathways taking place on oxide-
based catalysts for the selective reduction of NO with hydrocarbons. (Reprinted from
reference 23.)
Catalysis, 2010, 22, 94118 | 103
these can only be observed during transient experiments such as tempera-
ture-programmed surface reaction monitored by in situ IR.
Like some other researchers, we have therefore proposed that the coup-
ling of nitrogen atoms to form N
2
could occur via the reaction between the
oxidised (e.g., NO(g), nitrate) and reduced (e.g, NCO, NH
3
) forms of ni-
trogen. This observation stresses that the reaction mechanism is very
complex since NO will react through a series of parallel pathways to form
numerous intermediates.
The relevance and rate of each step of the scheme represented in Fig. 6
depends on the nature of the reductant, the catalyst and experimental
conditions. The overall rate-determining step and the surface concen-
trations of each species will vary accordingly. For instance, the rate at which
acetates formed was shown to be dependent on the chain length of the al-
kane.
31
As a result, the relative surface coverage of acetates and nitrate
species can vary as a function of type of feed, catalyst and experimental
conditions used. In the case of the C
3
H
6
SCR of NO over Al
2
O
3
, the rate of
nitrate formation is slower than their rate of consumption and as a result
acetates predominate (Fig. 7, bottom spectrum). When Ag is added to the
Al
2
O
3
, the oxidation of NO to ad-NOx species is promoted and surface
nitrate species now predominate (Fig. 7, upper spectrum).
Other experimental parameters such as temperature, water vapour pres-
sure will aect the weight of the reactions as reported in Fig. 6. The possible
participation of homogeneous reactions must also be considered, especially
at the higher temperatures and bearing in mind that NO and NO
2
are
radicals.
32
Yet, it appears the majority of data reported on oxides/base
metals are consistent with this scheme.
1380
1400
1600
2910
3005
1555
1400 1800 2200 2600 3000 3400 3800
Wavenumbers /cm
1
CO
2
Absorbance
a.u.
C
H
O O
1460
1460
-Al
2
O
3
1% Ag /-Al
2
O
3
NOx (ads)
Fig. 7 In situ DRIFTS spectra of the surface species formed over Al
2
O
3
and 1.2% Ag/Al
2
O
3
during the SCR of NO with propene. Feed: 500 ppm NO500 ppm C
3
H
6
2.5% O
2
.
(Reprinted from reference 20.)
104 | Catalysis, 2010, 22, 94118
3.6 Conclusions on the study of HC-SCR of NO by in situ IR and
combined kinetics
The work reported in this section shows that a combination of kinetic,
thermodynamic, spectroscopic and gravimetric data proved useful in de-
termining some of the main aspects of the hydrocarbon selective catalytic
reduction of NO over oxide-based catalysts. One of the role of the Ag
promoter at low loadings was to favour the formation of surface nitrate/
nitrite species, but not directly NO
2
(g). The formation of NO
2
(g) occurred
via a complex reaction scheme involving the oxidation of organonitrogen
species, probably of the nitrito-type. A second major outcome of our work
was to evidence the occurrence of another distinct reactions mechanism at
higher silver loadings, similar to that taking place of platinum, based on a
decomposition-type mechanism. While no unambiguous conclusion could
be given on the true nature as reaction intermediates of the surface species
observed by in situ IR, the observed species nonetheless helped building a
realistic model of this complex reaction pathway.
4. Spectrokinetic operando investigation of catalytic reactions
As described in the previous section, the collection and comparison of
kinetic and spectroscopic data can be useful in gaining some understanding
of the mechanism of a catalytic reaction. However, data pertaining to dif-
ferent techniques are usually collected on separate apparatuses, each having
its own reactor. The simultaneous collection of various spectroscopic data
in a single reactor is currently receiving much attention as a means to
overcome the possibility of dierences in the actual experimental conditions
prevailing in separate reactors.
33,34
In order to identify more focussed analytical techniques a new expression,
i.e. operando, was put forward. The term operando spectroscopy refers
to spectroscopic measurements of catalysts under working conditions with
simultaneous on-line product analysis. This term was used in the literature
starting from 2002
35,36
with the aim to distinguish work in which on-line
activity measurement was performed alongside spectroscopic measurements
(i.e. operando) from those in which only spectroscopic data were recorded
(i.e. in situ).
The on-line analysis of the reactor euent is useful in many ways. Firstly,
it allows collecting kinetic data that are directly related to the spectroscopic
data simultaneously measured, which is particularly useful when carrying
out isotopic transients. Secondly, it ensures that the activity data obtained
in the operando reactor are consistent with those observed in a conventional
ideal reactor. These conditions required the (often challenging) devel-
opment of reaction cells operating in a kinetically relevant mode, able to
withstand extreme conditions, while still allowing the electromagnetic ra-
diation to escape from the reactor. In spite of the technical diculties, the
success of operando techniques is such that the number of teams switching
their studies towards this methodology is increasing.
37
The investigations reported in this section will describe how a DRIFTS
cell can be checked for kinetic relevance and the modication that can be
made to correct any aw. Quantitative aspects of DRIFTS work will also be
Catalysis, 2010, 22, 94118 | 105
addressed. Isotopic transient techniques (i.e. SSITKA) will be used to de-
termine the actual role of surface species seen by DRIFTS. The water-gas
shift reaction will be investigated in details and some data related to CO
hydrogenation will also be presented.
4.1 Development of a kinetically relevant DRIFTS cell reactor
Diuse reectance FT-IR spectroscopy (DRIFTS
38,39
) is increasingly being
used as a means to investigate the reactivity of surface species under re-
action conditions, but it is usually considered only as a qualitative techni-
que. However, it was demonstrated that DRIFTS spectroscopy can be an
accurate quantitative tool for operando studies, providing that an appro-
priate analytical transformation of the diused intensity is used (i.e. in most
cases the pseudo-absorbance rather than the Kubelka-Munk function
40
)
and that a calibration curve relating band intensity to adsorbate concen-
tration is available.
41
We also showed that an appropriately modied
DRIFTS cell reactor
19
led to reaction rates identical to those measured in a
linear quartz tube plug ow reactor.
41
DRIFTS reactors are particularly
suited to operando investigations since the catalyst powder can be used as
such, whereas FTIR-transmission techniques require pressing wafers, which
can lead to mass-transport limitations and catalyst modications.
The environmental DRIFTS chambers proposed by Spectra-Tech have
been widely used to carry out in situ and operando analyses. It has been
known for many years
42
that these cells present some bypass of the catalyst
bed. As a result, a large proportion of the incoming gas directly goes to the
outlet, without passing through the catalyst bed located on top of the cer-
amic crucible. This problem is made worse by the fact that the porous frit
used to support the catalyst presents a very high pressure drop. More, in the
case of the high-pressure cell, the ZnSe dome can be very close to the rim of
the crucible limiting its accessibility. As a result, the volume delimited by the
catalyst bed and the void above it can become a dead-zone, with very slow
diusion pathway to the circulating gas passing through the cell. The extent
of bed bypass can be assessed (i) by comparing the catalytic activity
measured in the DRIFTS reactor to that measured in a traditional tubular
reactor and (ii) measuring the time needed to purge the bed area, moni-
toring an IR-sensitive tracer.
19
The DRIFTS cell that was used throughout this section was the high-
temperature model, in which at ZnSe windows are several millimeters
apart from the crucible, therefore not limiting the access to the catalyst bed.
The bed bypass when using a owrate of 100 ml min
1
, which was the
owrate value typically used during our operando experiments, was esti-
mated by measuring the extent of CO conversion during oxidation with an
excess of O
2
over a Pt-based catalyst. A complete conversion of CO to CO
2
would be expected above the light-o temperature, when no bypass is taking
place. The oxidation data showed that almost 80 % of the feed bypassed the
catalyst bed in the case of the original cell, as the CO conversion leveled o
at ca. 20% after the light-o.
19
The cell was modied by replacing the original crucible with a custom-
made ceramic reactor. The crucible presented no signicant pressure drop as
106 | Catalysis, 2010, 22, 94118
a metallic mesh (mesh size 45 micron) was used to support the catalyst in-
stead of the ceramic porous frit of the original cell. The catalyst powder was
sieved using the same mesh as that located in the crucible and only the
fraction that did not cross over the mesh was used for the DRIFTS analysis.
No study was carried out to investigate the eect of the particle size on the
intensity of the IR signal obtained.
The gap between the crucible stem and the metallic base was sealed by
wrapping the lower part of the crucible stem with Teon-tape before in-
serting into the base. The Teon tape was in close contact with the ther-
mostated cell metal base, the temperature of which always remained
moderate (typically less that 120 1C even when the crucible itself was heated
up to 400 1C). Therefore, the PTFE tape did not show any signicant level
of degradation under standard conditions of use. A level of CO combustion
higher than 98.5% was achieved above the temperature light-o on the
modied system, indicating that the bed bypass was negligible. A further
validation of the kinetic relevance of our modied DRIFTS cell come from
the fact that the catalytic activity measured during the WGS reaction using
the modied cell was shown to be equal to that measured in a conventional
tubular plug-ow reactor.
41
Note that no conversion of reactant was ob-
served when the crucible was heated up to the reaction temperature in the
absence of the catalyst.
The DRIFTS and mass spectrometry (MS) data collected during our
DRIFTS-MS experiments actually relate to dierent regions of the reactor.
The DRIFTS data are collected at the front (and top) part of the bed, while
the MS data are collected at the exit of the cell, i.e. after the bed (Fig. 8a). If
the evolution of the MS signals of reactions products during an isotopic
switch is to be compared to the evolution of the DRIFTS intensities of
surface intermediates, then the gas phase all along the catalyst bed should be
H
2
+
CO
2
adsorbates
CO + H
2
O
Pt /CeO
2
DRIFTS
signal
ca. 0.2 mm
2 mm
CO
2
+ H
2
MS signal
0
0.2
0.4
0.6
0.8
1
0 100 200 300 400 500
Time after isotopic switch /s
R
e
l
a
t
i
v
e

M
S

o
r

D
R
I
F
T
S

i
n
t
e
n
s
i
t
y



Kr
13
CO
2
(IR)
x (MS)
(a) (b)
Fig. 8 (a) Schematic representation of the catalyst bed and the zone probed by the DRIFTS
beam. The MS data are collected at the exit of the DRIFTS cell, i.e. after the bed. (b) Relative
intensity of the Kr tracer (solid line),
13
CO
2
measured by mass spectrometry () and
13
CO
2
measured by the IR signal of the DRIFTS cell (&) following a
12
CO
13
CO isotopic switch under
steady-state WGS conditions over a 2% Pt/CeO
2
. T=473 K, feed: 1%
13
CO10% H
2
O in
2% Kr/Ar. The feed was 1%
12
CO10% H
2
O in Ar before the switch. (Reprinted from
reference 19.)
Catalysis, 2010, 22, 94118 | 107
homogeneous (to avoid chromatographic eects). This is to ensure that the
variation of the gas-phase composition at the front of the bed, which dir-
ectly relates to the surface species observed by the DRIFTS, is equivalent to
that measured by MS after the bed.
It is therefore important to use dierential conditions throughout the bed
by keeping a conversion lower than ca. 15%. In this way, the concentration
of surface species should be essentially constant throughout the catalyst
bed. The fact that only a fraction of the bed volume is analysed by DRIFTS
still allow doing quantitative analysis knowing the full bed mass, providing
calibration curves are available based on the very same sample impregnated
by known concentrations of adsorbates (see Section 4.5). The DRIFTS
signal of the surface species of interest measured under reaction condition
and that measured over the calibrated samples are related to a same analysis
volume (or mass) and knowing the concentration (in mol/g) in the sample
allows deriving the full amount of sorbate present (in mol) using the actual
sample mass. It is clear that using a dierent sample for calibration pur-
poses (e.g. with a dierent particle size, surface area or composition) would
lead to a dierent calibration curve, as shown in reference 45, and does not
allow quantitative insights. Bed packing must also be carried out in a re-
producible manner, which is usually the case when using the same operator.
In an example treated here based on water-gas-shift data, we are fortu-
nate that the reaction product CO
2
can be observed both by using the
DRIFTS signal and by the MS. Note that the bands measured by DRIFTS
are related to the surface species present in the upper volume of the catalyst
bed (typically at less than 200 microns depth for a total bed length of ca.
2 mm), while the signal of CO
2
(g) is both coming from the same volume and
the free gas volume above the bed.
An isotopic exchange of CO
2
was followed during a SSITKA-DRIFTS-
MS experiment over the Pt/CeO
2
catalyst (see subsequent sections for the
description of the method). The CO conversion was 10% in these con-
ditions, ensuring dierential conditions. The evolution of the
13
CO
2
signals
following the switch to the
13
CO-containing feed is given in Fig. 8b. The MS
signal of the Kr tracer is also reported for the sake of completeness. The Kr
prole (Fig. 8b) (and that of the reactant CO, not shown here) was essen-
tially a step-function in comparison with the CO
2
signals, indicating that the
variation of the
13
CO
2
concentration was not limited by mass transport (i.e.
by the supply of labeled gas).
Note that this is not the case in the work reported by Jacobs and Davis,
43
in which the isotopic exchange of surface and gaseous compounds is limited
by a very slow gradual introduction of the labeled gas (as the switching
valve is located before the CO mass ow controller). The disadvantage of
the technique used by Jacobs and Davis is that all processes with a time
constant lower than that of the supply of the labeled compounds (several
minutes) will not be resolved, while the time constant of our method with
this modied cell is ca. 7 s.
It is clear that the relative variations of the DRIFTS and MS signals
associated with
13
CO
2
(Fig. 8b) were identical, displaying an almost ex-
ponential increase with a 50%-exchange time of about 55 s. These data
unambiguously show that the signal of the reaction product CO
2
measured
108 | Catalysis, 2010, 22, 94118
by the MS after the catalyst bed perfectly corresponded to that measured at
the bed entrance, which was measured using the DRIFTS signal. Therefore,
the gas-phase prole in the thin (ca. 2 mm) catalyst bed was homogeneous,
in the reaction conditions used here. This fact justies the comparison of the
curves obtained by DRIFTS for the surface species at the top of the bed and
the curves obtained for the products of reaction by MS (or any other
analytical techniques) after the reactor, at least as long as dierential con-
ditions apply.
4.2 Quantitative DRIFT analysis of adsorbates concentrations
There is a widespread misconception that the IR signal measured in the
diuse reectance mode of species adsorbed at surfaces must always be
reported as Kubelka-Munk units, which are given by the equation below
(eqn. 8), in which R
N
=I/Io is the reectance of the sample, that is the ratio
of the intensity diused (noted I) to that incident (noted Io):
F(R

) =
K
S
=
(1 R

)
2
2R

(8)
In fact, a dierent expression (eqn. 9) has been proposed to account for
the concentration of the adsorbates,
44
in which R is the reectance measured
in the presence of the adsorbate:
Mathyshak Krylov(R) = [c[ = a
(R

R)
R

1
R
R

(9)
Based on these equations, we have shown
40
that the relative absorbance,
i.e. = log R
/
with R
/
=relative reectance =R/R
N
, is a more linear
function of the surface concentration than the Kubelka-Munk function in
the range of relative reectance R
/
comprised between 100 and 60%. This
range of relative reectance is pertinent to most DRIFT studies of surface
species, for which the signal loss due to the absorption of the adsorbed
species is weak. The use of the absorbance function also overcomes the
problem associated with baseline drifts during measurements.
40
It is only in
the case of low values of reectance that using the Kubelka-Munk trans-
form may be more appropriate.
Further evidence that units of absorbance are appropriate when investi-
gating surface species by DRIFTS is given by the data reported in Fig. 9,
which relate to the decomposition of
12
C-containing surface formates spe-
cies during the water-gas shift reaction over a ceria-based catalyst (vide
infra). The intensity of the formate bands was expressed in absorbance
units. An almost perfect exponential decay was observed (Fig. 9a), as ex-
pected in the case of rst order processes, since the corresponding semi-
logarithmic plot yielded a straight line (Fig. 9b). As a consequence, the
absorbance units were always used during our investigations whenever any
quantitative work was carried out. Another a common misconception is
that DRIFTS work cannot be quantitative, contrary to the case of trans-
mission IR data. On the contrary, we were able to draw calibration curves
to accurately quantify the concentration of formates and use these curves to
quantify the concentration (in mol/g) during our operando work.
41,45
Catalysis, 2010, 22, 94118 | 109
4.3 The operando SSITKA-DRIFTS-MS method
Spectroscopic studies are more powerful when combined with isotopic
transient methods (SSITKA
46,47
), which allow operating at the chemical
steady-state. The operando DRIFTS-SSITKA method described here relies
on using a single catalytic bed, which allows the characterisation by DRIFT
spectroscopy of the surface of the very same catalyst particles that are re-
sponsible for the catalytic activity measured at the exit of the cell by gas-
chromatography or mass-spectrometry.
48
The group at Queens University
Belfast was the rst to report data coupling in situ DRIFTS with activity
measurement using a mass spectrometer (MS) during a steady-state isotopic
exchange kinetic analysis (SSITKA) using a single bed reactor. This
methodology is similar to that developed earlier for transmission FTIR by
Chuang et al.
14,49
Note that mass transport limitations may occur with
wafers and that the temperature control can also be dicult (as is for
DRIFTS cells at high temperatures). These techniques derived from the so-
called isotopic jump technique of Tamaru et al.,
5
which relied on a two-
bed IR cell (see Section 2 of this report).
The principle of the DRIFTS-MS-SSITKA method that was developed
for the operando investigation of catalytic reactions is schematically rep-
resented in Fig. 10. The use of SSITKA method allows us assessing the
chemical reactivity of surface species with respect to the formation of a
reaction product under chemical steady-state conditions. This technique
consists in replacing one of the reactants (e.g.
12
CO) by an isotopomer (e.g.
13
CO) during reaction and following simultaneously the exchange of the
labelled reaction product (here
13
CO
2
) by mass-spectrometry and the sur-
face species (e.g.
13 or 12
C-containing carbonyl and formates) by DRIFTS.
The DRIFTS bands of the surface species typically shift in wavenumbers
during the analysis, and various integration methods can be used to
quantify accurately the band heights or areas.
19
A surface species observable by IR can only be a main reaction inter-
mediate if it exchanges at least as fast as the reaction product in the
0
0.2
0.4
0.6
0.8
1
0 500 1000 1500
Time after isotopic switch /s
P
r
o
p
o
r
t
i
o
n

o
f

1
2
C
-
c
o
n
t
a
i
n
i
n
g
s
u
r
f
a
c
e

f
o
r
m
a
t
e
s

-2
-1
0
0 500 1000 1500
Time after isotopic switch /s
L
o
g
1
0

o
f

t
h
e

p
r
o
p
o
r
t
i
o
n

o
f

1
2
C
-
c
o
n
t
a
i
n
i
n
g

s
u
r
f
a
c
e

f
o
r
m
a
t
e
s
(a) (b)
Fig. 9 (a) Relative DRIFTS signals measured in absorbance units associated with the
12
C-
containing formate species following a
12
CO
13
CO isotopic switch under steady-state WGS
conditions over a 2% Pt/CeO
2
. T=473 K, feed: 1%
13
CO10% H
2
O in 2% Kr/Ar. The
sample was initially at steady-state under 1%
12
CO10% H
2
O in Ar. (b) Logarithmic plot of
the data reported in (a). The dotted line is a straight line used as an eye guide. (Reprinted from
reference 19.)
110 | Catalysis, 2010, 22, 94118
gas-phase (e.g., species I in Fig. 10). A signicantly slower exchange or no
exchange at all indicates a minor reaction intermediate and a spectator
species, respectively (e.g., species S in Fig. 10). Using a single bed and dif-
ferential conditions ensures that any observed variations of surface species
concentrations can be related to that of products in the gas-phase. We have
reported the rst use of this setup in an investigation of the reverse water-
gas shift (RWGS) reaction:
48
RWGS : CO
2
H
2
=COH
2
O (10)
The importance of using chemical steady-state conditions for the study of
the reverse water-gas shift reaction was highlighted during our investigation
comparing the rate of removal of surface species during a purge in an inert
gas and during an isotope exchange.
50,51
Our data clearly showed that the
reactivity of surface species, in particular that of carbonate species, was
markedly dierent under these two gas streams (Fig. 11). We believe that the
dierence of reactivity observed was related to the dierence in the oxi-
dising/reducing nature of the feed, which altered ceria surface oxidation
state, which in turn modied the strength of the adsorbate bonding to the
ceria surface.
52
Another example of the importance of using chemical steady-state was
recently reported by Mims and co-workers in the case of methanol synthesis
over Cu/SiO
2
catalysts.
53
The authors measured the rate of decomposition
of the formates formed at the surface of Cu supported on silica during
methanol synthesis from CO/H
2
mixtures. The formate decomposition rate
Fig. 10 Schematical representation of the DRIFTS-MS-SSITKA technique for the operando
investigation of catalytic reactions. This technique is based on the utilisation of a single reactor
(i.e. the DRIFTS reactor) and allows following the kinetic of exchange of both gas phase
products P (by MS) and surface intermediates (by DRIFT) during a SSITKA-type experiment.
The surface species noted I represent a true reaction intermediate, while the surface species S is
a spectator (better called a minor intermediate). I* and S* are the corresponding labeled
surface species.
Catalysis, 2010, 22, 94118 | 111
was up to 3-fold lower in the case of a CO-free feed, as compared to the full
CO/H
2
mixture. Note that in this particular example,
53
formates seen by
IR were conclusively shown to be the main reaction intermediate. The
lower reactivity observed under not chemical steady-state was assigned to
the loss of co-adsorbates eects. These two examples strongly emphasise
that not using chemical steady-state conditions may lead to awed kinetic
investigations.
4.4 Operando SSITKA-DRIFTS-MS study of the RWGS
An example of the application of our DRIFTS-MS-SSITKA technique is
given below for the RWGS reaction.
48
Fig. 12 shows the typical DRIFT
spectra of formate, carbonyl and carbonate species during the isotope ex-
change
12
CO
2
to
13
CO
2
of the reactant. The replacement of
12
C with a
heavier isotope led to a red-shift of most of the wavenumber of the vibration
of the surface species of interest. Note that we were able to integrate in an
unequivocal manner the concentrations of the formate, carbonyl and car-
bonate species.
The corresponding exchange data of the surface species are reported in
Fig. 13, which showed that carbonates and carbonyl species were typically
half-exchanged in about 60 s. On the contrary the exchange time of formate
species was much longer, i.e. about 11 min. The corresponding MS data
showing the exchange of the gas-phase product CO is also shown in Fig. 13.
It is clear that CO was exchanged at a timescale similar to that of the car-
bonyl and carbonates, and therefore these species are potentially main re-
action intermediates, contrary to the formates. Formates should be named
as minor intermediates, rather than spectator species, since those still ex-
changes and probably led to some CO, albeit at a much lower rate than
those formed via the other surface intermediates.
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20 25 30 35 40
Time /min
R
e
l
a
t
i
v
e

D
R
I
F
T
S

i
n
t
e
n
s
i
t
y
Fig. 11 Relative intensity of the IR bands of the formate (
7
,
3
), carbonyl (,&) and car-
bonate (v,) species as a function of time on stream under Ar (solid symbols) and under
RWGS stream containing
13
CO
2
(open symbols). The sample was at steady-state state in 1%
12
CO
2
4% H
2
and T=498 K before switching to either Ar or the
13
CO
2
-containing feed.
(Reprinted from reference 50.)
112 | Catalysis, 2010, 22, 94118
4.5 Operando SSITKA-DRIFTS-MS study of the WGS
An example of DRIFTS-SSITKA-MS data relating to the water-gas shift
(WGS, 11) reaction over a 2% Pt-CeO
2
is given in Fig. 14.
54
WGS : COH
2
O =CO
2
H
2
(11)
The comparison of the exchange curves of the reaction product (here
CO
2
) and formate was more intriguing that in the case discussed above. The
2700 2800 2900 3000
Wavenumber / cm
-1
0.05 log 1/R
2841 cm
-1
2947 cm
-1
2825 cm
-1
2916 cm
-1
a
f
d
c
b
e
1800 1900 2000 2100
Wavenumber / cm
-1
0.1 log 1/R
2057 cm
-1
1977 cm
-1
2010 cm
-1
1904 cm
-1
a
f
d
c
b
e
800 820 840 860 880 900
Wavenumber / cm
-1
0.1 log 1/R
851 cm
-1
866 cm
-1
831 cm
-1
862 cm
-1
a
f
d
c
b
e
Fig. 12 Typical DRIFTS data of a DRIFTS-MS-SSITKA experiment during the RWGS over
Pt-CeO
2
: exchange of (top) formate (middle) carbonyl and (bottom) carbonate species at
various times after an isotope exchange
12
CO
2
to
13
CO
2
. Feed: 1% CO
2
4% H
2
. (Reprinted
from reference 41.)
Catalysis, 2010, 22, 94118 | 113
formate exchange was signicantly slower than that of CO
2
at 160 1C,
suggesting that formates were unimportant reaction intermediates at these
temperatures (Fig. 14). However, the exchange of these two species was
essentially identical at 220 1C, suggesting that formates could potentially be
a main reaction intermediate under these conditions.
The relevance of the formates seen by DRIFTS in the formation of CO
2
was ascertained by a quantitative comparison of the specic rate of CO
2
formation (measured by GC analysis of the DRIFTS cell euents, which is
more precise than that obtained by MS) and the specic rate of formate
decomposition. The latter was calculated as the product of the formate
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20 25 30
Time (min)
R
e
l
a
t
i
v
e

I
R

/

M
S

i
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Formate
Carbonyl
Carbonate
13CO
Fig. 13 Comparison of DRIFTS and MS data during a SSITKA experiment relating to the
RWGS over Pt-CeO
2
: the carbonate and carbonyl species are exchanged at a time scale similar
to the reaction product CO and are potentially reaction intermediates. On the contrary, for-
mates are clearly not main kinetic intermediates. (Reprinted from reference 48.)
0
0.2
0.4
0.6
0.8
1
0 5 10 15 20
Time / min
R
e
l
a
t
i
v
e

I
R

a
n
d

M
S

s
i
g
n
a
l
s
Formate, 220 C
Formate, 160 C
CO
2
, 220 C CO
2
, 160 C
Fig. 14 Comparison of the relative exchange of the gas-phase CO and CO
2
and surface for-
mate species during an isotopic exchange over the Pt/CeO
2
at various temperatures. Feed: 2%
13
CO, 7% H
2
O in Ar. The sample was initially at state-state under the corresponding non-
labeled feed. (Reprinted from reference 54.)
114 | Catalysis, 2010, 22, 94118
concentration by the pseudo-rst-order rate constant (noted k) of formate
decomposition:
45
Rate of formate decomposition = k [formate[ 100%
The value of k was determined from the formate exchange curve fol-
lowing the isotopic switch, which showed a rst order decay (i.e. ex-
ponential curve) (see Fig. 14). The formate concentration was determined
under reaction conditions via the calibration curves described else-
where.
41,45
The term 100% is introduced to indicate that we arbitrarily
assumed that the formate totally decomposed to CO
2
H
2
and not at all to
COH
2
O. Therefore, the decomposition rate of the formate species yielded
the upper limit of the rate of formate decomposition to CO
2
, since it is likely
that formates were not only decomposing to give CO
2
, but instead gave a
mixture of CO and CO
2
. Even assuming that formates decomposed solely to
CO
2
, the rate of formate decomposition for highly active Pt/CeO
2
WGS
catalysts accounted for less than 10% of the total rate of CO
2
formation in
the range of temperatures and experimental conditions used here, respect-
ively (Fig. 15). Therefore, the formates seen by DRIFTS are minor reaction
intermediates over this very active WGS catalyst. These observations
stresses that the similarity of the time constant of formates and CO
2
is not a
sucient condition to guarantee that formates seen by DRIFTS are main
reaction intermediates.
In some cases, formates seen by IR have been also considered essentially
as buer surface species;
55
whether those participate or not to the main
reaction pathway is unclear. In any case, while our work cannot indicate
what the main WGS reaction pathway is, it certainly stresses that observing
formates displaying some sort of reactivity is not a sucient criterion to
elect those as important reaction intermediates as proposed in many
instances.
56,57
Of course, our conclusions are based on the samples that
we investigated under our experimental conditions; therefore any extrapo-
lation outside this system is hazardous. DFT-based work carried out both on
ceria-supported noble metals and copper seems to favour the role of
R
a
t
e


/
1
0
-
6

m
o
l

s
-
1
g
-
1
CO
2
formation
Formate
decomposition
0
2
4
6
8
10
12
160 C
Reaction temperature
220 C 180 C
Fig. 15 Rate of CO
2
production and rate of formate decomposition over the Pt/CeO
2
at three
dierent temperatures under 2% CO7% H
2
O in Ar. (Reprinted from reference 45).
Catalysis, 2010, 22, 94118 | 115
carboxyl species (HOCO) as main reaction intermediate and exclude any
signicant role of formates.
58,59
The surface concentration of the carboxyl
intermediates was estimated to be more than a thousand-fold lower than
that of the buer formates, suggesting that a direct observation of these
short-lived species may be impossible by the current IR investigation
techniques.
58
4.6 Conclusions on the spectrokinetic investigation of catalytic reactions
A reliable study of a catalytic system using spectroscopic tools must to take
into account the following points:
i. It is crucial to check the kinetic relevance of the spectroscopic cell to be
used for operando work. Appropriately modied DRIFTS reaction cells
can behave as true kinetic reactor.
ii. DRIFTS work can be performed in a fully quantitative manner. In
most cases, the absorbance units are more appropriate than Kubelka-Munk
units.
iii. Chemical steady-state must be used to determine the true operando
reactivity of surface species, particularly for catalysts whose composition
are aected by the reaction conditions.
iv. The DRIFTS-SSITKA-MS is a truly operando technique and proved
useful in unravelling the (minor) role of formate species seen by DRIFTS
for the water gas shift reaction or CO hydrogenation over our samples. The
nature of the true reaction intermediates remains unknown over these
materials.
5. Overall conclusions
The examples reported here show that combining spectroscopic and kinetic
studies can greatly benet to the understanding of heterogeneous catalytic
reaction. The example dealing with the selective reduction of NOx showed
that reaction steps and/or elusive reaction intermediates could be postulated
by the observation of side-products and the reactivity of model compounds.
The use of fully quantitative methods also revealed that slowly reacting
surface species (i.e. spectators) can sometimes be easily mistaken for true
reaction intermediates. The conclusions derived from in situ/operando
spectroscopic work should therefore always be carefully thought through
and the corresponding limits of validity clearly dened.
We must be aware that far too often species observed by in situ/operando
spectroscopic analysis are spectators or minor reaction intermediates (be-
longing to a slow parallel pathway), and it is careless to jump to the con-
clusion that these species are important, simply because those can be seen
and even react. We hope that a more sensible view will now prevail, that is
because it can be seen, it is very possibly irrelevant to the main reaction
pathway and a proper quantitative spectrokinetic analysis is then carried
out to relate the specic rate of decomposition of these surface species to the
specic rate of product formation.
116 | Catalysis, 2010, 22, 94118
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118 | Catalysis, 2010, 22, 94118
Oxidative conversion of lower alkanes
to olens
K. Seshan
a
DOI: 10.1039/9781847559630-00119
1. Introduction
In the current scenario of decreasing oil reserves, light alkanes oer choice
as feedstock for chemicals, fuels and energy. They are available as Natural
Gas (NG, methane, ethane) and Liqueed Petroleum Gas (LPG, propane,
butanes) in the earths crust. Gas reserves are expected to last for a number
of years and will thus become important feedstocks, compared to crude oil,
for reneries and petrochemical plants for years to come.
13
Light olens
(ethene, propene, butenes) are the current building blocks for the synthesis
of: (i) bulk chemicals, e.g., ethylene oxide, acrolein (ii) polymers, e.g., poly-
ethylene, -propylene or -butenes or (iii) fuels such as diesel, gasoline, e.g., by
butene/butane alkylation.
Direct synthesis of these bulk products from alkanes is still not exten-
sively commercialized maleic anhydride from butane being one of the few
example.
4
Alkane conversion to olens is therefore a key step in the
manufacture of bulk chemicals and fuels. As the title suggests, this review is
restricted in scope to oxidative alkane conversions to lower olen, which are
intermediates to fuels e.g., gasoline, and chemicals e.g. oxygenates such as
acrolien, acetone, maleic anhydride etc, via various chemical routes as
practiced in a renery/petrochemical complex.
Direct/single step conversion of alkanes to such chemicals is equally inte-
resting from the scientic and economic point of view. There has been tre-
mendous amount of attention in the academic and industrial laboratories for
the development of ecient catalysts for such routes. This topic is beyond the
scope of the current review, and readers are directed to reviews on these topics.
Some key areas that have dominated in the last years are (i) direct oxidation of
methane to methanol or formaldehyde,
57
ethane to acetic acid/acetal-
dehyde
810
(iii) propane to acrolien,
11,12
acetone,
1315
propylene oxide,
16
(iv) butane to maleic anhydride.
4,17
The present industrial capacity for lower olens (C
=
2
C
=
4
) is expected to be
insucient, as the demand for these important components in the modern
renery/petrochemical industry grows.
18
These light olens are currently
produced using fossil oil, e.g., from catalytic or steam cracking of naphtha and
associated gas, or from uid catalytic cracking of vacuum gas oil. While these
two routes are well developed, increasing the capacity of these processes is only
possible to some extent, as changing regulations limit the use of byproducts
(notably aromatic molecules) in fuel. In this context, methane as a feedstock
has drawn wide attention. Tremendous eorts both at academic and industrial
laboratories in the 80s and 90s to convert methane to ethylene via catalytic
oxidative coupling did not lead to commercial success.
19,20
The research failed
a
Catalytic Processes & Materials, Faculty of Science & Technology, University of Twente,
#ME-361, PO Box 217, 7500 AE, Enschede, The Netherlands
Catalysis, 2010, 22, 119143 | 119
c
The Royal Society of Chemistry 2010
to develop catalysts that resulted in appreciable ethylene yields the maximum
yields reported were o30%,
21
and this was the major stumbling block.
Oxidative coupling of methane basically requires two elementary steps,
viz., (i) CH bond cleavage in methane to produce CH
d
3
or CH
d
2
radicals,
and (ii) coupling of these radicals to produce ethane or ethylene, respect-
ively. The former is an endothermic reaction and considering the strength of
the CH bond (232 kJ/Mol) in methane, requires very high temperatures
(W750 1C).
22
Unfortunately, the CC coupling is an exothermic reaction
favored at lower temperatures. There is thus a fundamental barrier to at-
tempts to convert methane via oxidative coupling, and the failure to achieve
appreciable ethane or ethylene yields is not surprising. Methane activation
at lower temperatures where the exothermic coupling is more favorable
could be a more promising method, as will be shown later in this chapter.
18
The conversion of propane and butanes is more straightforward, as (e.g.)
steam cracking is well established and is commercially practiced for the
production of C2 to C4 olens. Steam cracking follows a radical chemistry
route, the carbon radicals (primary or secondary) formed initially via CH
bond cleavage result in smaller primary radicals after subsequent b-cleavage
(see Fig. 1). As radicals do not undergo isomerisation, every further
b-cleavage of the primary radicals formed results in C2 product. Steam
cracking therefore maximizes ethylene yields, and this route becomes less
attractive when propylene demand grows faster than that of ethylene.
23
Catalytic cracking over zeolitic and other solid acid catalysts, on the other
hand, follows an ionic mechanism (Fig. 2) involving carbo-cations (carbe-
nium ions mostly, C
n
H

2n1
). Carbo-cations do undergo isomerisation
easily, since hydride (H

) transfer is facile over the ionic zeolite lattice.

Isomerisation leads to the more favorable secondary carbo-cations, which
on b-cleavage lead to olens with three or more carbon atoms depending on
the carbon chain length in the reactant hydrocarbon. Catalytic cracking is
thus an option for higher olens, however, most of the capacity in Fluid
Catalytic Cracking units is used for fuels, e.g. gasoline production.
Dehydrogenation of alkanes to olens is an excellent option for three
reasons: (i) alkanes are cheap feedstocks (ii) it has the advantage that it
generates olens, e.g.,
C
3
H
8
!C
3
H
6
H
2
DH 117 kJ mol
1
with the same carbon number as the alkanes and (iii) byproduct hydrogen is
in extremely high demand. However, dehydrogenation reaction technology
+
Fig. 1
+
+
Fig. 2
120 | Catalysis, 2010, 22, 119143
has some major disadvantages, as the yields are limited by thermodynamic
equilibrium, and there is a strong tendency to coking and consequently
catalyst deactivation can be severe, leading to short lifetimes.
2428
Catalyst
lifetimes are indeed small in practical commercial applications, e.g., eight
hours to a few seconds (continuous catalyst regeneration) are reported. The
existing processes for the dehydrogenation of light parans such as OLE-
FLEX (UOP, Pt/Al
2
O
3
catalyst),
25
CATOFIN (ABB and Lummus Crest,
Cr catalyst),
26
STAR (Phillips Petroleum Company, Pt based catalyst),
27
and FDB-4 (Snamprogetti-Yarsintez, Chromium oxide)
28
typically consist
of catalyst regeneration (i.e., carbon burn-o) in combination with heat
integration. These processes appeared in the early 80s but have made only
limited breakthrough commercially.
Continuously increasing global demand for light alkenes has, therefore,
spurred substantial interest in the development of alternative routes in-
volving light alkanes as feedstocks. The incentive for alternative processes is
predicted to grow in the future as the increase in the availability of light
alkenes from reneries is expected to be quite limited.
29
Therefore oxidative
conversion of alkanes to olens presents an available option. This is
achieved via selective combustion of the hydrogen formed in the conversion
of alkanes to olens,
C
3
H
8

1
=
2
O
2
!C
3
H
8
H
2
O DH 126 kJ mol
1
and the reaction is termed oxidative dehydrogenation.
30
The major ad-
vantages of oxidative dehydrogenation over conventional dehydrogenation
is that it: (i) overcomes the thermodynamic equilibrium limitations on olen
yield faced in the direct catalytic dehydrogenation (ii) minimizes the coke
formation and the related catalyst deactivation during conversion due to the
presence of oxygen and (iii) avoids the need for heat input, as the reaction is
exothermic and can be run adiabatically and at lower temperatures.
30,31
Oxidative conversion (coupling) of methane was extensively studied, as
mentioned earlier, however olen yields have not been impressive enough
for commercial applications. Oxidative dehydrogenation of ethane has also
been studied by more or less the same researchers and over similar catalysts
also without success.
32
Currently, there is tremendous interest in the oxi-
dative conversion of propane and butane.
Oxidative dehydrogenation of alkanes to olens is therefore still at a de-
velopmental stage despite the enormous amount of research and develop-
ment activities carried out by academic/industrial laboratories. No
commercial process is operative at the moment. Development of catalysts
that minimize combustion and maximize olen yields is still the bottleneck.
33
This review addresses the eorts over the last few years, by us specically
and by others, toward characterizing the catalyst materials and discerning
their relation to the kinetic and mechanistic sequences involved in the
conversion of alkanes to olens in the presence of oxygen. This review is
spread into three general areas. Many catalysts reported are essentially
oxides,
34
and they operate via a Mars van Krevelen redox type mechanism
and generate olens with the same carbon number. These are discussed
rst. Recent studies on oxidic catalysts with no formal redox properties
have shown tremendous improvement in olen yields. In this situation, in
Catalysis, 2010, 22, 119143 | 121
addition to the CH bond scission via oxidative dehydrogenation, CC
bond cleavage is also observed and this results in a mixture of olens with
dierent carbon numbers. This process is termed oxidative cracking and
discussed next. Finally, recent eorts in alkane activation using cold plasma
at ambient conditions in micro reactors shows that oxidative CC bond
coupling is possible at these conditions. This leads to molecular weight
buildup, i.e., the formation of olens with a higher C-number than the
starting alkanes, and promises exciting new chemistry and applications.
This is discussed last. A few thoughts on futuristic scenarios complete the
manuscript.
2. Oxidative conversion of alkanes to olens over oxide catalysts with
redox properties
Among the alkanes, methane conversion to olens has been the most
studied process. Most of these developments took place in the 80s and
90s. All sorts of oxidic catalysts were attempted, with alkali and alkaline
earth oxides the most studied.
1,2
In the case of methane, attempts
were focused in the catalyst/oxygen assisted cleavage of CH bonds to
yield CH
2
, CH
3
radicals. Coupling of these radicals was expected to yield
ethylene or ethane, respectively, and the process was termed oxidative
coupling. In spite of the enormous amounts of research and development,
C2 yields were limited (o30 mol%), breakthroughs did not appear and
eorts stopped in the 90s. The major barrier to conversion was that se-
lective CH bond activation in methane required very high tempera-
tures (700800 C), even in the presence of a catalyst and oxygen. At these
high temperatures, radical coupling, which is essentially exothermic, was
not a facile process and hence C2 yields never were appreciable. We do not
attempt to go into these details and readers are directed to excellent
reviews from M. Baerns, J.R.H. Ross
1
and Lunsford.
2
Later in this
manuscript, we will show that if the activation of CH bonds in methane
can be achieved at lower temperatures, CC coupling reactions can be
facilitated.
18
Ethane is a relatively cheap feedstock and is mostly associated with me-
thane in the natural gas stream. As in the case of methane, ethane con-
version focused on (oxy)dehydrogenation to ethylene. Most of the research
was carried in the same laboratories that were studying oxidative coupling
of methane. The catalysts studied were therefore similar to those attempted
for methane.
32
Again, no signicant breakthroughs were made. Results
from Union Carbide on V-Nb-Mo based catalysts showed initial promise
(very high ethylene selectivities were reported), but did not lead to com-
mercial success.
35,36
Conversion to syngas (COH
2
) by oxidation with water (steam re-
forming), carbon dioxide (dry reforming) or oxygen (partial oxidation) re-
mains still the main route for the valorization of these alkanes, especially
methane.
The ever increasing demand for higher olens such as propene and
butene, their limited availability from steam/catalytic cracking operations
and the cheapness/abundance of propane and butane (LPG) has meant that
122 | Catalysis, 2010, 22, 119143
development of catalysts for oxidative dehydrogenation of these feed stocks
is still an attractive option.
Most of this work was focused on vanadia- or molybdena-based oxide
systems which undergo redox changes during the conversion. Acidic (Al
2
O
3
,
SiO
2
) and basic (MgO, CaO) oxides have been used as supports. Basic
supports such as MgO have been the most benecial, because they minimize
re-adsorption of product olen and thereby minimize combustion. Rela-
tively high yields were reported for Mo-Ni-O catalysts,
37
(30% conversion
of propane with 60% selectivity at 600 1C) and V-Mg-O catalyst
34
(33%
conversion of propane with 42% selectivity, also at 600 1C). However,
limited olen selectivity at higher alkane conversions is linked to strong
olen adsorption (on cationic Lewis acid sites) and the subsequent oxi-
dation to carbon oxides. This is clearly visible in the results shown in
Fig. 3.
31
This behavior is typical for almost all the catalysts studied. At
higher propane conversions, sequential oxidation of the propylene product
to carbon oxides becomes signicant. Among the vanadia based catalysts
reported, use of niobia as a support has been shown to improve propylene
selectivity
31
up to 80 mol%. Niobia is a non acidic support it is reported to
lose all its Bronsted and Lewis acidity when calcined above 350 1C.
38
The
absence of acidity clearly reduces product olen re-adsorption, and min-
imizes its sequential combustion. Such catalysts give higher olen selectiv-
ities, but the presence of residual acidity, which cannot be completely
removed, is still detrimental. However, even on these catalysts, higher
propane conversions lead to loss of olen selectivity, as can be seen from
Fig. 4. Higher temperatures give better yields, but the secondary com-
bustion of olen cannot be avoided.
Lattice oxygen in these oxides participates in the oxidation (oxidative
abstraction of hydrogen) of the alkane. It is suggested by Kung et al.
34
that
the CH bond is split homolytically over the vanadia catalysts, creating
propyl radicals. Kung et al. further elucidated the role of homogeneous
radical reactions in oxidative dehydrogenation of propane over V-Mg-O
catalysts, revealing the contribution of each component (homogeneous and
0 2.5 5 7.5 10
0
2
4
6
Contact time [s]
Y
i
e
l
d

[
m
o
l
%
]
Propene
CO
2
CO
425 C
Fig. 3 Oxidative dehydrogenation of propane over V
2
O
5
/MgO catalyst, inuence of contact
time (conversion) on yields.
Catalysis, 2010, 22, 119143 | 123
heterogeneous) in the overall process.
39
The hydroxyls thus formed are
released to the gas phase as water, reducing the catalyst. Alternatively, the
lattice oxygen also takes part in the combustion of the alkane. Re-oxidation
of the catalyst by gas phase oxygen completed the catalytic cycle and re-
generates the catalyst.
The nature and concentration of surface active sites determine propane
conversion and product selectivity (olen vs. CO
x
). Low Energy Ion Scat-
tering is a useful technique to determine surface concentrations of oxide
species. Compared to XPS, which probes a few atom layers, LEIS allows
measurement at the outermost layer. Hence it is an optimal method to
determine activity correlations. Fig. 5 shows a correlation between intrinsic
activity (TOF, s
1
) for propane conversion as a function of surface vanadia
concentration for a series of catalysts determined by LEIS.
40
An increase in
0 5 1 15 20
0
4
8
Propane conversion [mol %]
P
r
o
p
e
n
e

y
i
e
l
d

[
m
o
l

%
]
V-Nb-O bulk
V-Nb-O monolayer
Vanadia
Niobia
425C
Fig. 4 Conversionyield plots for a series of vanadia based catalysts at 425 1C.
0
1
2
3
4
0 10 20 30 40 50 60
I
n
t
r
i
n
s
i
c

a
c
t
i
v
i
t
y

p
e
r

s
i
t
e
(
A
r
b
i
t
r
a
r
y

U
n
i
t
s
)

Surface V concentration (mol %)
Fig. 5 The intrinsic activity per V site as a function of the surface V site concentration de-
termined by LEIS. The intrinsic activity per site is determined by dividing the propane con-
version by the surface V concentration and is normalized to 1 for the lowest activity.
124 | Catalysis, 2010, 22, 119143
intrinsic activity (activity per site) as a function of vanadium concentration
suggests that dierent vanadia sites of varying catalytic activity must be
present at the surface.
51
V solid-state NMR allows one to discriminate various vanadia species
41
based on chemical shift anisotropies (see Fig. 6). Our measurements showed
that three types of vanadia species were present i.e., vanadium in an isolated
tetrahedral oxygen environment, in corner sharing tertrahedra, and in dis-
torted octahedra. The number of octahedral sites increased with increasing
vanadium concentration. Thus when the vanadium concentration is chan-
ged the types of species on the surface and their concentrations change.
Larger vanadia clusters (Q1, Oct) have linking oxygen bonds between them
which are susceptible to redox changes under the oxidative dehydrogenation
conditions. Vanadium in dierent oxygen environments and their dierent
redox natures would be the reason for the changes in intrinsic activities
when catalysts with dierent vanadia loadings are considered.
Oxides typically contain a variety of oxygen species, e.g., vanadia exhibits
both VOV bonds holding the vanadia octahedra together or dangling
V
Q
O bonds. These bonds can be easily characterized by IR spectroscopy.
There is debate over the role of these oxygens in the selective oxidation and
combustion of propane. It has been claimed that V
Q
O bonds lead to
combustion while VOV bonds are involved in selective oxidation to
olens.
42
This is based on the observation that V
2
O
5
, which exhibits V
Q
O
bonds, mostly gives combustion. Supporting V
2
O
5
on MgO results in the
formation of magnesium orthovanadates, which do not have V
Q
O bonds.
These catalysts are more selective to propylene formation and combustion is
minimized. Alternatively, the oxygen present in the VOV bond has been
characterized as responsible for olen formation as well as combustion.
However, oxide based catalysts which show facile redox properties tend to
catalyze sequential combustion of the olen formed. A detailed survey by
Cavani and Triro showed,
37
the limits achieved olen yields were almost
always below 30 mol%. This situation has changed very little in the last few
Fig. 6 Width of the static
51
V chemical shielding anisotropy as a function of the vanadium
coordination.
Catalysis, 2010, 22, 119143 | 125
years, and the search for an ecient catalyst to convert C3C4 alkanes to
olens is still on.
In order to eciently convert alkanes to olens, the critical issue for
catalyst development is to minimize olen sorption and further oxidation.
This issue is discussed in the next section.
3. Oxidative conversion of alkanes over oxide catalysts with no formal
redox properties
Despite the tremendous amount of work reported in the litera-
ture,
19,20,33,34,3743
a commercial breakthrough for oxidative conversion of
alkanes to olens is still lacking. As discussed in the previous section, one of
the major diculties in developing ecient catalysts has been the fact that
the product olen is more prone to combustion than the starting alkane.
45
Thus higher olen selectivities can be obtained only at low conversions, and
olen yields decrease at higher conversions due to sequential oxidation of
the olen.
31
Olen re-adsorption and subsequent combustion on the re-
ducible oxide catalyst is indeed claimed as the reason for the lack of exciting
progress in the eld of oxidative conversion/dehydrogenation of al-
kanes.
23,3133,45
One way to overcome this problem may be to minimize the olen sorp-
tion on the oxide catalyst, even modifying it to favor desorption. Olens are
nucleophilic, electron rich, and thus an oxidic surface with basic (non-
acidic) properties would be a proper choice.
23
Basic alkali and alkaline earth oxides have been attempted as catalysts for
the oxidative coupling of methane to ethylene
9,43
and the oxidative de-
hydrogenation of ethane to ethylene.
32,44
One of the most studied catalysts
is Li/MgO. Work in the last years shows that it is also a promising catalysts
for the oxidative conversion of propane and butane.
23
As expected (Fig. 7),
the Li/MgO catalyst shows olen selectivity for the oxidation of propane
that is almost independent of conversion. This is dierent from the case of
redox-type catalysts reported in the previous section. It can be seen from
0
0 30 60
2
4
6
8
10
conversion (%)
m
o
l
%
olefin selectivity
yield
585C
Fig. 7 Oxidative dehydrogenation of propane selectivity to olens function of propane con-
version for 1 wt% Li/MgO catalyst, results obtained varying space velocity.
126 | Catalysis, 2010, 22, 119143
Fig. 8 that the olen yields vs. conversion are almost linear and no sec-
ondary conversion of olens to CO
x
is observed. This also implies that high
olen yields (50 mol%) can be achieved, as seen from Fig. 8.
As reported often in the case of methane coupling, the catalytic activity of
Li-promoted MgO is determined by surface [O

] species, and their exist-

ence in MgO was mainly shown using the electron paramagnetic resonance
(EPR) technique.
43,46,47
Lunsford suggested that the [O

] species was cre-

ated by the substitution of Li

for Mg
2
ions to allow charge balance, and
was stabilized in the MgO lattice as [Li

] centers.
48
Remarkably, [O

]
are reported to be very stable at high temperatures and can exist in the
crystal lattice of metal oxides even in the absence of oxygen in the gas
phase.
49
The similar ionic radii of Li

(r
Li
=0.76 A

) and Mg
2
(r
Mg2
=0.72 A

)
allows easy accommodation of Li

in the lattice of MgO.

50
Replacement of
Mg
2
by Li

creates lattice defects, i.e., oxygen vacancies (positive holes)

(Scheme below). The proposed active site [Li

] is produced by a hole
adjacent to a Li

site trapping an oxygen atom.

51,52
2Li
0
Mg
O
x
O
V
O
d

1
=
2
O
2
!2Li
0
Mg
O
O
d
O
x
O
Scheme: Proposed mode of formation of the [Li

] (shown in Kroger-
Vink notation above) active site in Li/MgO catalysts. A hole trapped at
the O
2
is adjacent to Li

sites.
51,52
Unlike conventional Li/MgO catalysts prepared by impregnation, sol gel
methods used recently give high surface area Li/MgO, where such defect
sites are enhanced and lead to improved catalyst activity.
53
Evidence for the presence of [Li

] defect sites in these catalysts also

comes from IR spectroscopy measurements.
54
In the case of MgO-based
materials, surface sites of low coordination, i.e., Mg
2
LC
O
2
LC
pairs can be-
have as strong acid-base pairs. The weak adsorption of CO (hence the low
0
25
50
0 25 50 75 100
Conversion (mol%)
Y
i
e
l
d

(
m
o
l
%
)
600C
Total olefins
COx
Propene
Fig. 8 Oxidative dehydrogenation of propane over Li-MgO based catalysts.
Catalysis, 2010, 22, 119143 | 127
temperatures required to observe them, at 193 1C) on Lewis acid sites
such as Mg
2
LC
produces IR bands at frequencies higher than the stretching
frequency of the free CO molecule in the gas phase,
55
and thus provides a
tool for probing these surface sites.
IR spectra of CO adsorbed on Li/MgO catalysts prepared by sol gel
methods, at 193 1C, (Fig. 9) show evidence for the presence of such sites.
In the case of 1 and 3 wt% Li/MgO, the spectra show three bands at ap-
proximately 21642168, 21522155 and 21462148 cm
1
. These bands were
also present in the spectra of CO adsorbed on MgO-sg and are assigned to
CO adsorbed on Mg
2
4C
single sites, Mg
2
5C
single sites, and anchored to
Mg
2
4C
and Mg
2
5C
at the step site, respectively. For the sample with the
highest lithium loading (5 wt%), additional weak bands at 2200 and
2184 cm
1
were also present. The band at 2200 cm
1
is attributed to a CO
molecule interacting with a Mg
2
3C
site.
56
Based on DFT calculations, the
adsorption at 2184 cm
1
can be attributed to the addition of a second CO
molecule to the CO-Mg
2
3C
adduct, resulting in the formation of dicarbonyl
species.
56,57
In addition, changes in the relative distribution of all the
components present in the spectra were observed. The appearance of sites of
lower coordination of lithium atoms due to a decrease of the particle size
can be certainly excluded, since the addition of lithium causes a substantial
decrease in surface area and increase in particle size. Thus, sites of low
coordination such as Mg
2
3C
, which require oxygen vacancies near them,
indicate incorporation of lithium in the lattice structure of MgO, creating
the oxygen vacancies.
2105 2125 2145 2165 2185 2205
Wavenumber cm
-1
A
b
s
o
r
b
a
n
c
e

(
a
.
u
.
)
a
C
=
O
C=O
C
=
O
C
=
O
b
c
Mg
2+
5C
Mg
2+
5C
Mg
2+
4C
Mg
2+
3C
Mg
2+
4C
Fig. 9 IR spectra of CO adsorption at -193 1C over (a) 1 wt% Li/MgO, (b) 3 wt% Li/MgO and
(c) 5 wt% Li/MgO catalysts prepared using sol-gel method.
128 | Catalysis, 2010, 22, 119143
Extensive work from the groups of Lunsford et al., and Ross et al., Seshan
et al., have shown, in the case of Li/MgO catalysts, that the rst step in the
oxidative conversion of methane involves the homolytic scission of CH
bonds forming surface OH groups and alkyl radicals (1):
19,23,43,46,47
O
S
CH
4
!OH
S
CH
3
d
1
The resulting radicals are released from the catalyst surface and sub-
sequently initiate gas-phase chain propagation reactions to yield products.
23
In the case of vanadia-type redox catalysts, the only products obtained in
the case of propane or butane were the corresponding olens (i.e., propene
or butene), and carbon oxides. The product distribution obtained during the
oxidative dehydrogenation of propane over a Li/MgO catalyst is given in
Table 1. The presence of C1C2 hydrocarbons in the products indicates that
both CH scission (oxidative dehydrogenation) and CC bond splitting
(oxidative cracking) occur over Li/MgO.
In order to explain these observations, reaction sequences similar to that of
oxidative coupling of methane over Li/MgO catalysts have been proposed
(Fig. 10). These sequences involve initiation at the catalyst surface followed by
gas phase homogeneous reactions.
43
Leveles et al.
23
discussed the perform-
ance of the catalyst tested in relation to the reaction mechanism for propane
ODH and reported that propane activation occurs via a CH bond splitting
Table 1 Oxidative dehydrogenation of propane over Li/MgO catalysts at 550 C,
propane conversion 15%
Component COCO
2
Methane C
2
C
=
2
C
=
3
Selectivity (mol%) 15 10 30 45
HO
2

O
2
H
2
O
2 2 HO
CH
3
C
3
H
8
C
3
H
8
CH
4
H
2
C
2
H
4
C
3
H
6 H
nC
3
H
7

iC
3
H
7

O
2
CO
x
CH
2
O
H
2
O
Fig. 10 Proposed reaction mechanism for gas phase propyl radicals.
Catalysis, 2010, 22, 119143 | 129
which is also the rate determining step. Propane activation takes place on the
[Li

] active site by homolytic hydrogen abstraction, forming [Li

OH

]
and propyl radicals equation (1). There is general evidence that the two dif-
ferent primary radicals formed after heterogeneous activation, n- and iso-
propyl radicals, are released from the catalyst surface to the gas phase, and
radical chain reactions lead to the nal products. For the propyl radicals
formed, two dierent decomposition routes have been proposed for the gas
phase: (i) the isopropyl radicals can undergo scission of CH bond at the a-
position and decompose into propylene and H an radical and (ii) the n-propyl
radical undergoes CC cleavage in the b-position, forming a methyl radical
and ethylene (Fig. 10). Thus, the cleavage of a CH bond (dehydrogenation)
versus cleavage of a CC bond (cracking) is the processes controlling the
selectivity to, respectively, propylene and ethylene. At a relatively low T
(o600 1C), and at a low conversion level of propane, the contribution of the
gas phase reactions is less, and a propylene to ethylene ratio higher than 1 was
observed.
23
At higher temperatures (Z600 1C), a decrease in the rate of de-
hydrogenation and an increase in cracking was recorded.
Surprisingly, for identical conversions, increasing the number of defect
[Li

] sites improved selectivity to olens and higher propylene to

ethylene ratio in the products was observed. Indeed, as Kondratengo et al.
reported, in the case of propane ODH over vanadium oxides systems in-
creasing the density of active sites aected the olen distribution.
58
In
particular, they suggested that a high density of oxidizing sites is essential
for further ODH of the propyl radicals to propylene, and therefore sup-
pression of the concurrent cracking reaction pathway to ethylene.
Similarly, in the case of Li/MgO-sg catalysts with a high density of active
sites (per volume of catalytic bed), heterogeneous H-atom abstraction from
C
3
H
d
7
-radicals yielding propylene eq. (2) can be more ecient than reaction
of C
3
H
d
7
-radicals in the gas phase and this can aect the propylene to
ethylene ratio.
Li

C
3
H
!
7
Li

OH

C
3
H
6
2
Propane activation on [Li

] active centers, leading to the propyl

radical, is a single site interaction. The chance that the propyl radicals may
further react with a second [Li

] active site leading to propylene

(multiple site interactions) strongly depends on site density. The nal
step
43,59
is the regeneration of the active site, which involves electron
transfer to the anion vacancy and the dissociative chemisorption of oxygen,
respectively eqn. (3) and (4):
Li

O
2
Li

V
a
!Li

Li

a
3
Li

a
O
2
!Li

O 4
However, certain features in the Ito-Lunsford mechanism appear to be
unlikely, especially at lower temperatures. In particular, removal of oxygen
from the lattice is not facile and this would be the rate-limiting step of the
catalytic cycle rather than hydrogen abstraction.
59
Moreover, migration of
a proton would require: (i) substantial energy to overcome the electrostatic
barrier
60
and (ii) the proximity of [Li

] centers.
61
130 | Catalysis, 2010, 22, 119143
Alternatively, Sinev
62,63
proposed a new mechanism for regeneration of
the active sites that does not require the removal of lattice oxygen and thus
the formation of oxygen vacancies. In fact, the re-oxidation of the catalyst
can proceed by the mechanism of oxidative dehydrogenation of surface OH
groups, which requires the scission of strong OH bonds. More specically,
the regeneration reactions proposed by Sinev (Fig. 11) are summarized as:
64
O
2
OH

!O

HO
2
d
5
HO
2
d

OH

!O

H
2
O
2
6
H
2
O
2
!2OH 7
OHOH

!O

H
2
O 8
It is appropriate to stress that the overall reaction for regeneration is the
same as in the mechanism proposed by Ito and Lunsford.
59
In fact, it in-
volves the participation of two surface [OH

] groups and the formation of

water. However, it does not require removal of lattice oxygen. It is known
that Li/MgO catalysts deactivate if no oxygen is present during reaction.
Additionally, the deactivation was not accompanied by water formation.
This implies surface deactivation without any lattice oxygen removal and,
most likely, that formation of oxygen vacancies as intermediates does not
take place. To conclude, under these deactivation conditions surface [OH

]
groups are formed, and are stable in the absence of gas phase oxygen. Thus,
Li/MgO catalysts do not show any reducibility at 550 1C.
Remarkably, only during the interaction of oxygen with the catalysts
pretreated in propane or hydrogen was the evolution of water was observed.
This may suggest, as proposed by Sinev, that at 550 1C the re-oxidation of
Li/MgO catalysts proceeds as some sort of oxidative dehydrogenation of
surface hydroxyl groups (Fig. 15). Our observations suggest that only at
higher temperatures (700 1C) i.e., at methane coupling conditions, the
scheme proposed by Lunsford is operative. But, in the case of oxidative
dehydrogenation of higher alkanes, which occur at lower temperatures
(500 1C) the catalyst regeneration goes via traditional re-oxidation with a
de-hydroxylation step involving the formation of oxygen vacancies.
4. Catalytic alkane oxidation at ambient conditions using cold plasma CC,
CH scission vs CC bond coupling
Oxidative conversion of alkanes to olens, as shown in the last two sections,
is reported to be initiated by homolytic splitting of a CH bond resulting in
O O
H H
O
2
H
2
O
Fig. 11 Schematic drawing: mechanism of regeneration of the active sites as suggested by Sinev.
35
Catalysis, 2010, 22, 119143 | 131
radicals.
23,39,40,43,46,47,53,6567
In the case of catalysts with pronounced
redox properties, e.g. supported vanadia catalysts such as V
2
O
5
/MgO,
39
further conversions of the alkyl radical, adsorbed on the nucleophilic oxy-
gen of the catalyst, occur on the oxide surface in a typical Mars-van
Krevelen type redox mechanism. Oxygen from the gas phase regenerates
the oxide, which is reduced during alkane oxidation.
40
Accordingly, Kon-
dratengo et al. have shown recently that in the case of vanadium oxide
systems, a high density of oxidizing sites can favour H-atom abstraction
from C
3
H
7
radicals yielding propene.
58
In the case of oxide catalysts with no formal redox properties, e.g.
Li/MgO, the initial activation involves, again, homolytic CH bond split-
ting forming alkyl radicals. Because the oxygen in these type oxides is less
nucleophilic, the radicals are then released to the homogeneous gas phase
where radical chain reactions determine the composition of olens
formed.
53,58
Thus alkane to olen conversion on such catalysts involves a
route of heterogeneously-initiated homogeneous reactions. Results also
indicate that total oxidation (combustion) reactions occur both in the gas
phase and on the surface of the oxide.
68
The contribution of such homogeneous gas phase routes in heterogeneous
catalysis has been especially discussed in the last 20 years in the case of
oxidative coupling of methane to higher hydrocarbons
43
and oxidative de-
hydrogenation of light alkanes (ODH) to olens.
23
By varying the post
catalytic volume of the reactor and observing that this caused an increase in
conversion,
66
it was concluded that gas phase radical reactions make a
major contribution to such processes. In addition, direct evidence for the
presence of surface-generated gas-phase radicals has been provided by
spectroscopic methods, in particular by techniques such as matrix isolation
electron spin resonance (MI-ESR) and infrared spectroscopy (MI-IR), in
tandem with a catalytic reactor.
46
In the case of oxidative dehydrogenation of alkanes, using Li/MgO
catalysts, an increase in olen selectivity could be achieved by increasing the
number of active sites per volume of catalytic bed.
68
We suggested recently,
that the propyl radicals formed
Li O

C
3
H
7
d
!Li OH

C
3
H
6
9
could undergo a second hydrogen abstraction at the active sites leading to
propene,
68
indicating that olen formation on the catalyst surface is
possible.
Generally, propane activation involving CC or CH bond scission
37
requires higher temperatures (TW550 1C) even in the presence of a strong
[H
d
] abstractor such as [Li

]. Lowering the temperature of the reaction

can facilitate further radical conversions on the catalyst surface as in
equation (1). Therefore the olen selectivity can be manipulated by de-
veloping more active catalysts.
The use of cold plasma is one way to achieve CH bond activation at
ambient temperatures. Stable and cold gaseous plasma can be generated at
room temperature inside a micro reactor by dielectric barrier discharge.
70,71
The advantage of using a microreactor is that it allows generation of non-
thermal plasma at higher pressures, i.e., without the need for vacuum. This
132 | Catalysis, 2010, 22, 119143
plasma consists of energetic electrons which can activate alkane CH bonds
as a result of inelastic collisions.
71
Additionally, performing the reaction in a
micro scale system (channel dimensions 101000 mm) with intrinsically high
surface to volume ratio provides extreme quenching conditions on the
catalyst surface.
72,73
Thus a micro plasma reactor containing catalyst can be used to convert
light alkanes into more valuable molecules at room temperature and at-
mospheric pressure.
74
Incorporation of a stable catalyst layer on the reactor
wall is crucial in such a situation. In the case of catalytic reactions many
attempts have been made to deposit catalysts on the walls of micro reactors,
instead of introducing powder-type materials in the micro channels in
packed-bed fashion, which leads to a high pressure drop.
75
Figs. 12,13 show, respectively, the top and schematic cross sectional view
of the microplasma reactor used by Trionfetti et al.
68
It consists of a Pyrex
rectangular chip of 50 mm length15 mm width. Microchannels of 30 mm
length5 mm width and a channel depth of 500 mm were realized in the
chip by means of chemical etching using aqueous HF. Sandwich thermal
bonding of three Pyrex plates (one with, two without a channel) allowed
fabrication of the micro reactor. Details of the processing scheme are given
elsewhere.
76
Gas inlet and outlet holes were created by powder blasting
using Al
2
O
3
particles. The two copper ribbon electrodes connect to an ex-
ternal power supply in order to generate plasma by dielectric barrier dis-
charge (DBD) at atmospheric pressure.
90,91
A power output between 2 and
25 W is easy to stabilize. The power absorbed by the plasma can be calcu-
lated from the corresponding VQ Lissajous Figures.
77
The plasma gener-
ated in the DBD conguration consists of high energy electrons and is
characterized by a large number of micro-discharge laments (ionization of
the medium by the electrons), each lasting few nanoseconds.
78
These high
energy electrons (in the range 34 eV) are able to activate hydrocarbons and
oxygen at room temperature and atmospheric pressure.
79
The short life time
of the current spikes (ns) helps in minimizing local heating. Moreover, the
Fig. 12 Top view of the employed microplasma reactor made of Pyrex. The inlet and out let
are indicated (A, B). The copper plate is also well visible (C). This is connected to a power
supply using adhesive copper foils (D).
Catalysis, 2010, 22, 119143 | 133
small volume and the large surface to volume ratio of the micro reactor
allow fast removal of the heat produced during oxidation of alkanes.
The channels of the micro reactor were coated with Li/MgO catalyst layer
by wetting the walls with sol via micro-pipetting, allowing the sol to gel and
subsequently calcining at 500 1C to get the catalyst coating.
68,69,8083
Details
of the characteristics of the reactor and catalyst system are extensively
discussed elsewhere.
68,8083
Results obtained by us for propane oxidation highlight some very exciting
chemistry.
68
Fig. 14 shows the optical emission spectrum of C
3
H
8
He
plasma with 3 W power input. Electronic excitation of CH corresponding
to the A
2
D-X
2
P transition at 431.5 nm was used to determine the kinetic
gas temperature in this emission region.
77
The resolution of the spec-
trometer, calibrated using a UV lamp, was determined to be 0.7 nm (full
width at half maximum). This is not enough to resolve the individual ro-
tational lines of the Q, R and P branches of the CH band. However, the
rotational temperature, which reects the gas temperature inside the la-
mentary discharge, was calculated by comparing the CH band in Fig. 14
with those in simulated spectra at various temperatures using the LIFBASE
software.
84
The best t was obtained in the region of 2575 1C. Remarkably,
a thermocouple inserted inside the micro channel measured 75 1C at the
highest power of 24 W supplied from the source. In the case of the 3W used
in our experiments an average gas temperature of 25 50 1C was obtained.
Thus, the spectra in Fig. 14 indicate that propane activation occurs at close
to room temperature.
The existence of CH and H bands in the spectra shown in Fig. 14 indi-
cates decomposition of propane via both CC and CH bond scission. In
agreement with this supposition, the product stream showed components
typical of the oxidative cracking of propane as discussed earlier, i.e., CO
x
,
ethane, propene and acetylene. Most remarkably, in the case of the Plasma
Surface
Discharges
Dielectric-Pyrex
Catalyst layer
additional dielectric

Copper
Electrode
Fig. 13 Schematic drawing of the cross-sectional view of the employed microplasma reactor.
The 3 Pyrex plates forming the microreactor are schematically represented.
134 | Catalysis, 2010, 22, 119143
He
He
He
CH A
2
X
2

C
2
(d
3
-a
3
)
H
400
500 600 700
Wavelength (nm)
I
n
t
e
n
s
i
t
y

(
a
.
u
.
)
Fig. 14 Optical emission spectrum for a gas mixture of 10% propane in helium in the presence
of plasma; 3W power was applied.
C
3
H
6
CO
x
C
2
H
6
C
2
H
2
CH
4
C
4
>C
4
S
e
l
e
c
t
i
v
i
t
y

(
m
o
l
%
)
C
2
H
4
Products
0
10
20
30
Fig. 15 Selectivity to the main products for a plasma microreactor. Conditions: ow rate
15 ml/min, feed composition 10% propane, 1% oxygen and balance helium; activation at room
temperature. Formation of hydrogen was detected but not quantied.
Catalysis, 2010, 22, 119143 | 135
microreactor a substantial amount (37 mol%) of products with higher
molecular weights than propane, i.e., C
4
, C

4
, were also observed (Fig. 15).
The presence of products containing four or more C atoms requires CC
bond formation under the conditions present in the microreactor.
For Li/MgO catalysts, propane activation requires the presence of oxygen
and higher temperatures (TW600 1C)).
35,53,85
In these catalysts [Li

]
type defect centers are the active sites and their formation requires the
higher temperatures. The [Li

] site is claimed to have a high H-atom

anity and, at relative high temperature, is able to abstract H
d
from pro-
pane molecules forming n- and iso-propyl radicals as primary intermedi-
ates.
8587
These propyl radicals are formed depending on whether primary
or secondary hydrogen is abstracted from propane. At the higher tem-
peratures required for the reaction, endothermic decompositions are
favored and the two types of radicals (n & iso) undergo dierent unim-
olecular reaction routes in the homogeneous phase: iso-propyl radicals
undergo CH bond scission at the a-position, yielding propene and a
hydrogen atom, while n-propyl radicals preferentially undergo b-scission of
the CC bond, forming a methyl radical and ethylene.
88
The various
products formed can be accounted for by a series of radical chain reactions
in the gas phase, details of which were discussed earlier.
89
In a plasma microreactor, C
3
H
8
molecules are directly activated/con-
verted via collisions with energized electrons. Activation produces radicals
such as C
3
H
7
d
due to cleavage of CH bonds (2). These can initiate radical
chain reactions. Thus, reaction (10) is strongly inuenced by the number of
charges transferred or accumulated on the dielectric surface,
92
and therefore
by the relative permittivity.
C
3
H
8
e

!C
3
H
7
d
H
d
e

10
The reactivity of micro-plasma towards propane is improved when a layer
of Li/MgO was present. This is due to the larger permittivity of oxide layer
(9.7 C
2
/N
*
m
2
for MgO) compared to Pyrex (4.8 C
2
/N
*
m
2
).
9395
This allows
more impacts (and more inelastic collisions) giving rise to excitation of a
higher number of propane molecules.
In addition, propane activation can also occur via an indirect route, i.e.,
activation of gas phase oxygen by the plasma. It is also observed that in the
presence of oxygen and plasma the propane conversions are higher. Among
the atomic processes taking place in a non-thermal plasma, the electron
impact dissociation of O
2
to form charged and
e

O
2
!2Oe

!O

O 11
e

O
2
!O

2
e

!OOe

12
neutral oxygen has been reported in literature and is described in reaction
equations 3 and 4.
96
The O

species, present in the homogeneous phase, has

been reported to cause CH bond scission in alkanes e.g., methane,
97
eth-
ane.
98
In the case of propane this will result in the formation of propyl and
hydroxyl radicals as shown below:
O

C
3
H
8
!OH

C
3
H
7
d
13
136 | Catalysis, 2010, 22, 119143
Further, C
3
H
7
radicals react fast with O
2
forming hydroperoxyl (HO
2
d
)
radicals, which can react with propane molecules to form H
2
O
2
. De-
composition of H
2
O
2
results in hydroxyl radicals (OH
d
), which become the
main chain propagators.
47
[Li

] sites are defect sites and their existence at lower temperatures

has been investigated and conrmed, using EPR spectroscopy, by Lunsford
and others.
48,59,100
Improved propylene yields suggest that defect [Li

]
sites may already be present at low temperature in the presence of plasma
and oxygen, and that these sites abstract hydrogen from propyl radicals
forming propylene.
99
Alternatively, the presence of plasma can also help to
create other defect sites which are able to selectively terminate radicals.
Detailed studies are present in the literature describing the emission of UV
light during dielectric barrier discharge (DBD).
101
Nelson et al.
102
and later
E. Knozinger et al.
103
reported, using EPR studies, that interaction between
UV light and MgO particles can give rise to surface paramagnetic centers
(trapped electrons, typically F-centers, [V
d
O
]). Goodman et al. suggest that
these oxygen vacancies, containing one or two electrons (F-type defects), are
able to activate CH bonds during methane oxidative coupling.
104
Bond
scission occurs and the H
d
is trapped at the defect site. Thus, the presence of
[V
d
O
]-type defect sites caused by the plasma may allow H
d
abstraction from
propane and even from propyl radicals, and in the latter case enhanced
selectivity to propene can be expected.
Optical spectra recorded in presence of plasma (Fig. 18) show that CH-
type radical species are formed. Dimerization of such species can result in
ethyne, which is often detected in experiments with plasma and hydro-
carbons.
108
Hydrogen redistribution during this reaction, associated with
the formation of dehydrogenated products such as ethyne, may account for
the observation of methane.
This argument regarding dimerisation and formation of ethyne
105107
can
also be logically connected to the large amounts of C
4
and C

4
products that
we observe. The role of plasma is in the activation of propane and the for-
mation of radicals at ambient temperatures. The formation of C
4
and C

4
products from propane essentially requires CC bond formation, which
is an exothermic process and therefore favored at lower temperatures.
Therefore it is not surprising to see CC bond formation reactions under our
conditions. In conventional xed bed reactors, propane activation occurs at
higher temperatures (TW600 1C) in the presence of catalyst. These con-
ditions favor the rupture of CC bonds, and thus we see only products of
cracking or combustion, i.e., with molecular weights lower than that of
propane.
Considering that similar amounts of C
4
C

4
products are formed in the
microreactor both with and without catalyst, it is suggested that the
coupling of the radicals occurs predominantly in the homogeneous phase.
Unlike propane, ethane and methane contain only primary carbon atoms.
It would thus be interesting if CH bond activation is possible in these
molecules with plasma under oxidative catalytic conditions.
Under identical conditions ethane is less active than propane, as expected.
Table 2 shows typical product selectivities. Again, an appreciable amount
(22 mol%) of CC coupling products (C
4
C
3
) were observed.
Catalysis, 2010, 22, 119143 | 137
C
2
products were the most abundant species when methane was the
feedstock (Table 3). Appreciable amounts of C
3
(11%) and C
4
(2%)
products, demanding multiple CC couplings, were also found. Thus
activation by cleavage of the CC and CH bonds and CC coupling at
ambient temperatures are consistently observed for all three hydrocarbons
studied, viz, propane, ethane and methane.
109
Alkane activation occurs in the presence of plasma via collisions with
energized electrons, e.g., C
3
H
8
e

-C
3
H
7
d
H
d
e

.
110
In the presence
of helium this mechanism might become more ecient because the mean
free path of the electrons increases
111
due to the small cross section of highly
excited helium species created during electric discharge. These excited spe-
cies of helium, can also possess higher energy, up to nearly 20 eV, enough to
activate a hydrocarbon by collisions.
112
Alkane activation can also occur via an indirect route, i.e., activation of
gas phase oxygen by plasma. Among the atomic processes taking place in a
non-thermal plasma, the electron impact dissociation of O
2
to form charged
and neutral oxygen has been reported in the literature and is described in
equations 11 and 12.
113,114
The O

species, present in the homogeneous

phase, have been reported to cause CH bond scission in alkanes,
e.g., methane,
115
ethane.
116
In the case of propane this will result in the
formation of propyl and hydroxyl radicals as in equation 13. The reaction
between C
3
H
7
d
radicals with O
2
results in hydroperoxyl (HO
2
d
) radicals
which react further with a propane molecule to form H
2
O
2.
Decomposition
of the latter gives two hydroxyl radicals (OH
d
), which become the main
chain propagators.
23
All these reactions can initiate radical chain reactions,
but the main dierence is that these propagation and termination reactions
now take place at ambient temperature.
Eorts to make C
2
products by the oxidative coupling of methane,
extensively studied over several years,
117
had the inherent diculty that
methane activation required high temperatures and at the high temperatures
CC bond formation would be expected to be less favorable. Typically,
formation of CC bonds is an exothermic process and therefore favored at
lower temperatures. Therefore, it is not surprising to see CC bond
Table 2 Oxidative conversion of ethane. Selectivity (mol%) to the products
observed in a plasma microreactor. Conditions: 10% ethane and 1% oxygen
in helium, ow rate 15 ml/min, RT; 15% conversion level of ethane (mol%)
CO
x
C
3
H
8
C
3
H
6
C
2
H
4
C
2
H
2
CH
4
C
4
13 12 23 15 27 10
Table 3 Oxidative conversion of methane. Selectivity (mol%) to the
products observed in a plasma microreactor. Conditions: 10% methane
and 1% oxygen in helium, ow rate 15 ml/min, RT; 10% conversion level
of methane (mol%)
CO
x
C
3
H
8
C
3
H
6
C
2
H
4
C
2
H
6
C
2
H
2
C
4
30 11 49 8 2
138 | Catalysis, 2010, 22, 119143
formation reactions under the mild conditions present during plasma
experiments. CC bond coupling is also observed during olen metathesis
type reactions, also at room temperature, but requiring a transition metal
catalyst. Current scenarios for upgrading light hydrocarbons (increasing
molecular weight) for, e.g., alkylation,
118
metathesis
119,120
or oligomerisa-
tion
121,122
reactions (e.g., SHOP process
123,124
) involve at least one olen.
However, in our studies direct homologation of alkanes is observed. This
represents an interesting development for upgrading cheap low molecular
weight alkanes to commercially useful fuels and/or feedstock materials for
the chemical industry.
Acknowledgements
The author wishes to state his pleasure and thanks to students and col-
leagues who helped to carry out the work. In the hope of not missing
anyone, they include J. R. H. Ross, R. H. H. Smits, J. G. van Ommen,
H. M. Swaan, S. J. Korf, J. A. Lercher, I. Babich, S. Fuchs, L. Levels,
L. Leerts, A. Agiral, J. G. E. Gardeniers and C. Trionfetti.
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Catalysis, 2010, 22, 119143 | 143
Asymmetric hydrogenation of activated
ketones
Jo zsef L. Margitfalvi
a
and Emlia Ta las
a
DOI: 10.1039/9781847559630-00144
In this contribution key features of the asymmetric hydrogenation of
activated ketones over cinchona-Pt catalyst system are reviewed. Both
historical backgrounds and recent results are evaluated and discussed.
The focus is laid on the peculiarities of these reactions, such as (i) methods
and approaches used, (ii) substrate specicity, (iii) rate acceleration,
(iv) the form of conversion-ee dependencies; (v) inversion of ee,
(vi) nonlinear phenomena, (vii) origin of enantio-dierentiation and (viii)
character of modier Pt, substrate-modier and substrate-modier-Pt
interactions.
1. Introduction
1.1 General information
In order to reduce the environmental and health hazards the demand for
optically active compounds in high enantiopurity is increasing in the eld of
pharmaceutical, agrochemical and cosmetic products. Although the most
common applications are bio-related, there is also a great interest in the area
of materials science for chiral compounds, such as chiral polymers or chiral
liquid crystals. For this reason the interest to produce chiral compounds in
highly pure form is expanded over the past decades. There are dierent
approaches to obtain compounds in high enantiopurity. One of the most
environmentally friendly methods is the use of chiral catalysts.
13
There are
dierent approaches in chiral catalysis, such as homogeneous,
4
hetero-
geneous,
5
enzymatic,
6
and articial catalytic antibodies.
7
The common
feature of all approaches is that relatively small amount of chiral auxilarities
is required to produce chiral compounds in high enantiopurity. In this re-
spect the term multiplication of chirality
8
is often quoted. When het-
erogeneous catalysts are applied, the chiral auxilarities used are often called
as chiral modiers.
In the past decades, signicant progress has been achieved in homo-
geneous enantioselective catalysis, what is reected by the Nobel Prize
awarded in 2001 to Sharpless, Noyori, and Knowles. Variety of transition
metal complexes containing unique chiral ligands have been developed to
induce enantioselectivity by homogeneous catalysts. These chiral metal
complexes were used in various catalytic reactions, such as hydrogenation,
9
dihydroxilation,
10
epoxidation,
11
Diels-Alder reaction,
12
CC bond for-
mation
12,13
Michaels reaction,
14
etc. These reactions are considered have
great importance for the production of ne chemicals and pharmaceutical
products.
15
a
Institute of Surface Chemistry and Catalysis, Chemical Research Centre, Hungarian Academy
of Sciences, POB 17, 1525, Budapest, Hungary
144 | Catalysis, 2010, 22, 144278
_c
The Royal Society of Chemistry 2010
Homogeneous catalytic reactions are highly selective and require rela-
tively small amount of catalyst, however the chiral ligands and the metal
complexes used are relatively expensive. Homogeneous catalysts are sensi-
tive both to oxygen and moisture, for this reason the handling of these
compounds is quite troublesome. Additional serious problem is the catalyst
recovery. As the remaining trace impurities of metals have a denite en-
vironmental and health hazard the development of complex methods for the
removal of traces of transition metals increases signicantly the production
costs in homogeneous catalytic reactions. The immobilization of metal
complexes into inorganic or organic supports is one of the approaches to
overcome the above problems as immobilized catalysts can be separated by
ltration or can be used in continuous-ow reactors.
Homogeneous catalysts can be immobilized both to inorganic
16
and
polymeric supports.
17
Most of the cases the solid contains a ligand, what is
considered as an anchoring site.
In case of inorganic supports the reactivity of surface OH groups is used
to immobilize a given type of ligand upon using the reactive trimethoxy (or
trichloro) silane derivatives.
18
However, in this type of immobilized
homogeneous catalysts leaching of the metal-complex has often been
observed.
Among the new strategies to heterogenize transition metal complexes the
encapsulation of a chiral metal complex in micropores
19
and the use of
tethered type metal complexes have to be mentioned.
20
The tethered metal
complex catalysts were recently developed by Augustine and coworkers.
2123
These catalysts showed high activity and high chemo- and/or enantioselec-
tivity in various hydrogenation reactions.
When metal-complexes (both homogeneous and immobilized one) are
used the enantio-dierentiation is controlled by the structure of the metal
complex. In this respect the molecular character of the catalytic step has to
be emphasized, although the exact form or structure of the [metal complex
substrate] adduct is often unknown. In these enantioselective catalytic re-
actions the chirality and the helicity of ligands has a great importance to
control the enantio-dierentiation step.
24
This control can be either ther-
modynamic or kinetic in character. The distinction between these two
modes of control is often very dicult. Here we should like to refer to the
classical contribution made by Halpern and coworkers.
25
The most important class of ligands used in asymmetric reactions has a
chiral organic backbone with tertiary phosphino, amino and alcoholic
functional groups. Highly eective chiral ligands are often bidentate; i.e.
they have two coordinating sites for the coordination of the substrate
molecule. In chiral homogeneous catalysis, due to the high substrate spe-
cicity high enantioselectivities can only be achieved for a dened class of
substrate molecules, i.e., the right combination of metal and ligands has to
be found for each individual catalytic reaction.
26
Even though enantioselective homogeneous catalysis is still a relatively
young discipline, several enantioselective homogeneous catalytic processes
have already been used on an industrial scale.
27,28
As concerns the performance (enantioselectivity), the mechanistic insight
and general understanding heterogeneous enantioselective catalysis is far
Catalysis, 2010, 22, 144278 | 145
behind to its homogeneous analogue. Only a relatively narrow range of
prochiral compounds with C
Q
O and C
Q
C bonds can be hydrogenated
with high enantioselectivity. However, due to the above-mentioned draw-
backs in homogeneous catalysis, such as separation, reuse, and stability, the
interest for heterogeneous asymmetric catalysis increases permanently.
The rst publication related to asymmetric heterogeneous catalytic
hydrogenation was published by Schwab in the early thirties.
29
In the rst
attempts intrinsically chiral solids, such as quartz has been applied.
30
In other approaches chiral biopolymers or natural bers, such as silk broin
were used,
31
but due to the low optical yield and severe reproducibility
problems this approach has been almost completely discarded.
The discovery of the Ni/tartrate system for the enantioselective hydro-
genation of beta-diketones or their analogs was the rst real breakthrough
in this eld. This area has been recently reviewed.
3235
Optical yields over
90% were obtained for various substrates using the Ni-NaBr/tartrate sys-
tem.
36
In general this catalytic system requires a pre-modication of the
parent nickel catalyst with tartaric acid prior to the reaction in order to
form chirally modied sites involved in enantio-dierentiation. Recently,
the use of in situ modication procedures for Ni/tartrate system has been
described.
37
In this catalytic system reactive chemisorption of tartaric acid to the
nickel surface resulting in some leaching of the nickel to the liquid phase has
been evidenced.
38
Due to the interaction with tartaric acid the formation of
imprinted sites on the nickel surface has been suggested. The enantio-dif-
ferentiation takes place over this type of chirally modied sites.
Since the discovery of the cinchona-platinum catalyst system by Oritos
group
3943
for the enantioselective hydrogenation of methyl pyruvate
(MePy) or ethyl pyruvate (EtPy) the platinum-cinchona system has been
successfully applied in the enantioselective hydrogenation of a variety of
a-functionalized activated ketones, such as various a-ketoesters, keto-
pantolactone (KPL), a-ketoamides, a-diketones, a-keto acetals, a-ketoe-
thers, triuoromethyl ketones, and pyrrolidine-2,3,5-triones. Recently the
method has been extended to other types of ketones.
44
This type of asym-
metric hydrogenation reaction is considered as the most intensively studied
heterogeneous enantioselective hydrogenation reaction.
Since the early eighties great amount of knowledge accumulated on this
catalytic system. The topic has been reviewed by dierent authors.
15,33,35,4554
The most important characteristic features of the platinum-cinchona system
are as follows:
v
Variety of activated ketones can be used as substrate;
v
Under properly chosen conditions the cinchona alkaloids can induce
high enantioselectivity (ee W97%);
55,56
v
When a-keto esters are used the enantio-dierentiation ability is lost if
the basic nitrogen at the quinuclidine moiety of the cinchona alkaloid is
blocked by alkylation;
57
v
Upon using various substrates the addition of the cinchona alkaloid
results in signicant rate acceleration;
58
v
The amount of modier required to induce high enantioselectivity is in
the range of 1 10
5
M, or in other words the substrate/modier ratio can
146 | Catalysis, 2010, 22, 144278
exceed a value above 100.000 (in case of KPL the above ratio was
276.000);
59
v
The replacement of the quinoline ring of the modier by phenyl or
pyridyl resulted in complete loss of ee;
60
v
Inversion of ee is observed under various experimental conditions.
In the last twenty years step-by-step progress has been made in the pro-
cess of understanding the peculiarities of the platinum-cinchona system.
This progress covers the following main issues: (i) elucidation of both the
rate acceleration and the origin of enantio-dierentiation, (ii) clarication
of the nature of species formed both in liquid phase and on Pt surface by
using various spectroscopic methods, (iii) establishment of general and
specic kinetic patterns, and (iv) theoretical calculations and related
modeling.
As far as several reviews have already been published on the enantiose-
lective hydrogenation of activated ketones in the presence of cinchona-Pt
catalyst in this review an attempt was done focusing on (i) methods and
approaches used, (ii) recent achievements, and (iii) recalling historical
events.
Contrary to earlier reviews in this contribution the mechanistic con-
siderations will be treated without any preconception. It means that it will
be a priori not accepted that all phenomena involved in the rate acceleration
and induction of enantio-dierentiation can be related to events taking
place exclusively over Pt surface.
61
Consequently, in this review we shall
also refer to the general aspects of chiral induction generated by cinchona
alkaloids. Possible interactions in the liquid phase will also be discussed.
Enantio-dierentiation is a phenomenon characteristic mostly for organic
reactions. There are various synthetic methods in organic chemistry to in-
duce chirality. It has to be emphasized that cinchona alkaloids are well-
known chiral compounds used by organic chemists to bring about chiral
induction.
62
This issue will be briey discussed in Section 2.1
We shall try to demonstrate that the enantioselective hydrogenation of
activated ketones is a very complex reaction. Depending on the conditions
of catalyst pretreatment, the accomplishment of the hydrogenation reaction
and the type of substrate and modier used the key interactions responsible
for the transformation of the chiral information can takes place both at the
Pt surface and in the liquid phase. Methods and approaches used in this
area will also be discussed as these issues were not treated in previous
reviews.
1.2 Oritos followers
After Oritos publications
39,4043
intensive research programs were started
by dierent research groups. First two groups in Switzerland, one at Ciba
Geigi in Basel under supervision by Dr. H.U. Blaser,
63
the other in Zurich at
ETH with professor A. Baiker.
64
Parallel to that professor P.B. Wells
65
in
Hulls (Great Britain) started a program related to the use cinchona alkal-
oids in heterogeneous catalytic asymmetric hydrogenation.
Later on other groups in the USA (Dr. D. Blackmond at Merck,
66
Pro-
fessor R. Augustine
67
in Seaton Hall), in Hungary (Prof. Tungler
68
at
Catalysis, 2010, 22, 144278 | 147
Technical University in Budapest, Prof. J.L. Margitfalvi
69
at the Hungarian
Academy of Sciences and Prof. M. Bartok
70
at University of Szeged ), in
Finnland ( professors T. Salmi and D. Murzin
33,71
at Abo Academy Uni-
versity) joined to this research area. Today there are around 1520 in-
dependent research groups all around the word that are involved in the
investigation of one of the aspects of Oritos reaction.
It is interesting to emphasize that the method developed by Orito was
quickly modied as the pre-modication approach was replaced by in
situ modication technique. In this respect the pioneering works were done
by the two Swiss groups. Only one group has continued for a while to apply
the pre-modication approach: (the group in Hulls), however today this
approach is almost forgotten. Further details about modication pro-
cedures will be given in Section 4.
In the rst approaches mostly Pt/Al
2
O
3
catalysts and EtPy were used in
order to elucidate the general kinetic patterns.
58,73
Later on the focus was
laid on (i) the elucidation of the reaction mechanisms,
61,65,67,74,75
(ii) the use
of new substrates,
76,77
(iii) the application of new modiers,
60,78
(iv) new
type of catalysts,
79,80
(v) the formation of by-products,
81
(vi) the role of
impurities,
82
(vii) modeling substrate modier interaction.
8385
Today so-
phisticated experimental and computational techniques, such as reaction
calorimetry,
86
the AFM,
87
NMR,
88
FTIR,
89
in situ reection-adsorption
infrared spectroscopy (RAIRS),
90
attenuated total reection infrared
spectroscopy (ATRIR),
91
surface-enhanced Raman spectroscopy (SERS),
92
circular dichroism,
93
electrochemical methods,
94
Near-edge X-ray ab-
sorption ne structures (NEXAFS)
95,96
studies, DFT calculations
97,98
are
used to get as much as possible information about these unique asymmetric
hydrogenation reactions.
Oritos approach later on was extended to other type of activated ke-
tones. The substrates were classied according to the observed rates and
enantioselectivities. This classication is given in Fig. 1. Further discussion
of substrate specicity will be given in Section 5.3.
From the above discussion it can be concluded that the enantioselective
hydrogenation of activated ketones is the most detailed studied asymmetric
hydrogenation reaction. However, despite of the extensive studies there are
plenty of unanswered questions related to the origin of enantio-
dierentiation.
High rate high ee
(a) (b) (c)
Medium rate medium ee Low rate low ee
8 9 10
1 2 3 4
5 6 7
11 12 13
14 15
Fig. 1 Classication of substrates according to their ability to give high rate and high ee.
(Reproduced from ref. 72 with permission.)
148 | Catalysis, 2010, 22, 144278
1.3 Specicity of heterogeneous enantioselective catalysis
Heterogeneous catalysis is a complex eld in physical chemistry. However,
the state-of-the-art current knowledge in this area requires additional
knowledge in the eld of materials science, surface chemistry, surface sci-
ence, surface analysis, computational chemistry, chemical engineering, etc.
Heterogeneous enantioselective hydrogenation requires an additional
knowledge, i.e. an education in the eld of organic reactions. As far as
enantioselective reactions are a specic area of organic catalysis the
knowledge in this area should also be very specic.
It has to be emphasized that those who joined to this research area have
dierent scientic background and dierent research interest. In most of the
cases we are witnessing the prevalence of approaches and views reecting
the mode of thinking of a chemical engineer or a surface scientist.
Although excellent reviews were written in the last ten years,
4652
those
who have a solid background in organic chemistry can realize that both the
structure and the conclusions of these reviews reect the view of those who
have a surface science or chemical engineering background.
The investigation of heterogeneous catalytic reactions requires a complex
knowledge and the use of various experimental techniques. Among these
methods reaction kinetics and surface characterization has the greatest
importance. Detailed reaction kinetic studies can provide sucient infor-
mation to suggest or create a proposed reaction mechanism. However, even
if reaction kinetics can completely be described by the given system of
dierential equations the elucidation of the exact reaction mechanism
cannot be guaranteed. This would require the comparison of several pos-
sible or potential kinetic equations derived from other possible reaction
mechanisms. Unfortunately, such kind of comparison is only seldom is
performed in studies related to the elucidation of reaction mechanisms of
asymmetric hydrogenation of activated ketones.
In the enantioselective hydrogenation of activated ketones the accom-
plishment of detailed reaction kinetic measurements is strongly hindered by
the peculiarities of the reaction, such as (i) the ability of modiers to induce
enantio-dierentiation at very low modier/substrate ratio, (ii) the high
reactivity of the substrates resulting in the formation of various by-prod-
ucts, (iii) the loss of alkaloid during the reaction, and (iv) the catalyst poi-
soning. All these issues will be discussed latter in separate sub-paragraphs.
Due to the formation of byproducts, the loss of alkaloids and catalyst
poisoning the analysis of the full kinetic curve is almost impossible. Con-
sequently, the use of initial (or maximum) reaction rates cannot provide a
proper background for exact kinetic analysis or for the establishment of
correct reaction mechanism. The use of in situ calorimetry is one of the most
precise methods to obtain direct reaction rates,
99
although this method is
not common. The preliminary analysis of results obtained by in situ cal-
orimetry indicates that the rate follows the Michaelis-Menten mech-
anism,
100
what is characteristic to enzyme catalytic reactions.
101
The fact, that only trace amount of cinchona alkaloid can result in ee
values above 90%, strongly indicate that this catalytic system is extremely
unique. In this respect the results obtained in the enantioselective
Catalysis, 2010, 22, 144278 | 149
hydrogenation of KPL has to be emphasized, where the substrate/modier
ratio is 276 000:1.
59
In other studies related to the enantioselective hydro-
genation of EtPy the above ratio is in the rage of 50 000 to 166 000.
102
Such
a high value of chiral amplication is characteristic only to enzymes.
Cinchona alkaloids, due to their high extent of chiral amplication, their
distinct substrate specicity and their exible structure, can be considered as
a mini-enzyme.
93
This aspect is often forgotten by those working in this
area; although in a recent study the similarity to enzymes has already been
mentioned.
103
The other key approach for the elucidation of reaction mechanism is the
investigation of the formation of dierent surface intermediates by dierent
surface analytical tools. These approaches will be described in details in
Section 6. In this respect the key issue is to answer the following question:
can the given observed surface entity be involved in the reaction route or
does it represent a dead-end in the given reaction scheme? In the former
case we talk about actors, while in the letter case about spectators.
Unfortunately, this kind of questions is only seldom raised. It has to be
emphasized that the dierentiation between actors and spectators is a
long dispute in the area of heterogeneous catalysis. Even in gas phase re-
actions taking place at atmospheric pressure neither the in situ nor the
operando spectroscopy can always provide an unambiguous exact answer
about the involvement of a given surface species in the reaction network.
When we are dealing with heterogeneous hydrogenation reactions taking
place in a three-phase system at high hydrogen pressure the accomplishment
of in situ or operando spectroscopy is very dicult.
Catalysis scientists like very much to refer to sophisticated spectroscopic
data and use these data in favor of their ideas with respect to the reaction
mechanism. Even one of the authors of this contribution walked into this
catch. In early eighties the direct route for the hydrogenation of acetylene to
ethane was conrmed by a sophisticated double isotope labeling techni-
que.
104
Based on surface science results we proposed that the formed
ethylidyne species (RCCH
3
) are responsible for the direct route of ethane
formation. Of course, we did not detect these species; we just referred to one
of recently published LEED results.
105
Later on it turned out that the
ethylidyne species are so stable that they cannot be removed from the Pd
surface by hydrogen at room temperature.
106
Of course, several similar
misinterpretations can be found in the literature.
It will be discussed latter on that in the hydrogenation of activated pro-
chiral ketones the presence of hydrogen at the Pt surface is very crucial.
It strongly determines the performance of the catalyst. The hydrogenation
of ketones requires relatively large abundance of hydrogen at the Pt surface.
Probably, it is the reason that these enantioselective hydrogenation re-
actions cannot be performed under conditions of transfer hydrogenation.
Any disturbance in the amount of available hydrogen can result in signi-
cant alteration is the performance of Pt-cinchona catalytic system. It is
especially notable when the hydrogenation is performed in a continuous-
ow reactor under trickle bed condition.
107
However, too much hydrogen at the Pt sites will result in the hydro-
genation of the quinoline ring of cinchona alkaloids. This leads to the loss of
150 | Catalysis, 2010, 22, 144278
ee at low concentration of cinchona alkaloids.
108,109
Contrary to that
hydrogen starving conditions increases the chance for undesired side re-
actions, such as oligomerization and polymerization. Consequently, if in situ
measurements cannot be performed under optimum hydrogen coverage the
chance to detect spectators is very high. For this reason all spectroscopic
data presented so far should be treated with denite precaution.
2. Cinchona alkaloids
2.1 Characteristic features of cinchona alkaloids
Cinchona alkaloids are used in many elds of our everyday life. They are
widely used in the pharmaceutical and chemical industry. Quinine, derived
from the bark of Cinchona ledgeriana Moens ex Trimen is the oldest known
natural antimalarial drug. Cinchona alkaloids as easy available chiral
agents have great importance both in the academic research and in large
scale industrial use. In this respect the classical separation of racemic
naproxene can be mentioned.
110
An explanation why cinchona alkaloids are
universal molecules for so many purposes was given by Wynberg.
62
This is
shown in Fig. 2.
Various parts of the molecule ll the following functions: (a) hydrogen
bond formation (interaction with metals); (b) basic amine; (c) bulk aliphatic
hydrocarbon moiety; (d) handle to modify; (e,f) chiral pocket (epimers
available; conformer formation); (g) bulk aromatic hydrocarbon, polariz-
able, p-p interaction; (h) handle to modify; steric and polar inuence. In
this section the use of cinchona alkaloids in chiral separation and chiral
catalysis will be reviewed very briey. More detailed reviews can be found
elsewhere.
62,111,112
2.2 Use of cinchona alkaloids as chiral auxiliaries
2.2.1 Chiral separation. The rst example of resolution through for-
mation of diastereomeric salts was made by Pasteur
113
who used quinicine
and cinchonicine, derivatives of quinine and cinchonidine, respectively.
Since that time Cinchona alkaloids have been largely employed for the
Fig. 2 Multifunctional nature of quinine as a catalyst. (Reproduced from ref. 62 with
permission, (Figure 19))
Catalysis, 2010, 22, 144278 | 151
separation of various racemic mixtures.
114
In the sixties quinine and some
other cinchona alkaloids were used to prepare chiral sorbents.
115
Alkaloids
of this type were covalently bonded to a silica support via their olenic
group. In this way several functional groups in a bulky chiral system pro-
vided multiple contact points with the racemate to be resolved.
Up to now big variety of separation techniques using cinchona alkaloids
has been reported. A two-dimensional liquid chromatographymass spec-
trometry (LCMS) system was developed for the separation of both dia-
stereomers and enantiomers of peptides.
116
Generally the presence of
electron-decient aromatic N-acyl constituents and bulky, highly lipophilic
side chains enhances enantioselective adsorption, reecting the importance
of intermolecular p-donor-acceptor and hydrophobic interaction with the
chiral selector.
117
Mixed ternary ion associate formation between xanthene
dye, cinchona-alkaloid and quaternary ammonium ion has been applied to
determinate the trace amount of quaternary ammonium salts in pharma-
ceuticals by UV spectrophotometry.
118
2.2.2 Chiral catalyst. In the eld of chiral catalysis huge amount of
work has been done and cinchona alkaloids have been involved the in the
following areas:
v
chiral basic and nucleophilic catalysts in organo-catalytic reactions,
v
chiral ligands coordinating metals like osmium in homogeneous cata-
lytic reactions,
v
phase transfer catalysts in form of quaternary ammonium derivatives,
v
chiral modiers (templates) in heterogeneous catalytic asymmetric
reactions.
The cinchona alkaloid catalysed reaction of diethylzinc and aldehydes has
lead to optically active alcohols having enantiomeric excess up to 92%.
119
Cinchona alkaloids have been used both in solute form in liquid phase
and in bounded form immobilized into polymer or oxide type supports. In
organo-catalysis based on cinchonas large variety of substrates and types of
the reactions has been reported. In 1954 Prelog and Wilhelm described the
behaviour of dierent cinchona alkaloids and some of their derivatives in
the asymmetric cyanhydrin synthesis.
120
A review of cinchona alkaloid-
catalyzed reactions covering the period prior 1968 was given by Pracejus.
121
Cyanohydrin reaction, the Michael reaction, the 1,4-thiol and thiolace-
tate additions, selenophenol addition reactions, epoxidation of electron-
poor olens, formation of the phosphorus-carbon bond using chiral amine
catalysis, 1,2-additions in the presence of cinchonas has been detailed by
Wynberg in 1986.
62
Highly enantioselective Reformatsky reaction of ketones has been ac-
complished using cinchona alkaloids as chiral templates.
122
Cinchona al-
kaloid-derived chiral bifunctional thiourea organocatalysts were
synthesized and applied in the Michael addition between nitromethane and
chalcones with high ee and chemical yield.
123
The osmiumtetraoxide catalyzed asymmetric dihydroxilation (AD) is a
very important eld of cinchona utilization (see Fig. 3).
10,124
Cinchona al-
kaloid backbone is ideally suited for providing high ligand acceleration as
well as enantioselectivity in AD. It has been found that the
152 | Catalysis, 2010, 22, 144278
enantioselectivity is inuenced mainly by the nature of O9 substituent of the
cinchona alkaloid backbone. Three dierent classes of ligands are very
eective for the dihydroxylation of almost any olen (PHAL-,
125
PYR-
126
and IND-class
127
). Large scale of substrates (monosubstituted, 1,1-di-
substituted, 1,2-disubstituted, trisubstituted even tetrasubstituted olens,
enol ethers, cyclic olens, amides, enones, sulfur-containing olenes, pro-
tected divinyl ketones, conjugated dienes, trienes etc) can be successfully
dihydroxylated.
10
Phase transfer catalysis (PTC) based on cinchona alkaloids
128153
is a
continuously developing practical method for asymmetric synthesis because
these catalysts are very selective. Enantioselective epoxidation of a,b-un-
saturated ketones utilizing cinchona alkaloid-derived quaternary ammo-
nium phase-transfer catalysts bearing an N-anthracenylmethyl function
gave also appropriate results.
Common to all successful applications of cinchona alkaloid derived phase
transfer catalysts is that the reaction conditions have to be optimized,
consequently structures of substrate, reagent, and catalyst must t toge-
ther: An attempt has been made to understand the role of dierent
structure units of cinchona derivatives in PTC. The N-anthracenylmethyl
group introduced by Lygo
139,143
and Corey
141
has been good for an increase
in selectivity, although 1-naphthylmethyl was almost as eective.
144
Phase
transfer catalysts having diaryl substitution at the 3-and 4-positions of the
N-benzyl group in cinchonidinium salts were prepared to check how sub-
stituted aryl groups aect the asymmetric induction in the benzylation re-
action as compared to those having at linear aryl systems like
naphthylmethyl and anthracenylmethyl groups.
149
Tremendous amount of work has aimed the preparation and investigation
of supported cinchona alkaloids as catalyst.
154170
Polymer bound cinchona
alkaloids have been employed for a number of heterogeneous catalytic re-
actions e.g. asymmetric Michael additions,
154156,171
asymmetric synthesis of
a-amino acids,
169
enantioselective a-chlorination of acid chlorides,
170
asym-
metric aminohydroxilation
167
asymmetric dihydroxilation of alkenes.
160,163
To recycle the alkaloid-OsO
4
complex in asymmetric hydroxilation reaction
Fig. 3 Role of structural elements of Cinchona ligands in osmium-catalyzed asymmetric
dihydroxilation (AD) reactions. (Reproduced from ref. 10 with permission (Figure 4))
Catalysis, 2010, 22, 144278 | 153
Kim and Sharpless
159
have synthesized four dierent polymers, Pini
et al. have examined copolymers of acrylonitrile and substituted quinidine
and quinine and reported very low optical purity of diols (up to 45% ee).
160
Lohray et al. prepared several copolymers of styrene and 4-phenylstyrene
with 10% DHQD-4-vinylbenzoate aording the most eective catalyst for
heterogeneous AD.
161
A nice example of immobilized quinine used as a
catalyst for enantioselective a-chlorination of acid chlorides was given in
ref. 170. Large scale of dierent type of polymers has been reported for
immobilization of cinchonas.
155,157,158,163,165,166
Silica gel supported
cinchona alkaloids have been used also as catalysts in asymmetric dihydroxy-
lation and aminohydroxylation.
167
Norcinchol supported on silica via
ethoxy-silane compound has been applied for enantioselective hydrogenation
of a-keto esters with moderate success.
47
For dierent purposes dierent
cinchona alkaloids are suitable. In methanolysis of dierent tricyclic
anhydrides quinidine and quinine has given higher ee than cinchonidine or
cinchonine.
172
For asymmetric dihydroxylation also quinine (QN) and quinidine
(QD) have been found as the most eective ligand.
10
In a few cases etheral
type cinchona alkaloids
173
are also successfully used as chiral template,
e.g. b-isocupreidine has been used in the asymmetric Baylis-Hillmans
reactions of aromatic imines with 1,1,1,3,3,3-hexauoroisopropyl acrylate
giving (S)-enriched, N-protected-a-methylene-b-amino acid esters. In
contrast to the corresponding aldehydes, imines have shown the opposite
enantioselectivity.
173
Based on the above short review it can be concluded that cinchona al-
kaloids and their derivatives due to their multifunctional structure and easy
availability have been widely used for chiral induction in asymmetric syn-
theses as well as chiral separations for a century. When new problems in
asymmetric techniques have to be solved the application of cinchonas often
provides the proper solution again.
All of these results clearly indicate that cinchona alkaloids have been used
by organic chemists in various areas in order to induce chiral induction or
chiral recognition. Consequently, the use of these alkaloids in Oritos re-
actions is only one of the opportunities provided by the unique chemical
properties of these natural compounds. Any attempt to describe the action of
cinchona alkaloids exclusive to surface phenomenon seems to us a mistake.
2.3 Structure of cinchona alkaloids, conformational analysis, and
NMR studies
2.3.1 General information. Conformational investigations of cinchona
alkaloids based on computational or spectroscopic methods have been
made with the aim of understanding of chiral discrimination process.
88,174
The most frequently investigated cinchona alkaloids and cinchona deriva-
tives are summarized in Fig. 4. Cinchona alkaloids consist of two rigid cyclic
systems, a heteroaromatic quinoline ring and a saturated cyclic quinuclidine
ring connected by two carbon-carbon single bonds. They have four asym-
metric centers: C3, C4, C8, and C9. However, their congurations dier
from each other only at C9 and C8.
154 | Catalysis, 2010, 22, 144278
N
H
N
R
2
R
4
R
3
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1
4

9
8
3
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4
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R
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8
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4

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3
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4
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2
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Catalysis, 2010, 22, 144278 | 155
2.3.2 Conformational analysis. Crystallographic structure of QN,
177
QD,
178
CD
179
and cinchonine (CN)
180
is well described. In solution how-
ever, existence of several other conformers can be supposed. Conformation
of quinine and quinidine was a key issue in dierent studies
62,120,121,179,180
and the C8-C9 and C4
/
-C9 bonds were considered most important in de-
termining the overall conformation of these compounds. Hiemstra and
Wynberg
181
have proposed that the most stable conformation of quinine
have the largest substituent-the quinuclidine ring-on one side of the quinoline
ring, and hydrogen at C8 and the hydroxyl at C9 on the other side. Prelog
120
and Meurling
180
found this conformation to be the most favorable too.
In their pioneer work, Dijkstra and coworkers have combined NMR
study and molecular modeling approaches to elucidate the conformational
properties of QN and QD.
175,176,183
By use of the molecular modeling
program CHEMX, the conformational freedom with respect to the C8-C9
and C9-C4
/
bond was investigated.
175
Molecular mechanics studies showed
that cinchona alkaloids can in principle adopt four dierent conformations:
two open one in which the quinuclidine nitrogen points away from the
quinoline ring and two closed one in which the quinuclidine nitrogen
points toward the quinoline ring
176
(see Fig. 5). One of the calculated con-
formations of QD (open conformation (3) in Fig. 5) has almost the same
geometry as the crystal structure.
175
Dierent dihydroquinidine (DHQD)
Fig. 5 The four minimum energy conformations of quinidine (Reproduced from ref. 176 with
permission, Figure 2)
156 | Catalysis, 2010, 22, 144278
derivatives as model substances behave in dierent way. Acetyldihy-
droquinidine exhibits the closed conformation in CDCl
3
.
183
Hydroxy cinchona alkaloids exist in open conformation (3) (see Fig. 5) at
least in 90%, wherein some conformational freedom of the quinuclidine
ring exists. Methoxy derivatives predominantly adopt the open conform-
ation (3) and to a lesser amount the closed conformation (2) in CDCl
3
.
However, in CD
2
C1
2
the closed conformation (2) is found in excess.
183
Hydroxy cinchona alkaloids exist in open conformation (3) (see Fig. 5)
at least in 90%, wherein some conformational freedom of the quinuclidine
ring exists. Methoxy derivatives predominantly adopt the open conform-
ation (3) and to a lesser amount the closed conformation (2) in CDCl
3
.
However, in CD
2
C1
2
the closed conformation (2) is found in excess.
183
The combination of variable temperature ( 20 to 100 1C) NMR and
circular dichroism spectroscopy as well as molecular mechanics compu-
tations have shown that in ether solution dihydroquinidine existed in two
conformations, the open conformation (3) (anti, open) (8090%) and
closed conformation (1) (syn, closed) (1020%) separated by a barrier of
8.3 kcal/mol.
184
The results of computations favoured to the closed conformation (1) in
the gas phase and this discrepancy was explained by preferential solvatation
of hydroxy group, which is sterically more available in anti conformation.
Bulky substituents on the hydroxy group, such as in the p-chlorobenzoate
ester have the same eect.
184
The conformation of cinchonidine in solution has been investigated by
NMR techniques as well as with theoretical tools.
88
Three conformers of
cinchonidine (CD) are shown to be substantially populated at room tem-
perature, closed conformation (1), closed conformation (2), and open
conformation (3). The latter is the most stable in apolar solvents. The sta-
bility of the closed conformers relative to that of open conformer (3),
however, increases with solvent polarity. In polar solvents the three con-
formers have similar energies. The relationship between relative energies
and the dielectric constant of the solvent is not linear but resembles the form
of an Onsager function.
88
In o-dichlorobenzene or dimethyl sulfoxide solution the dihydroquinidine
(DHQD) and (p-chlorobenzoyl)dihydroquinidine (p-ClBzDHQD) were
found to exist as an equilibrating mixture of two main conformers, see
Table 1.
174
The relative amounts of these two conformers depend on con-
centration as well as on solvent and temperature. Changes in the ratio of the
two conformers of DHQD can explain the observed changes of the enan-
tioselectivity in the indene rearrangement when the solvent was changed
from o-dichlorobenzene to dimethyl sulfoxide.
Solute-alkaloid interactions are also able to inuence the conformational
behavior.
183
In case of ester derivatives the energy dierence between closed
and open conformation is less and is probably of the same order of mag-
nitude as the amount of stabilization caused by interactions with solutes,
such as methanol or weak acids, or with strong electrophiles, such as os-
mium tetraoxide.
In case of the methoxy derivatives the energy dierence between closed
conformation (2) and open conformation (3) has vanished. In non-
Catalysis, 2010, 22, 144278 | 157
coordinating solvents like CD
2
C1
2
, the methoxy derivatives are still pre-
dominantly found in the closed conformation (2), but in the presence of any
electrophile the equilibrium shifts towards the open conformation (3).
Quinine and quinidine (and other hydroxy derivatives) by themselves al-
ready possess a distinct preference for the open conformation (3) and thus
do not depend on extra stabilization caused by interactions with solute.
183
Upon investigation of the above mentioned cinchona alkaloid catalyzed
Michael addition of thiols to enones, it was found from the NOESY spectra
of QD and QN in the presence of 4-methylbenzenethiol that the alkaloid
conformations do not change on formation of an ion pair.
175
When cinchona alkaloids are used as chiral bases, the main interaction
with the substrate comes from protonation of the tertiary nitrogen in the
quinuclidine ring and a subsequent formation of an ion pair between the
protonated alkaloid and the deprotonated substrate molecule.
183
When the alkaloids are used as chiral ligands, the main interaction is the
formation of a dative bond between the tertiary nitrogen of the quinuclidine
ring and the metal atom of the substrate molecule (osmium tetraoxide).
183
Investigation of the temperature eect has led the authors to come to an
important nding. Low temperature experiments at 20 1C and 60 1C in
CDCl
3
, did not alter the
1
H NMR spectra, no line broadening has been
observed, and averaged spectra were still recorded at 40 1C. Thus, even at
these low temperatures, it was not possible to freeze out dierent con-
formers. This was an indicative of a fast exchange between the dierent
conformations on the NMR time scale and thus of a low energy barrier.
176
The syn-anti barrier was estimated ca 8 kcal/mol and the closed-open
barrier only half of this.
174
The
1
H NMR relaxation method was applied to QD. The proposed
conformation had the following dihedral angles: o(C11C10C3C4)
=
1501 and o(C4
/
C9C8C7)
=
701. The conformation of side-chain
o(C11C10C3C4) was found to be dierent from the one found for
crystalline form by X-ray analysis.
186
Potential energy surface (PES) for QD
has been comprehensively investigated using the molecular mechanics
Table 1 Populations of open (A) and closed (B) conformers of dihydroquinidine (DHQD) and
(p-chlorobenzoyl) dihydroquinidine (p-ClBzDHQD) calculated from J
H8 H9
.
a
(Reproduced
from ref. 174 with permission, Table 7)
Base Solution (25 1C) J (A)
a
J (A)
b
J(obs) P(A)
b
P(B)
b
DHQD CDCl
3
, 0.2 M 2.6 8.29 4.2 0.72 0.28
DHQD CDCl
3
, 0.02 M 2.6 8.29 5.0 0.58 0.42
DHQD THF-d
8
, 0.02 M 2.6 8.29 4.2 0.72 0.28
DHQD o-DCB-d
4
, 0.005 M 2.6 8.29 4.8 0.61 0.39
DHQD o-DCB-d
4
, 0.02 M 2.6 8.29 5.0 0.58 0.42
DHQD dioxane-d
8
, 0.02 M 2.6 8.29 5.0 0.58 0.42
DHQD acetone-d
6
, 0.02 M 2.6 8.29 6.3 0.35 0.65
DHQD DMSO-d
8
, 0.02 M 2.6 8.29 7.2 0.19 0.81
p-ClBzDHQD CDCl
3
, 0.2 M 2.5 8.73 7.4 0.21 0.79
p-ClBzDHQD o-DCB-d
4
, 0.02 M 2.5 8.73 7.8 0.15 0.85
a
Based on AM1 structures, J values calculated with substituent corrections by Gandour et al.
185
b
Populations of open (A) and closed (B) conformer.
158 | Catalysis, 2010, 22, 144278
(MM) and quantum mechanical semi-empirical AM1 and PM3 methods.
Theoretical results were in agreement with the experimental NMR data, i.e.,
there are two conformations of the quinidine molecule in solution.
187
Structures of etheral and D
3,10
isomers of cinchona alkaloids were also
determined by NMR and supported with molecular mechanics.
188
NOE
interactions in quinuclidine moiety of the cinchona ethereal isomers are
shown in Fig. 6. Further structural information on cinchona derivatives will
be given in Section 6.1.
2.3.3 Solute-solute interaction. Intermolecular interaction of the alkal-
oid molecules in solution can also be observed. Signicant dierence be-
tween the NMR spectra of optically pure and racemic dihydroquinidines
was found under the same conditions (0.35 M in CDCl
3
). The spectral
dierences were greatly reduced when CD
3
OD was used as solvent. The
acetates of optically active and racemic dihydroquinine showed signicantly
smaller dierences than those observed with dihydroquinine. The authors
have explained the observations by solute-solute interactions of the
enantiomers.
189
Osmometry was used to measure average molecular weight for quinine.
Results of these experiments have indicated the presence of particles larger
than monomeric quinine at 37 1C for a 16 mM solution in toluene. For
concentrationso4 mM the quinine was almost completely monomeric.
182
The coexistence of monomer and dimers of quinidine was established in
quinine-chloroform solutions by investigating the temperature and con-
centration dependence of the NMR spectral parameters by combination of
2D NOESY and proton-selective relaxation rate measurements. Similar
conformation of the alkaloid was found both in the dimer and monomer
forms. It was shown that the quinuclidine ring is on one side of the quin-
oline ring and the CHOH moiety on the other, with the quinoline plane
almost bisecting the angle between C-H8 and C-OH
190
see Fig. 7.
Fig. 6 NOE interactions in quinuclidine moiety of the cinchona ethereal isomers. (Repro-
duced from ref. 188 with permission, Scheme 2)
Catalysis, 2010, 22, 144278 | 159
Upon investigation the circular dichroism spectra of cinchona alkaloids,
exciton type Cotton eect at 230 nm band of free bases (0.4 mM) was found
in CH
2
Cl
2
or dioxane, but not in MeOH. This eect was attributed to the
week association of alkaloid molecules in non-polar solvents via N?HO
hydrogen bonds.
191
3. Alkaloids used in Oritoss reaction
Studies aimed at systematic variation of cinchona modiers and their
analogs have played a denite role in building up hypotheses for the
mechanism of Oritos reaction. The structural units of cinchona alkaloids
have been discussed in previous section. There are dierent reviews
46,192,193
related to the analysis of modiers used in asymmetric hydrogenation of
activated ketones. For this reason in this section only the key issues will be
briey mentioned.
We shall apply the following classication for chiral modiers applied (i)
exible cinchona alkaloids, (ii) exible cinchona derivatives, (iii) rigid cin-
chona derivatives, (iv) exible cinchona analogues, and (v) other type of
chiral templates.
3.1 Flexible cinchona alkaloids and their derivatives
Chiral templates most often used in the heterogeneous catalytic asymmetric
hydrogenation of activated ketones are natural cinchona alkaloids such as,
Fig. 7 Conformation of quinine dimer from NMR results (Reproduced from ref. 190 with
permission, Figure 8)
160 | Catalysis, 2010, 22, 144278
CD, CN, QN and QD (see Fig. 8).
33,40,51
CD is the most frequently in-
vestigated chiral template used in these reactions.
Upon hydrogenation of pyruvates QN and CD (C8(S), C9(R)) result in
(R)-lactate while QD and CN (C8(R), C9(S)) give (S)-lactate.
33,40,194,195
In
general CD is a better modier than CN. This dierence is more pro-
nounced in ethanol than in toluene, but in AcOH the dierence is negligible.
With the exception of epicinchona alkaloids
196
and isocinchonines
197
it is a
general observation, that the conguration of C8 or C8 and C9 atoms of the
cinchona alkaloid determines the product distribution.
57,192,198
Already in
one of the rst studies it was evidenced that tertiary N in the quinuclidine
moiety of cinchonas plays crucial role
194,198,199
although in recent studies it
was shown that in case of ketopantolactone
200
even N-alkylated derivatives
of CD can induce very slight enantioselection.
Surprisingly the N-oxide derivative of CD has also resulted in enantio-
selection. A possible reason is that N-oxide can be reduced very fast under
the reaction conditions and than acts like 10,11-dihydrocinchonidine
(DHCD)
57
which is the most easily forming derivative of CD.
63
Not only the vinyl group of cinchona alkaloids can be hydrogenated, but
its quinoline ring. This is an undesired side reaction leading to the sub-
stantial loss of enantioselectivity.
57,195,199
It has been suggested that the
decrease in the ee values upon using CD derivatives with partially hydro-
genated quinoline be attributed to a weaker adsorption of the alkaloid to
the Pt surface.
192
The phenomenon can also be explained by the loss of the
shielding eect of the aromatic p-system required for chemical shielding via
pp interaction
83
(see Section 8.3).
In a detailed study
18
dierent cinchona analogs and 8 dierent substrates
were investigated. The results indicated that no best chiral template exists
Fig. 8 Structure of natural cinchonas used in Oritos reactions.
Catalysis, 2010, 22, 144278 | 161
for all substrates.
201
This nding indicates that interactions between the
substrate and the chiral modier template depend on various factors.
201
C9 substituted compounds represent an important group of exible cin-
chona alkaloids. 9O-methyl-10,11-dihydrocinchonidine (MeODHCD) the
most frequently used C9 derivative generally behaves slightly better than
CD in the hydrogenation of a-ketoesters.
194,199,202,203
Similar positive re-
sults were obtained upon using other substrates.
44,199,204
However dike-
tones, such as 1-phenyl-1,2-propanedione produces lower ee in the presence
of MeODHCD than in the presence of CD.
205
Detailed studies on the use of
these alkaloid derivatives can be found elsewhere.
202,206
With respect to the
use of O-substituted derivatives the inversion of ee has to be mentioned.
These results will be discussed in Section 5.5.4. The inversion of ee in the
case of bulky O-substituted derivatives of CD relative to DHCD has been
attributed to a tilted mode of adsorption of these chiral templates to the Pt
surface
206
(see Sections 6 and 8).
3.2 Rigid cinchona derivatives
C8(S) C9(R) type of cinchona alkaloids, such as CN, QD and cupreidine
can form inner ether derivatives. These derivatives are called rigid as in
these alkaloids the rotation around the bond C8C9 as an axis is not
possible.
These alkaloids were used to demonstrate that the formation of closed
conformation of alkaloids is not a prerequisite for the formation of sub-
strate-modier complex suggested by the shielding eect model.
83
3.3 Flexible cinchona analogues
Synthetic analogues of alkaloids have all of the key elements of cinchona
alkaloids, such as aromatic ring, chiral moiety, and basic nitrogen. Im-
portant feature of these new analogues is the presence of an aromatic group
in the close neighbourhood of the stereogenic center. Dierent types of
enantiomerically pure primary and secondary aminoalcohols
78
and amines
have been tested as chiral templates in the hydrogenation of pyruvate
esters,
207,208
ketopantolactone,
209
triuoromethyl ketones,
210
1,1,1-tri-
uoro-2,4-diketones, etc.
44
3.3.1 Aminoalcohols. Series of enantiomerically pure 2-hydroxy-2-ary-
lethylamines (see Fig. 9) has been prepared from the corresponding ole-
ns.
78
Upon using compound A in the hydrogenation of EtPy ee values
higher than 75% was achieved.
207,208
The replacement of the naphtyl ring
by an anthracenyl one resulted in further increase of ee the up to 87%.
60,211
However 1-(9-triptycenyl)-2-(1-pyrrolidinyl) ethanol resulted in signicant
decrease in both ee (o5%)
60
and reaction rate.
3.3.2 Amines. Upon using (R)-1-(1-naphthyl) ethylamine as chiral
template in the asymmetric hydrogenation of EtPy 82% ee has been
achieved in AcOH. It has been shown that (R)-1-(1-naphthyl) ethylamine is
only a precursor of the actual chiral template, which is a secondary amine
(aminoester) formed in situ from (R)-1-(1-naphthyl) ethylamine and EtPy
by condensation to the corresponding imine and subsequent reduction of
162 | Catalysis, 2010, 22, 144278
the C
Q
N bond.
46,199,212
The conguration at the stereogenic center a to the
ester group has no eect on the enantioselectivity.
199
Substituent at the
amino group of naphthylethylamine can inuence the enantiodierentiation
ability; in general, more bulky substituent at the N atom is detrimental to
enantioselectivity in the hydrogenation reaction of EtPy.
199
Further details
can be found elsewhere.
210,212
3.4 Other type of chiral templates
Other natural alkaloids and their derivatives were also applied as chiral
templates in the asymmetric hydrogenation of activated ketones although
the ee values obtained were much lower than over CD and its derivatives.
Blaser and coworkers tested about 100 dierent chiral auxiliaries, but they
never found any meaningful enantioselectivity.
213
Ephedrine has given low
or moderate optical yields in the hydrogenation of a-ketoesters.
214
Codeine,
strychnine, and brucine have provided only 212% ee.
215
Using tri-
uoromethylcyclohexyl ketone substrate brucine has not resulted in optical
yield.
216
( )-Dihydro-apovincaminic acid ethyl ester has also been applied
as chiral template for EtPy substrate (2730% ee).
68,217219
Other vinca
derivatives have also been tested but ( )-dihydro-apovincaminic acid ethyl
ester has been found to be the most eective one.
68,220,221
Upon using other
compounds as chiral templates in the hydrogenation of EtPy (S)-a,a-
diphenyl-2-pyrrolidinemethanol
222
resulted in moderate ee (max 25%) de-
pending on the type of the solvent. (S)-proline chiral auxilary has also been
tested.
223
During the hydrogenation of EtPy in the presence of (S)-proline
resulted in the formation of N-alkylated proline while in case of isophorone
substrate a diastereoselective oxazolidine type intermediate was formed in a
condensation reaction. Hydrogenation reaction itself proved to be
Fig. 9 Preparation of enantiomerically pure 2-hydroxy-2-arylethylamines. (Reproduced from
ref. 78 with permission)
Catalysis, 2010, 22, 144278 | 163
diastereoselective. Isophorone has produced ee up to 60% but (R)-ethyl
lactate has been formed in very low optical purity (15% ee).
223
(S)-proline
derivatives, such as Z-(S)-proline 2-naphthyl ester, Z-(S)-proline 2-(2-
naphthyl)-ethyl ester, Z-(S)-proline 3-ethyl-indole ester and (Z)-(S)-proline-
3-ethyl-indolamide, (S)-proline-2-naphthylamide hydrochloride has also
been tested as chiral templates of new type in case of EtPy.
224
a,a-Diphenyl-
L-prolinol chiral template resulted in 14% (S) in the hydrogenation of tri-
uoromethylcyclohexyl ketone.
216
Dextrocarbinol base has induced no
enantioselectivity in the same reaction.
216
Tro gers base ((5R,11S)-( )-
2,8-dimethyl-6H,12H-5,11methanodibenzo[d,f][1,5]diazocin) as a chiral
templates has given 65% ee using acetic acide solvent in the asymmetric
hydrogenation of EtPy.
225
(R)-( )-2-phenylglycinol has induced poor
enantioselectivity in the hydrogenation of 1,1,1-triuoro-2,4-diketones.
44,217
Other compounds tested in the hydrogenation of EtPy as ((R)-( )-N-(a-
methylbenzyl) phtalic acid monoamide, (R)-( )-1-1-naphthyl) ethyliso-
cyanate has given moderate ee (23%, 59% respectively).
225
It has been shown that 1-naphthyl-1,2-ethanediol
226
is an eective chiral
modier in the hydrogenation of KPL and ethyl-4,4,4-triuoroacetoacetate.
It is the rst eective nonamine-type chiral template used in Oritos
reactions.
4. Methods and approaches used
4.1 General information
In this section methods and approaches applied in the enantioselective
hydrogenation of activated ketones will be described. One of the charac-
teristic features of this catalytic system is the need for catalyst pretreatment
in hydrogen at 350400 1C prior to the reaction. The omitting of pre-re-
duction step resulted in low rates and low enantioselectivities. The need for
catalyst pretreatment has already been described by Oritos group.
40
In a
later study it has been shown that the modication of the Pt surface by the
alkaloid requires pure Pt sites.
63
Recently a new type of Pt/Al
2
O
3
catalyst
has been developed by Degussa (catASium F214) which can be used without
pre-reduction.
227
This catalyst gives high rates and high ee values when it is
used as received.
Some authors claimed that the aerobic treatment of the catalyst, i.e. the
formation of chemisorbed oxygen on the Pt sites, is needed to improve both
the reaction rate and the ee values.
65,228,229
This issue will be discussed in
Section 4.3. The use of ultrasound resulted in also an improved performance
of supported Pt catalyst.
70,230
The other important issue is the mode of
introduction of the modier. In Oritos approach pre-modication has been
used.
40
The discovery of in situ modication was the next important nd-
ing.
63
Upon using in situ modication the ligand acceleration phenom-
enon has been discovered.
58
However, it has to be mentioned that rate
acceleration (RA) was not observed for all substrates and all modiers
investigated.
Based on this fact recently same groups questioned the validity of the rate
acceleration phenomenon.
232234
This issue will be discussed in Section
5.5.1.
164 | Catalysis, 2010, 22, 144278
Most of the authors are calculating either the initial rate or the maximum
rate observed after a short induction period. Unfortunately, due to side
reactions and the transformation of the alkaloid during the hydrogenation
reaction (see Section 5.1) the analysis of whole kinetic curve is very trou-
blesome, although there were attempts to do that.
100
We should like to emphasize that in order to get a full picture about the
peculiarities of these unique reactions reliable data with respect to both the
reaction rates and the optical yields should be provided. One of the most
serious problems is that in large number of recent publications the rates are
not given at all.
210,235237
Only conversion or yields values measured at the
end of the reaction are compared.
There were couples of papers devoted to the problems of reproducibility
and variation of the initial rates measured under identical conditions.
47,61
It has been shown that initial rates depend not only on the purity, but the
origin of the substrate as well as on the batch number.
69,93
Systematic
study of this eect was done by the Ciba group. These results are shown in
Table 2.
195
Of course, the purity of the reactant and solvent has a great impact on the
validity of kinetic results, consequently results obtained upon using un-
puried substrates, especially ketoesters, has to be treated with great
concern.
Researchers with sucient background in organic chemistry realized very
early that the purication of the substrates before the use is a must. The use
of puried modier is also very important.
238
There were strong disputes in
the literature concerning to the use of unpuried or contaminated sub-
strates.
66,69,82,228
The lack of background in organic chemistry often re-
sulted in strange and unreliable results. For instance, the reaction
mechanism was investigated by dierent groups in alcoholic solvent, despite
the fact that the most investigated substrates, i.e., EtPy or MePy, react with
linear alcohols in a side reaction catalyzed by tertiary amines. The
Table 2 Eect of substrate origin and quality on initial rate (100 mol/g catalyst/min) and ee
values in the hydrogenation of EtPy in the presence of CD under dierent conditions (catalyst,
solvent, pressure in bar). Bold numbers show the highest and lowest rate or ee values. (Re-
produced from ref. 194 with permission)
Origin
Undistilled Distilled
J, T, 20 J, T, 20 E, T, 20 J, Ac, 20 E, Et, 20 J,T,100 Average
rate ee rate ee rate ee rate ee rate ee rate ee Rate ee
Fluka91 3 63 12 69 10 69 12 83 25 74 56 82 20 73
Fluka92 4 78 44 80 50 80 64 88 90 74 96 83 58 81
Lancaster 7 71 14 78 14 77 26 87 36 77 48 85 24 79
ICN, Ohio 9 77 15 79 05 79 38 89 40 78 64 86 30 81
Sigma 9 76 24 80 20 80 46 87 40 78 114 87 42 81
Jansen 18 80 24 83 18 83 46 90 50 80 102 89 43 84
R.de Haen 5 73 30 81 21 79 46 87 50 78 148 87 50 81
Aldrich 50 84 70 85 36 85 76 91 70 84 132 90 72 87
TCI, 50 82 48 83 62 83 78 90 68 70 164 80 78 81
J
=
JMC, E
=
Engelhard, T
=
toluene, E
=
ethanol, Ac
=
AcOH, TCI
=
TCI, Tokyo
Catalysis, 2010, 22, 144278 | 165
formation semi-ketals will be discussed in Section 5.1. Despite all disputes
and argues even these days it is possible to nd papers, where no words is
said how the substrate was puried or what even is worst, there are publi-
cations where unpuried substrate has been used.
233,239
These facts often
resulted in misinterpretation of experimental results. These issues will be
described in Sections 5.5.1 and 5.5.2.
In all pioneering studies, i.e., in early nineties, the determination of op-
tical yield was not an easy task, especially at low conversion. For this rea-
son, the changes in the ee values with conversion were not investigated,
consequently the anomalous monotonic increase type ee-conversion de-
pendencies were not discussed till 1995 (see details in Section 5.5.2.).
In the last 10 years sophisticated physical or physical-chemical methods,
such as STM, ATRIR, AFS, Raman spectroscopy, etc. has been used in
order to elucidate the reaction mechanism or the origin of RA and enantio-
dierentiation (ED) (see Section 6.6). The common problem related to these
studies is that conditions of these measurements are far away from those
used in real hydrogenation reaction, although some measurement methods,
such as (ATR-IR) were performed under condition close to hydrogen-
ation.
240
A typical misused situation is when the chemisorption of CD was
investigated by electrochemical methods in concentrated H
2
SO
4
. Based on
these results it was concluded that the adsorption of CD on Pt (111) is ir-
reversible.
241
The problem with these results is that those who need some
additional proof with respect to surface induced RA and ED like these
results and refer to these false ndings quite often.
There is one more problem what can be formulated in the following way:
How to distinguish between surface species what are involved in the cata-
lytic step from those, what are formed on the surface of platinum, but are
not involved in the catalytic act? The latter species are often called as
spectators in a given catalytic reaction. In many cases the surface con-
centration of spectators can be much higher than that of the actors. In
this respect let us remind the reader for the classical problem in homo-
geneous catalysis discussed by Halpern.
225
In his classical study it was
demonstrated that in homogeneous catalytic enantioselective hydrogen-
ation not the most stable [substrate-catalyst] complex is involved in the ED
step, but the less stable one, what reacts with hydrogen much faster than the
former.
In connection to the above discussion the use of sophisticated surface
techniques for the elucidation of the origin of ED has to be mentioned.
None of these methods can fully guarantee that the observed surface species
is really involved in the given step of enantioselective hydrogenation.
Consequently, it is almost impossible to distinguish, whether an identied
surface entity is an actor or just a spectator.
4.2 Catalysts applied
4.2.1 Supported metal catalysts. In the enantioselective hydrogenation
of activated ketones supported Pt is the most commonly used catalyst. Pt/C
catalysts have been used by Orito in his original approach. Alumina sup-
ported Pt catalysts containing around 5 wt% metal are the most commonly
166 | Catalysis, 2010, 22, 144278
used catalyst. Two industrial catalysts, E 4759 from Engelhard and JMC 94
from Johnson Matthey, have been widely used by dierent research groups.
The Pt dispersion of these catalysts is in the range of 0.20.3.
57
E4759 has
rather small pores and a low pore volume, while JMC 94 is a wide-pore
catalyst with a large pore volume. There are reports related to the use of Pt
colloids both as prepared
79,100,242245
or stabilized on a support.
246
The use of other supported noble metals, such as Ir,
247249
Ru
250,251
and
Rh
252256
is considered as a curiosity, although recent results using rhodium
is very promising.
257
Supported iridium catalysts were used in the enan-
tioselective hydrogenation of diketones in order to suppress the hydrogen-
ation of the second carbonyl group.
258
Palladium is not a suitable metal for
the hydrogenation of keto carbonyl group.
Pt supported on HNaAY
259
and ZSM-5 zeolites,
260
MCM-41
261
meso-
porous materials, clays
262
and ion exchanges resins
250
were also tested in the
enantioselective hydrogenation of EtPy, however, the performance of these
catalysts was lower than that of the alumina or silica supported Pt.
It is interesting to mention that most of the Pt/C catalysts resulted in low
ee values (below 35%) and very moderate reaction rates.
263
There are re-
ports on the use of carbon nanotubes as support.
264
We consider that all
high surface area materials are inecient supports for this reaction, due to
their high adsorption power resulting in high modier concentration at the
support and lowering the modier concentration in the liquid phase.
In earlier studies it has been suggested that Pt dispersion has a decisive
inuence on both the activity and ee and it was suggested that in order to
obtain high optical yields the dispersion should be r0.2.
63
It has been
suggested that an appropriate at Pt surface be required to accommodate
the modier or the modier-substrate complex in order to get pronounced
ED.
265
Contrary to the above results and suggestions results upon using a
Pt/SiO
2
catalyst (EUROPT-1) relatively high ee values were also obtained,
although the dispersion of Pt in this catalyst is around 0.60.7.
228
Further
results on Pt nanocolloids prepared,
79,243246
indicated also that there is no
real need to have large at Pt surface to get high ee values.
4.2.2 Pt colloids. The common feature of Pt colloids is that they are
stabilized by nitrogen and oxygen containing ligands. Under properly
chosen experimental condition these Pt colloids show high activity and
relatively high enantioselectivity.
246
Pt colloids were also used in kinetic
investigations.
100
It was demonstrated that the RA could also be observed
when Pt colloids were used.
In this respect Pt colloids stabilized by cinchona alkaloids have the
greatest interest. The concept of using chiral stabilizing agent for the
preparation of Pt colloids has been applied by Bo nnemann.
79
These colloids
were used to hydrogenate EtPy. Upon using DHCD or CD as stabilizing
agent the mean size of Pt colloids was in the range of 1.52.8 nm. It is
interesting to note that upon using these colloids in the hydrogenation of
EtPy ee values in the range of 7580% were obtained. In a recent study Pt
nanocolloids stabilized by cinchona alkaloids were used in enantioselective
Catalysis, 2010, 22, 144278 | 167
hydrogenation of EtPy in as received form or immobilized on various
supports.
266
It is interesting to mention that colloids prepared by Bo nnemanns
method required addition of free alkaloid to induce high rate and high ee
values
,
. The addition of alkaloid to the solution increased both the reaction
rate and ee values in the range of 8085% were obtained in the
AcOHMeOH mixture.
244
The results indicated that two forms of the
alkaloids can be distinguished: (i) the stabilizing form ((CD)
st
or (CN)
st
),
and (ii) the excess form ((CD)
ex
or (CN)
ex
), i.e., the amount of alkaloids
added into the liquid phase. Under condition of enantioselective hydro-
genation these two forms are in dynamic equilibrium. The Pt colloid pre-
pared upon using cinchonine (Pt
CN
) was used to investigate the possible
exchange between the two forms of the alkaloid. These results are presented
in Fig. 10.
In the rst experiment the Pt
CN
colloid was used and the concentration of
(CN)
ex
was 6.8 10
3
M. In this experiment the ee was independent of the
conversion and leveled o at ee
=
0.6. In the second experiment instead of
(CN)
ex
(CD)
ex
was added and its concentration was also 6.8 10
3
M. The
initial ee values (ee
=
0.6) show that at low conversions the initial (CN)
st
form is involved in the events controlling the asymmetric induction. As the
reaction proceeded the (CN)
st
form was exchanged by (CD)
ex
resulting in a
decrease in the ee values. The nal ee value (ee
=
0) indicates that the above
exchange is almost quantitative. This result indicates that there is an ex-
change between the two forms of the alkaloid. In the third experiment the
(CD)
ex
was added prior to the treatment with ultrasound. In this experiment
-1.0
-0.6
-0.2
0.2
0.6
1.0
0.0 0.2 0.4 0.6 0.8 1.0
Conversion
e
e
Fig. 10 The ee conversion dependencies obtained in the presence of Pt
CN
varying the
character of excess alkaloid ((CN)
ex
or (CD)
ex
).
7
experiment in the presence of (CN)
ex
; D
experiment in the presence of (CD)
ex
without ultrasound treatment, E, B experiment in the
presence of (CD)
ex
after treatment with ultrasound. The concentration of excess alkaloids is
6.8 10
3
M; nanocolloid
=
0.020 g [EtPy]
0=
0.6 M, p
H2=
5 bar, solvent: CH
3
COOH/MeOH
(5/1), T
r=
12 1C. (Reproduced from 244 with permission)
168 | Catalysis, 2010, 22, 144278
the ee value was constant but was opposite in sign, i.e., during the ultrasonic
treatment full exchange between the two forms of the alkaloid ((CN)
st
and
(CD)
ex
) took place (see Fig. 10). The phenomenon appeared to be fully
reproducible.
According to computer modeling the above Pt nanocolloids have particle
size in the range of 1.62.8 nm, i.e., the size of accessible Pt (111) surface is
very small (3 4 or 5 5 Pt atoms). This small Pt colloid can accommodate
the shielded modier-substrate complex, while the accommodation of the
open modier-substrate complex would require much larger surface sites.
4.2.3 Characteristic features of supported Pt catalysts used. The results
discussed so far indicated there is no need to have a preferred particle size as
high ee values were obtained over catalyst having broad Pt dispersion range.
However, in active and enantioselective catalysts the Pt sites should be
relatively clean. Both the pre-treatment in hydrogen at 300400 1C and the
treatment in ultrasound can provide clean Pt surface.
Another important issue is that the catalyst used has to be relatively inert
related to in the hydrogenation of the quinoline ring of the alkaloid. Con-
ditions for ring hydrogenation of modiers were investigated in various
studies.
267271
Although it has been shown that upon using Al
2
O
3
support in AcOH Al
oxonium ions and their adducts with the alkaloid has been detected
272
the
involvement of these species in the catalytic reaction is quite doubtful. The
suggested electrostatic acceleration
273
needs further experimental proof.
As a rule the support should be relatively inert. Highly acidic supports
can induce acid catalyzed undesired side reactions. Both the high acidity
and the high surface area of supports decrease the amount of alkaloid
available for ED. It was shown that Cl containing alumina precursor and
chlorine-containing platinum salts exhibit signicantly higher optical yield
than similar catalysts prepared from chlorine free starting-materials.
265
It
has also been demonstrated that the modication of alumina support by
alkoxy-silanes decrease both the rate and ee values
274
(see Section 5.6.4).
4.3 Catalyst pretreatment
In the rst publication by Oritos group Pt/C catalyst was applied and the
benecial eect of preheating the catalyst in hydrogen at 300400 1C prior
to the modication was emphasized.
40,41
The selection of a proper pre-
treatment procedure for supported Pt catalysts is one of the basic issues.
Several other pretreatment methods were applied and dierent explanations
were given for the favourable eect of reductive, aerobic and ultrasonic
treatments. Fig. 11 shows the general scheme for catalysts pretreatment.
76
The common feature is the reduction of the catalyst used at relatively high
temperature (300400 1C). It is called reductive treatment. The catalyst can
be cooled either in hydrogen or in an inert atmosphere. In oxidative
treatment after the reductive treatment the catalyst is treated in air and
cooled down in an inert atmosphere. Most of the authors agree that
upon using supported Pt catalyst a reductive treatment is a must and special
care has to be done to prevent contamination of reduced catalyst with
Catalysis, 2010, 22, 144278 | 169
oxygen. However, there are groups using pre-reduced catalysts kept or
stored in air.
275
4.3.1 Prereduction in hydrogen. In one of the rst publications using
in situ modication of Pt/Al
2
O
3
catalyst
63,276
it was mentioned that the
thermal treatment at 400 1C hydrogen has pronounced eect both on the
activity and the enantioselectivity. After thermal treatments in hydrogen at
400 1C, 1520% higher ee values were obtained than over untreated
catalysts.
In a recent review
195
the role of pretreatment was formulated as follows:
(i) pretreatment cleans up the surface of the catalyst by removing oxygen as
well as impurities; (ii) residual Pt salts are converted to metallic Pt; (iii) the
average particle size of Pt increases, (iv) the morphology of Pt particles, i.e.
the distribution of exposed face, edge and corner atoms is also altered
favourably; (v) it promotes adsorbate-induced surface restructuring.
Restructuring during pretreatment of Pt/alumina catalyst used in enan-
tioselective hydrogenation of KPL was also studied.
277
The inuence of
reductive and oxidative heat treatment on the enantioselectivity of chirally
modied Pt/alumina has been reinvestigated. Enhancement in ee by
3949% has been observed after treatment in hydrogen at 250600 1C, as
compared to untreated or pre-oxidized catalysts. The changes in ee after
reductive and oxidative treatments are reversible, and always the nal
treatment is decisive. A HRTEM study indicates that adsorbate-induced
restructuring of Pt crystallites during hydrogen treatment at elevated tem-
perature can play a role in the selectivity improvement, but the changes are
superimposed by the strong structure-directing eect of the alumina
support.
Fig. 11 A general scheme for catalyst pretreatment. (Reproduced from ref. 76 with permission)
170 | Catalysis, 2010, 22, 144278
4.3.2 Inuence of oxygen. The eect of oxygen on the performance of
cinchona Pt catalyst system has been studied by dierent groups under
various conditions.
65,229
In these studies dierent solvents, dierent type of
supported Pt catalysts and dierent experimental conditions were used. For
this reason it is very dicult to make any right conclusion or interpretation
related to the given observation; is a particular nding a general phenom-
enon or an experimental artifact?
In a recent review
33
a generalized comment was given, namely the eect of
modication atmosphere of Pt-CD catalysts aects on the ee values. For
instance under air higher ee values has been achieved in EtPy hydrogen-
ation, whereas under anaerobic condition ee decreases drastically.
229,278
In
ref. 229 it was demonstrated that the addition of oxygen during the enan-
tioselective hydrogenation of EtPy has a positive eect both on the rate and
the ee values. The observed eect was attributed to restructuring of the
surface of Pt in the presence of oxygen. There is only one remark with re-
spect to these ndings, i.e., the nal ee value (below 40%) is extremely low
for the experimental conditions applied.
When anaerobic and aerobic treatments of Pt/SiO
2
catalyst was com-
pared after anaerobic treatment decreased enantioselectivity and greatly
reduced activity was observed using DHCD as modier in the hydrogen-
ation of MePy.
65
It has to be mentioned that this pretreatment was per-
formed in ethanol. In further studies it was shown that during this aerobic
treatment ethanol was oxidized over platinum catalyst into acetic acid
279
and probably the formed AcOH was responsible for the increased per-
formance. Similar prove has been obtained in our laboratory.
281
Table 3 shows the results obtained in the enantioselective hydrogenation
of triuoroacetophenone (TFAP).
76
These results clearly show that either
treatment in an oxygen atmosphere or stirring in air resulted in a decrease in
the enantioselectivity.
Barto k and coworkers have applied a reductive treatment prior to the use
of catalyst, but the catalyst is stored in air before its nal use. It was shown
that the increase of the storage time up to one week has no pronounced
eect on the performance of the catalyst.
277
With respect to the role of
oxygen it was also suggested that during this treatment PtO could be
formed. During the hydrogenation reaction PtO is reduced to metallic Pt
and water. It is not excluded that the presence of small amount of water can
result in some improvement in the performance.
76
In the enantioselective
hydrogenation of MePy or butane-2,3-dione over Pt in the presence of CD
the coadsorption of oxygen with the alkaloid resulted in a positive eect
Table 3 Inuence of catalyst pretreatment in the hydrogenation of TFAP (90 mg 5 w%
Pt/alumina, 1.28 g TFAP, 10 bar, 20 1C (Reproduced from ref. 76 with permission)
No Pretreatment Solvent (CD) mg Time (min) Conv. (%) ee (%)
1 toluene 2 63 89 16
2 reductive A toluene 2 50 96 33
3 reductive B toluene 2 86 95 33
4 reductive A 1,2-dichlorobenzene 4 105 95 45
5 oxidative 1,2-dichlorobenzene 4 105 91 29
Catalysis, 2010, 22, 144278 | 171
both on the rate and ee.
278
It was suggested that the presence of a strong co-
adsorbate, such as oxygen, the surface was not poisoned by CD. In a recent
study the promoting eect of helium treatment was also mentioned.
281
However, it was admitted that the eect is due to the small oxygen impurity
in the helium used.
4.3.3 Use of ultrasound and microwave heating. The eect of ultrasound
radiation was investigated in details by Barto ks group.
55,70,282284
The
method appeared to be highly ecient as the ultrasound radiation resulted
in and increase both in the reaction rate and the enantioselectivity. Table 4
shows representative results using three dierent substrates and three
modiers.
55
The decrease in metal particle size was given as an explanation
of improved performance.
282
In another study TFAP was applied as a
substrate and the use of sonication resulted in positive eect.
273
The results
indicated also that both the frequency of ultrasound and the duration of
sonication have a strong inuence of the enantioselectivity.
55
However, it was also pointed out that the presence of the modier is
absolutely crucial during sonication. It was proposed that the ultrasonic
irradiation created a more eective surface modication, resulting in the
formation of surface sites required for optimum enantio-dierentiation.
Besides it an additional positive eect of oxygen was also observed.
273
It
was suggested that ultrasonic irradiation helps the removal of the impurities
from the Pt surface.
195
Table 4 Sonochemical and silent enantioselective hydrogenation of a-ketoesters over 5%
Pt/Al
2
O
3
in acetic acid using dierent cinchona modiers under 10 bar hydrogen pressure.
(Reproduced from ref. 55. with permission)
Entry Substrate Modier Catalyst Major product
Optical yield (ee %)
silent sonication
1 1 4 E40665 R 85 97
2 1 5 E40665 S 78 83
3 1 6 E40665 R 93 98
4 2 4 E4759 R 88 92
5 2 5 E4759 S 34 57
6 2 6 E4759 R 60 68
7 3 4 E4759 R 79 92
8 3 5 E4759 S 50 92
6 3 6 E4759 R 83 96
Substrates: 1
=
EtPy; 2
=
PhGl, 3
=
Phenylethyl; Modiers: 4
=
CD, 5
=
CN; 6
=
O-Me-CD.
172 | Catalysis, 2010, 22, 144278
In enantioselective hydrogenation of 1-phenyl-1,2-propanedione over
5 wt% Pt/SF (silica ber) catalyst a notable enhancement of reaction rate, ee
and rs was observed under ultrasound compared to silent conditions.
231
In
mesitylene solvent four-fold increase in the reaction rate was observed
under ultrasound compared to identical silent conditions, while in methyl
acetate and in toluene the rate enhancement was only minor. Upon using
Pt/SF catalyst it was suggested that surface smoothening and cleaning take
place under ultrasound irradiation. However, no signicant dierences in Pt
particle size distribution between sonic and silent treated catalysts were
observed by TEM.
Summing up results related to the use of ultrasound its positive eect has
been ascribed to the following facts:
55
(i) through the decrease in metal
particle size, the platinum dispersion becomes close to optimal using a
catalyst of large metal particle size, (ii) the surface density of the modier
increases as a result of insonation, providing more chiral sites for the hy-
drogenation and, in parallel, suppresses the background reaction, i.e. ra-
cemic hydrogenation.
Enantioselective and racemic hydrogenation of EtPy over Pt/Al
2
O
3
catalyst was investigated under microwave dielectric and conventional
heating.
285
A homemade laboratory microwave loop reactor was applied
allowing dierentiating between dielectric and conventional heating. The
eects of polar and non-polar solvents on enantioselective hydrogenation of
EtPy were studied in toluene and ethyl alcohol. In case of toluene, which is
microwave transparent, no signicant dierences in the reaction rate and
enantioselectivity were observed between dielectric and conventional heat-
ing. In case of EtOH, the reaction rate remained unaected. However, the ee
dramatically decreased from 60 to 40% under microwave heating. No sig-
nicant improvement of the reaction rate with an increasing microwave
power input was observed. The authors suggested that this observation
caused by the local superheating of the polar EtOH in the cavity, which is
not possible in the non-polar toluene. Our explanation is dierent; namely
the decreased ee is due to the formation of semi-ketal from the substrate and
the alcohol used as solvent.
4.4 Premodication of the catalyst with the alkaloid
As it has already been discussed earlier that in Oritos pioneering studies a
premodication procedure was used to introduce the chiral modier into
the Pt/C catalyst pretreated in hydrogen at 400 1C.
40
It has to be emphasized
that the premodication was performed at higher temperature than that of
the hydrogenation reaction. During premodication the catalyst and the
cinchona alkaloid has been stirred in a given solvent for a relatively long
period (24 hours). This premodication procedure strongly resembled the
modication process used for Ni/tartaric acid catalysts developed earlier.
286
The premodication was followed by ltration and mild washing and the
premodied catalyst was introduced into the reactor containing the solvent
and the substrate.
Catalysis, 2010, 22, 144278 | 173
The Oritos original approach was followed by P.B. Wells group.
65,228,278
However, there were several drawbacks in the use of this method. Further
results indicated if the ltration and the washing is not carefully performed
solvated CD can be left in the pores of the catalyst support, for this reason,
as it was pointed out in one of the comments,
69
the exact amount of alkaloid
introduced was not really known. Probably it was the reason that in ref. 287
the authors admitted the erratic variation of the initial rates. After suc-
cessful introduction of the in situ methods
57
and demonstration of the ad-
vantage of premixing technique
64
the premodication method was almost
entirely forgotten. This approach is still used when the enantioselective
hydrogenation is investigated in the gas phase.
288
4.5 In situ modication
4.5.1 General Information. In situ modication of the catalysts prior to
the hydrogenation of activated ketones can experimentally be performed in
dierent way. These various approaches provides dierent surface coverage
at t
=
0, i.e., prior to the start of the hydrogenation reaction.
Let us consider that the Pt catalyst is pre-reduced in hydrogen around
400 1C and kept in an inert atmosphere prior to its use. The catalyst in this
form is introduced into the reactor containing the following components: (i)
solvent, substrate and modier (premixing method); (ii) solvent, substrate
(injection of the modier); (iii) solvent, modier (injection of the substrate).
It is easy to propose that the above three methods shall provide completely
dierent surface coverage at t
=
0, what can have dierent inuence both on
the kinetics and ED.
4.5.2 Premixing technique. This method has been applied rst by H.U.
Blasers group.
63
In this technique all components of the reaction are pre-
mixed prior to the hydrogenation reaction. This method provides high
coverage of substrate and a relatively low coverage of modier at the Pt site.
This new approach resulted in the discovery of the ligand acceleration
phenomena.
58
The rate increase was very pronounced and was proportional
to the amount of alkaloid used. This phenomenon will be discussed in
Section 5.5.1.
During premixing the substrate can decompose resulting in carbon
monoxide, which is considered as a strong catalyst poison. The substrate
interacts also with the modier and induces the formation of high-molecular
weight byproducts (see Section 5.1). These by-products have a negative
inuence on the initial rate by their poisoning eects. If the amount of
hydrogen in the overall hydrogen pool is high (i.e., when the catalyst is
cooled in the hydrogen atmosphere from the temperature of re-reduction) in
this case partial hydrogenation of both the cinchona alkaloid and the
substrate can also take place prior to the introduction of hydrogen.
Consequently, upon using the premixing technique a new problem ap-
peared, i.e. the reproducibility of the reaction rate. It was observed that the
rate of reaction depended on the duration of premixing, i.e. the time re-
quired to close the high-pressure autoclave, purge the reactor with nitrogen
and hydrogen, and pressurize the reactor and start stirring.
64
Reliable and
reproducible rate could only be obtained when the duration of premixing
174 | Catalysis, 2010, 22, 144278
was kept constant.
64
This problem is even more pronounced when alcohols
have been used as solvents.
4.5.3 Injection technique
Injection of the modier. This method excludes all undesired interactions
between the substrate and modier. It provides high coverage of the sub-
strate at the Pt site. However, if the catalyst is not cooled in an inert at-
mosphere racemic hydrogenation of the substrate can also take place before
starting the reaction (i.e. before t
=
0). Neither the spontaneous oligomer-
ization/condensation of the substrate or its decomposition into CO can be
excluded in this case.
Injection of the substrate. This method excludes also all undesired inter-
actions between the substrate and modier. It provides a denite surface
concentration of the modier. No oligomers or condensation products exist
at t
=
0. However, partial hydrogenation of the modier cannot be excluded
if the catalyst has been cooled in a hydrogen atmosphere.
The injection method gives an opportunity to get reliable kinetic data
provided a proper ratio between the batch and the injected volumes is
chosen. In this way the inuence of some of the undesired side reaction can
be eliminated, providing more chance to get intrinsic kinetic data. In this
approach either the modier or the substrate is injected by high-pressure
hydrogen.
69,93,195,289
4.6 Hydrogenation of a-keto esters in continuous-ow reactors
It is obvious that the separation, handling and reuse of the heterogeneous
catalysts become very ecient when the xed-bed reactor is used; con-
sequently it is very promising to introduce xed bed reactors with the aim to
industrialize the asymmetric catalysis. However, up to the late nineties there
were only scarce data related to the use of continuous-ow reactors in
asymmetric hydrogenation reactions.
As far as only trace amount of modier is required to induce high ee an
attempt was done to use a continuous xed-bed reactor for the enantiose-
lective hydrogenation a KPL.
290
This approach resulted in signicant pro-
cess intensication; consequently upon using a small tubular reactor (size of
a pencil) more than 14 kg (R)-pantolactone per hour could be produced.
Later on the approach was extended to use for other substrates.
291293
High reaction rates and high ee values were obtained by continuous
feeding of minute amounts of chiral modier to the reactant stream. The ee
values for KPL and EtPy without optimization was 83.4 and 89.9%, re-
spectively. Transient measurements by stopping of the ow of CD indicate
that continuous feeding of the modier in ppm concentration is crucial.
There was a short induction period prior reaching stable high ee values.
Knitted Pt/SiO
2
was used in enantioselective hydrogenation of 1-phenyl-
1,2-propanedione giving relatively high enantiomeric excesses.
294
The
knitted silica ber catalyst gave encouraging results in the continuous xed
bed operation with enantiomeric excesses comparable to those obtained in
the batch reactor.
EtPy was hydrogenated in a continuous-ow xed-bed reactor and high
ee value up to 89% was obtained at modier/substrate molar ratio of only
Catalysis, 2010, 22, 144278 | 175
307 ppm.
295
In another study
296
the enantioselective hydrogenation of ethyl-
2-oxo-4-phenylbutyrate (EOPB) on Pt/g-Al
2
O
3
catalyst in the presence of
CD was investigated in a xed-bed reactor with the aim to synthesize
enantiomerically pure (R)-( )-EHPB, a building block for the synthesis
of several commercially important A.C.E. inhibitors. The highest ee value
around 69% was obtained in toluene at 6 MPa hydrogen pressure. Al-
though stable conversion values were obtained in time on stream experi-
ments, the ee values decreased in time.
The transformation of isopropyl-4,4,4-triuoroacetoacetate to the cor-
responding hydroxyester was studied in a xed bed reactor over Pt/Al
2
O
3
in
the presence of MeO-CD and triuoroacetic acid.
297
Around 0 1C and upon
varying the pressure, the total liquid ow rate and the feed composition ee
values up to around 90% were achieved. However, the time on stream
pattern showed quite notable activity decrease.
Enantioselective hydrogenation of EtPy was performed in a continuous-
ow xed-bed reactor using supercritical carbon dioxide and supercritical
ethane (scC
2
H
6
).
299
In the latter solvent much higher catalytic activity was
observed.
Ethyl benzoylformate (EBF) was hydrogenated in a continuous-ow
xed-bed reactor over Pt/Al
2
O
3
catalyst in the presence of CD and CN.
299
Variety of chemical and physico-chemical methods was applied to pretreat
or clean the chiral xed bed between multiple hydrogenation reactions. It
was observed that after an enantioselective hydrogenation with CD as
modier at 0 1C, the continuous-ow reactor could be eectively cleaned at
0 1C, and that a racemic unmodied hydrogenation could be performed
thereafter. This implies the eective desorption of chiral species from the
surface during cleaning. Contrary to that cleaning of the reactor at 50 1C
resulted in a reproducible unmodied enantioselective hydrogenation, with a
marked inversion of enantiomeric excess. The inversion of ee will be dis-
cussed in Section 5.5.4.
In a recent study enantioselective hydrogenation of EtPy was also per-
formed in continuous-ow reactor in the presence of CD over Pt/Al
2
O
3
.
300
All these results indicate that the use of continuous-ow reactors should
be applicable to dierent substrates based on the use of chiral modiers and
supported metal hydrogenation catalysts. This approach provides more
ecient screening method for potential chiral modiers establishing the
basis for future technical applications. Based on the use of continuous-ow
reactors the so called chiral switch methodology has been developed for
the investigation of the relative adsorption strength or the competition of
chiral modiers on a metal surface.
238,301
4.7 Reuse and deactivation of catalysts
The reuse of the catalyst has a great practical signicance. The reuse is
strongly connected to the catalyst deactivation phenomena. Deactivation will
also be discussed in Section 5.2. Due to catalyst deactivation for the reuse of
supported Pt catalysts fresh modier has to be added before each hydrogen-
ation cycle,
302,303
or the modier is fed permanently in continuous man-
ner
108,290
to ensure good activity and high enantioselectivity.
176 | Catalysis, 2010, 22, 144278
Typical setup for these experiments is as follows: after the rst reaction
the mixing was stopped, the reaction mixture was left to settle for
30 min, the liquid was removed, and solvent, EtPy and occasionally modier
were added to the reactor. Hydrogenation was repeated as described
above.
268
An intelligent approach has been developed for the reuse of hydrogen-
ation catalyst.
304
Magnetic Pt/SiO
2
/Fe
3
O
4
catalyst was prepared and suc-
cessfully applied for the enantioselective hydrogenation of various activated
ketones. This catalyst modied with CD showed catalytic performance
(activity, enantioselectivity) in toluene comparable to the best-known Pt/
alumina catalyst. The new catalyst can be easily separated by an external
magnetic eld and recycled several times with almost complete retention of
activity and enantioselectivity.
Figs. 12A and B show two types of reuse experiments. In Fig. 12A fresh
modier has been added in each run, consequently the ee values are con-
stant; however there is a signicant catalyst deactivation. However, as
shown in Fig. 12B both the activity and ee decrease on reuse of the catalyst
if no fresh modier is added to the reaction mixture at the beginning of each
new run. It is known from other studies
246,248,261
that almost constant ee
values can be achieved in reuse experiments, where fresh modier is
added in every reuse.
Interesting observation was described in ref. 305. Stopping the enantio-
selective hydrogenation of EtPy at a conversion of approximately 70%,
long-term stability of the catalyst can be achieved. During 10 cycles of
hydrogenation, the activity and enantioselectivity of the repeatedly used
catalyst remain constant at high values even without adding fresh modier
at the beginning of each new run. These observations indicate that the loss
of modier takes place only at high conversion, i.e., the presence of excess of
substrate prevents the hydrogenation of the quinoline ring of the modier.
These results are shown in Fig. 13.
Fig. 12 Repeated use of catalyst for the enantioselective hydrogenation of EtPy. A: 5 ml
of toluene, [DHCD]
=
0.1 mmol/l, fresh DHCD was added each time to the reaction solution.
B: 5 ml of toluene, [DHCD]
=
0.01 mmol/l, no DHCD was added for reuse of catalyst.
(Reproduced from ref. 268 with permission)
Catalysis, 2010, 22, 144278 | 177
Dierent reuse methods and inuence of the solvent were investigated by
Barto k et al.
268
In the course of enantioselective hydrogenation of EtPy in
toluene, ee increased with catalyst reuse. The increase was in the range of
1020%, however this increase was not observed in acetic acid. The authors
considered that the phenomenon of increase in ee on reuse is an intrinsic
feature of the catalyst system used, i.e. new chiral centers making higher ee
possible are formed. It was suggested that during reuse due to the intensive
interaction of a solid surface and the chiral modier reconstruction of
the Pt surface takes place. This is in a good agreement with recent nd-
ings
306
that during reuse due to the intensive interaction of a solid surface
and the chiral modier reconstruction of the Pt surface takes place. The
authors believe that the surface atoms of the catalyst are continuously
reorganized during the reaction as a result of adsorption/chemisorption
steps. In this respect it was supposed that the presence of trace amounts of
oxygen might also play an important role in the reaction studied. The lack
of increase in ee on reuse in acetic acid may indicate that in this solvent the
reaction mechanism is dierent. The authors most important conclusions
with respect to the reuse of catalyst are as follows: (i) Pt/Al
2
O
3
catalysts
with a Pt-dispersion of 0.20.3 and a mean Pt particle size of 35 nm are the
best; (ii) prior to use, the catalyst should be prereduced at 673K for 11.5 h
in hydrogen ow; (iii) it is necessary to add fresh modier for each reuse of
the catalyst.
268
5. Specicity of Oritos reaction
As it has already been discussed that enantioselective hydrogenation of
activated ketones has several specicities. The main specicities are as fol-
lows: (i) side reactions, (ii) catalyst deactivation, (iii) solvent eect, (iv)
substrate specicity, (v) rate acceleration (enhancement), (vi) enantioselec-
tivityconversion (time) dependencies, (vii) non-linear phenomenon, and
(viii) inversion of enantioselectivity. In order to understand all peculiarities
of these unique reactions the specicities have to be discussed separately.
Fig. 13 Activity and ee values of the modied catalyst used repeatedly for the stopping after
complete conversion; right: stopping at 70% conversion) without addition of fresh modier.
(Reproduced from ref. 305 with permission)
178 | Catalysis, 2010, 22, 144278
5.1 Side reactions
The intrinsic reactivity of activated ketones is high. In this respect dierent
type of side reactions, such as (i) semi-ketal formation, (ii) oligomerization
(condensation, polymerization), (iii) hydrolysis, (iv) transesterication, (v)
deuterium exchange, and (vi) decarbonylation, can be distinguished.
Side reactions have a great inuence both on the rate and enantioselec-
tivity. The occurrence of side reactions depends on the mode of introduction
of the reaction components. The by-product formation can take place both
in racemic and enantioselective hydrogenation of activated ketones. In most
of the side reactions the substrates are involved. With respect to the modier
the hydrogenation of the quinoline ring has to be mentioned.
271
The rst thorough information related to the side reactions and by-
products formation was given in ref. 307 The formation of semi-ketals can
take place between the substrate and alcoholic solvent,
279
the substrate and
the reaction product,
233
the substrate and CD.
109
It has been demonstrated
in ref. 279 that CD catalyses the formation of semi-ketals. The extent of
semi-ketal formation increases in the following order: t-BuOHoi-PrOHo
EtOHoMeOH. Semi-ketals can be hydrogenolized to the corresponding
alcohols in a racemic reaction, i.e. this side reaction strongly decreases to
overall ee of the enantioselective hydrogenation.
Oligomerization and polymerization reactions have been discussed by
dierent authors.
109,308,309
In these reactions both Pt and alumina sites can
be involved. A dimer of the substrate is formed in the condensation reaction
of the enol and keto forms of EtPy.
233
The keto-enol transformation of
MePy has been recently investigated by using thermal programmed de-
sorption (TPD), STM and reectance adsorbance infrared spectroscopy
(RAIRS).
310
It was shown that MePy undergoes CH bond scission at room
temperature on clean Pt(111) leading to surface mediated enol formation
and assembly into H-bonded superstructure. The latter was severely in-
hibited by addition of hydrogen (10
6
Torr). STM data show no evidence
for an irreversible polymerization reaction.
In a recent study
311
it was suggested that base-acid sites on the g-Al
2
O
3
surface are responsible for the aldol reaction of EtPy to yield b-hydroxyl
ketone, which is subsequently dehydrated to generate C
Q
C containing
species (see Scheme 1). The formed condensation product can be involved in
cyclization reactions as shown in Scheme 2. These cyclic products were
considered as one of the key compounds poisoning the catalyst during the
hydrogenation of EtPy.
81
In ref. 311 side reactions with the involvement of
Pt sites were also investigated. Scheme 3 shows these reactions and the role
of hydrogen in their suppression.
The fact that the aldol condensation of EtPy on Al
2
O
3
can be suppressed
by adsorbed acetic acid may be interpreted as that the acetic acid adsorbs
and blocks some basic sites on alumina.
309
An additional set of side re-
actions was discussed in ref. 312. It was suggested that these reactions might
take place over the Pt sites resulting in strong poisoning eect.
312
Several adducts originating from the base-catalysed EtPy conden-
sation were detected by ESI-MS method.
313
Decarbonylation of both linear
(EtPy, MePy)
82,91
and cyclic a-ketoesters (KPL)
314
was evidenced by using
Catalysis, 2010, 22, 144278 | 179
ATR-FTIR method. It has been shown that both hydrogen and CD sup-
presses the decomposition of EtPy taking place on Pt surface.
91
The sta-
bilization of MePy against decomposition has been suppressed by
benzene
315
and 1-(1-naphthyl)ethylamine.
316
Scheme 1 Proposed mechanism for aldol condensation of EtPy catalyzed by the base-acid
sites on the g-Al
2
O
3
surface. (Reproduced from ref. 311 with permission)
O
O
O H
O
O
O
O
O
O H
OH
O
O
O
O
O
O
O
O
O
OH
O
O
-EtOH
2a
2b
1a
1b
Scheme 2 Further transformation of adduct formed in the condensation reaction of the keto
and the enol forms of EtPy. (Reproduced from ref. 81 with permission)
180 | Catalysis, 2010, 22, 144278
In a recent study it was shown that although adsorbed CD suppresses the
decomposition of EtPy it cannot suppress condensation and hydrolysis of
EtPy on g-alumina. Coexistence of CD and hydrogen is needed to suppress
all side reaction of EtPy over Pt/g-Al
2
O
3
.
311
Recently it has been suggested that the polymerization of EtPy takes
place preferentially at steps sites of Pt and CD or other tertiary amines
inhibits propagation of polymerization over Pt sites.
233
It is known that most of the products of the above side reactions are
considered as catalyst poison, consequently their presence signicantly alter
the intrinsic kinetic patterns of these reactions. All these facts strongly in-
dicate that experimental conditions have to be strictly standardized in order
to minimize the eect of by-products formed. The role of by-products to the
rate acceleration phenomena will be discussed in Section 5.5.1.
5.2 Catalyst deactivation
In the enantioselective hydrogenation of activated ketones catalyst de-
activation takes place both in batch and continuous-ow reactors. The
deactivation can be attributed to both of chemical and physical processes.
Scheme 3 Proposed mechanism for the side reactions of EtPy on Pt/Al
2
O
3
inhibited by H
2
.
(Reproduced from ref. 311 with permission).
Catalysis, 2010, 22, 144278 | 181
These processes can be explained as follows: (i) poisoning, (ii) coking, (iii)
sintering, (iv) restructuring and (v) phase transformation. Deactivation is
inevitable, but it can be retarded or prevented and some of its consequences
can be avoided with clever process design.
231
One of the main reasons for
catalyst deactivation can be ascribed to the formation of by-products as
described in the previous section.
Catalyst deactivation cannot be directly investigated in a batch reactor;
however the analysis of the time on stream behavior in continuous-ow
reactors provides useful information with respect to catalyst deactivation.
It has been shown that that irreversible deactivation of Pt catalysts by
condensation and oligomerization polymerization can be related to
hydrogen starvation.
312
In a recent study
311
it was found that only the
coexistence of CD and H
2
could thoroughly inhibit the side reactions of
EtPy on Pt/g-Al
2
O
3
.
The decrease of the catalytic activity due to the use of unpuried sub-
strates has been discussed in dierent studies.
66,69,82,317
Consequently,
purication of the reactant seems to be a necessary prerequisite to avoid
catalyst deactivation.
318
With respect to catalyst deactivation the dispute
related to the origin of rate acceleration has to be mentioned.
234,295
Further
discussion of this dispute will be given in Section 5.5.1.
Catalyst deactivation has been observed in kinetic experiments performed
in batch reactor.
233,289
Deactivation was also evidenced in continuous-ow
regime using various experimental designs.
291
It was also observed on
heating the platinum catalyst in either hydrogen or helium at 350 1C for two
hours and then using it without exposure to oxygen.
229
General principles of catalyst deactivation both in batch and continuous
ow reactors were given in ref. 319. In this work enantioselective hydro-
genation of 1-phenyl-1,2-propanedione was studied. An elegant way to
promote catalyst durability, activity and selectivity is to apply on-line
acoustic irradiation during the course of reaction.
320
Ultrasound can retard
catalyst deactivation by (catalyst) surface cleaning and exposing fresh,
highly active surface as well as by the reduction of diusion length in the
catalyst pores by alteration of the surface of catalyst. Furthermore, strongly
absorbed organic impurities that block active sites can also be removed by
sonication. In ref. 231 the deactivation was studied both under con-
ventional and microwave heating using EtPy as a substrate. No catalyst
deactivation was observed in three consecutive experiments with re-used
catalyst. Previously, it has been reported
107,321
that during continuous
hydrogenation of EtPy and 1-phenyl-1,2-propanedione; a notable catalyst
deactivation takes place.
Based on these results it can be concluded that in the enantioselective
hydrogenation of activated ketones deactivation is an inevitable phenom-
enon. However, there are measures to decrease the extent of deactivation.
These measures are as follows:
(i) application of acetic acid as solvent, which deactivates the amine
modier and the alumina support for aldol reaction;
295
(ii) decreasing the
modier/substrate ratio to reduce the rate of side reactions in solution;
(iii) working at high surface hydrogen concentrations, that is, at high
hydrogen pressure and in the absence of mass transport limitation; and
182 | Catalysis, 2010, 22, 144278
(iv) carefully avoiding the contact of Pt with pyruvate in the absence of
modier at low surface hydrogen concentrations, and (v) minimizing the
contact of the substrate and the modier before entering them into the reactor.
5.3 Substrate specicity
It is known that various prochiral ketones can enantioselectively be hy-
drogenated over Pt-cinchona catalyst system. This issue has been discussed
in various earlier reviews.
33,46,52,195,322
Characteristic feature of these sub-
strates is the presence of an activating group with strong electron-
withdrawing properties (ester, carbonyl, acetal, amido and a,a,a-triuoro
group) in the a-position to the prochiral keto group.
76
As most of the
substrates applied so far were extensively discussed in earlier reviews in this
section we shall give only a brief summary.
The rst substrates successfully hydrogenated asymmetrically were linear
and cyclic a-ketoesters,
48,84,282,290,323
a-diketones,
318,324327
a-ketoacetals,
328,329
aromatic a,a,a-triuoro-ketones,
284,330333
and linear and cyclic a-ketoa-
mides.
336338
The structure of these activated ketones is given in Fig. 14.
Later on the studies were extended to non-aromatic a,a,a-triuoro-
ketones
236
and substituted aromatic a,a,a-triuoroketones,
53,333,337
triuoro
substituted a, b-ketones,
44,338
b-ketoesters.
339
Pt-cinchona system has also
been used in the hydrogenation of substituted deactivated aromatic ketones,
such as 3,5-bis(triuoromethyl) acetophenone.
340
The types of substrates containing activated keto group and the highest ee
values in the presence of optimum modier are shown in Table 5.
50
Most of
the substrates, with the exception of the amido derivatives resulted in ee
values above 80%.
Additional results related to the inuence of substituents in a-keto esters
were published in refs. 338,341. In these studies both R
1
and R
2
substituents
(see Scheme 4) were systematically altered.
The Barto ks group found that in AcOH when R
1
was methyl, iso-propyl,
terc.-butyl, phenyl and phenylethyl or the R
2
group was methyl, ethyl and
isopropyl the sense of the enantio-dierentiation was not altered. The in-
crease of the size of R
1
and R
2
resulted in slight decrease in the reaction rate
and ee values.
Additional results presented by Baikers group are summarized in
Table 6.
338
In this series a of experiments the variation of the bulkiness both
at the keto and ester sides in nine dierent a-ketoesters was investigated
upon using CD and QN, as chiral modiers. In toluene in the presence of
CD good to high ee values (ee
max=
94%) were achieved. Consequently, in
the presence of CD the enantio- dierentiation is controlled by the ester
group, notwithstanding of the steric bulkiness or electronic structure of the
O
O
O
O
O
O
O
NH
O
O
R CF
3
O
O
O
O
Fig. 14 Structure of rst substrates successfully hydrogenated asymmetrically.
Catalysis, 2010, 22, 144278 | 183
T
a
b
l
e
5
H
y
d
r
o
g
e
n
a
t
i
o
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o
f
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t
i
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a
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k
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t
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s
o
v
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r
P
t
/
A
l
2
O
3
-
c
i
n
c
h
o
n
a
c
a
t
a
l
y
s
t
s
.
(
R
e
p
r
o
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c
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d
f
r
o
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r
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f
.
5
0
w
i
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m
i
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)
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i

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r
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b
s
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-
P
t
r
a
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(
%
)
R
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f
.
1
O
O
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Q
D
A
c
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H
1
5
4
0
1
6
4
0
9
8
c
3
4
4
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T
o
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8
6
8
3
0
0
9
8
5
6
3
O
H
O
O
M
e
O
C
D
E
t
O
H
/
H
2
O
3
5
0
4
4
0
8
2
3
4
5
4
O
O
O
C
D
T
o
l
u
e
n
e
2
9
6
0
0
0
1
0
4
0
9
1
d
3
2
3
5
O
O
N H
C
D
A
c
O
H
3
0
0
1
6
0
5
8
3
3
4
6
b
u
t
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d
i
o
n
e
C
D
T
o
l
u
e
n
e
4
0
2
1
0
0
6
3
3
2
6
7
O
O
C
D
E
t
O
A
c
1
4
3
6
6
9
4
e
3
4
6
184 | Catalysis, 2010, 22, 144278
8
N
O
O
C
D
T
o
l
u
e
n
e
3
2
0
2
1
0
9
1
3
3
5
9
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t
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D
H
C
D
T
o
l
u
e
n
e
7
2
0
7
1
0
8
6
3
4
7
1
0
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O
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A
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H
1
0
5
0
1
3
2
0
9
7
3
3
0
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1
3
0
1
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0
9
7
3
2
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1
1
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3
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-
T
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0
1
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0
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6
f
5
0
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3
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)
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8
1
C
.
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k
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e
t
i
c
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e
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f

2
0
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C
,
C
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:
c
i
n
c
h
o
n
i
d
i
n
e
,
D
H
C
D
:
1
0
,
1
1
-
d
i
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y
d
r
o
c
i
n
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o
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,
M
e
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:
m
e
t
h
o
x
y
-
H
C
D
,
M
e
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D
:
m
e
t
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o
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,
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:
t
e
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r
a
h
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r
i

u
o
r
o
a
c
e
t
i
c
a
c
i
d
.
Catalysis, 2010, 22, 144278 | 185
alkyl and functionalized aryl group on the other side of the keto group.
Other studies reveal also that ester, carboxyl, amido, carbonyl, acetal, and
triuoromethyl functions have similar directing eects. Results presented in
Table 6 show that structurally more demanding substrates show signicant
dierences between toluene and acetic acid. However, none of the mech-
anistic models developed for the enantioselective hydrogenation of acti-
vated ketones over Pt-cinchona catalyst system can explain the following
anomalies found in Table 6: (i) higher ee values in toluene in the presence of
CD for substrates (2), (4), (5) and (9); (ii) the strong increase of ee in acetic
acid in the presence of QN for substrate (1); (iii) almost complete loss of ee
in AcOH in the presence of QN for substrates (3) and (9).
In the presence of CD the greatest drop both in the conversion and ee
values was measured for the hydrogenation of 9 (see Table 6) when chan-
ging from toluene to AcOH. This observation was attributed by the authors
to the strong, competing adsorption of AcOH. It seems to us that it is a
very plausible explanation. We consider this observation as an artifact, as in
our independent experiment no similar observation was found.
342
There are additional controversial data with respect to the use of AcOH.
In ref. 338 based on a relatively early study
343
it has been mentioned that the
enantioselectivities in toluene and acetic acid are similar.
53
This statement is
not really correct as in various other studies
73
it has been shown that in
acetic acid both the rate and ee values are higher than in toluene. It has
already been shown that the addition of a small amount of acetic acid either
to toluene or ethanol has a very pronounced eect.
84
Derivatives of triuoroacetophenone with dierent substituents at the
aromatic ring (CF
3
, N(Me)
2
and Me) were hydrogenated over Pt/Al
2
O
3
in
the presence of CD, CDHCl and 9O-methyl-CD.
332
It was shown that
electron-withdrawing substituents increased and electron-releasing one de-
creased the rate and enantioselectivity in these reactions, although steric
eects (with m- or p-substituents) were also substantial. Cinchona alkaloids
were also used in the asymmetric hydrogenation of non-activated ketones.
In this case the enantioselectivity is rather moderate as it was emphasized in
a recent review.
195
Upon using various nonactivated triuoromethyl ketones, such as me-
thyl-, adamantyl, and terc-butyl
235
in the presence of CD low ee values were
obtained (ee
max=
44% for adamantyl derivatives). Positive eect of TFA
was also demonstrated, while the use of AcOH as a solvent resulted in low
yields and low ee values. In propanol inversion of the ee was observed.
These results conrmed again that in the hydrogenation of non-activated
ketones high ee values couldnt be expected. Unfortunately, the initial rates
were not determined in this study. The authors claimed that their result
indicates that enantioselectivity is guided by the triuoromethyl
Scheme 4 R
1
and R
2
substituents systematically altered in the hydrogenation of a-keto esters.
(Reproduced from refs. 338 and 341 with permission)
186 | Catalysis, 2010, 22, 144278
substitution rather than by the relative bulkiness of the substituents at the
two sites of the carbonyl group.
5.4 Solvent eect
In enantioselective hydrogenations of activated ketones both the rates and
the enantioselectivities are greatly inuenced by the type of solvents used.
Table 6 Enantioselective hydrogenation of various a-ketoesters in toluene and acetic acid
(Reproduced from ref. 438 with permission)
Substrate Reaction in toluene Reaction in AcOH
R
1
O
R
2
O
O
CD
ee(%)
[conv.]
QN
ee(%)
[conv.]
CD
ee(%)
[conv.]
QN
ee(%)
[conv.]
1 CH
3
CH
2
CH
3
80 (R) 21 (R) 88 (R) 92 (R)
[100] [100] [100] [100]
2
H
3
C
H
3
C
CH
3
CH
2
CH
3
56 (R) 12 (R) 27 (R) 2 (R)
[91] [61] [99] [99]
3 CH
2
CH
3
86 (R) 79 (R) 86 (R) 4 (R)
[100] [100] [100] [100]
4
H
3
C
H
3
C
CH
3
95 (R) 89 (R) 70 (R) 24 (R)
[94] [43] [73] [64]
5 CH
2
CH
3
92 (R) 75 (R) 80 (R) 31 (R)
[100] [197] [100] [100]
6
F
F
CH
2
CH
3
87 (R) 76 (R) 86 (R) 76 (R)
[100] [99] [100] [100]
7
F
3
C
CF
3
CH
2
CH
3
66 (R) 47 (R) 72 (R) 72 (R)
[94] [90] [98] [98]
8
O
O
CH
2
CH
3
94 (R) 84 (R) 94 (R) 84 (R)
[95] [100] [94] [91]
9 CH
2
CH
3
86 (R) 60 (R) 46 (R) 0 (R)
[100] [32] [31] [7]
Catalysis, 2010, 22, 144278 | 187
Both protonic and aprotonic solvents have been applied. The solvent can
inuence the enantioselective hydrogenation in dierent ways; it changes
the solubility of the hydrogen
99
and the substrate, the mass transport
properties of the reaction mixture, the adsorption behavior of substrates
and modier on the Pt active sites.
Solvents have also a great inuence on the conformation of alkaloid
used.
88,176,183
Furthermore, with less rigid substrates, e.g. alkyl pyruvates,
the solvent polarity can also aect the conformation of the substrate.
49
Unfortunately, there are no general rules for the selection of an optimum
solvent as both the rate and ee values were aected not only by the solvent,
but also by the substrate and the alkaloid applied.
In the rst studies ethanol was the most common solvent used; however
as it was shown latter the alcohols react with a-ketoester with the formation
of semi-ketals (see Section 5.1). This eect was also discussed in a recent
study related to the enantioselective hydrogenation of ethyl-4,4,4-tri-
uoroacetoacetate
348
in ethanol and propanol.
All these results indicate that the use of alcohols in kinetic or mechanistic
investigations
65,247,348,349
should be avoided as it was emphasized in ref. 53.
Upon using O-alkylated CD (R-O-CD) derivatives the use of AcOH or
TFA is not recommended as in their presence hydrolysis of R-OCD can
take place. AcOH was not a proper solvent for KPL.
77
In one of the rst studies the reaction rates and enantioselectivities were
compared in ethanol, toluene and acetic acid.
73
These results un-
ambiguously show the advantage of using AcOH. In another studies it was
shown that upon hydrogenating EtPy AcOH is the best solvent as the
highest ee values (ee
=
98%)
55
and highest reaction rates were obtained in
this solvent.
The inuence of the two most commonly solvents, i.e., toluene and acetic
acid, on the rates and ee in enantioselective hydrogenation of EtPy are
shown in Table 7. These data clearly show the superior inuence of AcOH
on the ee values. Not only higher ee values were obtained in AcOH, but also
the amount of modier required to get high ee values is one order less in
AcOH than in toluene. However, it is interesting to note that contrary to
earlier observations at atmospheric hydrogen pressure the rate of hydro-
genation in toluene is higher than in AcOH. In this respect it is worth for
Table 7 Hydrogenation of EtPy at atmospheric and at high pressure. Comparison of reaction
rates and ee values in toluene and acetic acid solvents. (Reproduced from refs. 267, 350 with
permission)
Modier,
Mmol/l
Hydrogenation
in AcOH at
100 bar
350
Hydrogenation
in AcOH at
1 bar
267
Hydrogenation
in toluene at
100 bar
350
Hydrogenation
in toluene at
1 bar
267
rate,
mmol/sec ee, %
rate,
mmol/sec ee, %
rate,
mmol/sec ee, %
rate,
mmol/sec ee, %
0.001 35 83 16 69 8 35 35 16
0.01 80 92 55 91 20 75 57 64
0.1 105 94 85 92 48 82 96 78
1 135 94 63 92 25 83 71 77
188 | Catalysis, 2010, 22, 144278
mentioning that in racemic hydrogenation of EtPy higher rates were
measure in toluene than in AcOH.
342
Other organic acids were also used to improve the enantioselectivity in Pt-
cinchona system. Fig. 15 shows the inuence of added triuoroacetic acid
(TFA) on the enantioselectivity in the hydrogenation of KPL in the pres-
ence of synthetic modier (R,R)-PNEA. The results showed that excess
TFA was needed to get maximum ee values. It was suggested that part of
the excess TFA be required to neutralize basic sites of the Al
2
O
3
support.
Excellent correlation was found between the dielectric constant of the
solvents used and both the enantiomeric excess and the population of
conformer Open(3) as calculated by density functional theory in combin-
ation with a reaction eld model (P
Open(3)
).
88
This dependence is shown in
Fig. 16. Earlier results indicated that both reaction rates and ee values de-
creased with the polarity of the solvent. Figs. 17AC show the dependence
of ee on the empirical solvent parameter E
N
T
in three dierent systems.
In the hydrogenation of EtPy (see Fig. 17A) good ee values are obtained in
moderately apolar solvents, in which the reactant and modier dissolve.
46
Interestingly, primary alcohols are also good solvent, although they react
rapidly with the substrate with the formation of corresponding semi-ketals.
The highest ee that time was 95% obtained in acetic acid, while the lowest
one in water. The former result was attributed to the protonation of the
quinuclidine nitrogen of CD by AcOH and suggesting the alteration of the
reaction mechanism in AcOH,
283
while the low activity in water can be
attributed to the side reaction between EtPy and water, i.e. to the formation
of corresponding vicinal diol, and the racemic hydrogenolysis of the diol
formed. The latter reaction is responsible for the loss of ee. Fig. 17A shows
that the solvent inuence is notable, although the slope in this gure is
relatively moderate. Contrary to that in Rh/Al
2
O
3
-b-ICN system used in the
hydrogenation of KPL the above slope is higher indicating that the solvent
has more pronounced inuence on the enantioselectivity (see Fig. 17B).
340
Fig. 15 Enantioselective hydrogenation of KPL over Pt/Al
2
O
3
in the presence of synthetic
modier (R,R)-PNEA. The solvent was toluene with increasing amount of TFA. (Reproduced
from ref. 209 with permission)
Catalysis, 2010, 22, 144278 | 189
The third system behaves in a completely dierent way. The correlation
between ee and E
N
T
is not really good, however it is more interesting that the
character of dependence is opposite compared to the systems given in
Figs. 17A and B. Nevertheless, the striking eect of solvent properties on
the ee values is obvious. The highest ee to (S)-3,5-di(triuoromethyl)
phenylethanol was obtained in the weakly polar solvent toluene and ethyl
acetate. The ee decreased in polar solvents. In dimethylformamide, iso-
propanol, and ethanol the ee inverted from the (S) to the (R) enantiomer.
This behavior indicates that in case of substituted acetophenones the
reaction mechanism is strongly altered.
There is another unusual behaviour of this type of substrates. In the
enantioselective hydrogenation of 3,5-bis(triuoromethyl)acetophenone the
addition of triuoroacetic acid (TFA) resulted in strong decrease in the
reaction rate at TFA/CD
=
around 5 and full inversion of ee at TFA/
CDW50.
340
Among the solvents AcOH and its triourinated derivative (TFA) has
their own peculiarities. The dierence in the rates in AcOH and other
solvents is well documented in one of the earlier results, where the addition
of small amount of acetic acid strongly increased the overall performance of
the reaction both in toluene and ethanol solvents
84
as shown in Table 8.
Results given in Table 8 reect also the inuence of semi-ketal formation in
alcoholic solvents on the reaction rate and ee. The rate decreases in the
following order: n-butanolWethanolWmethanol, i.e. it follows the reactivity
trend of alcohols to form semi-ketals: n-butanoloethanolomethanol.
Very pronounced solvent eect was observed in the hydrogenation of
1,1,1-triuoro-5,5-dimethyl-2,4-hexanedione using Pt/Al
2
O
3
in the presence
Fig. 16 Combined plot of the ee values obtained in the hydrogenation of KPL over Pt/Al
2
O
3
-
CD system (left axis) and the population of conformer Open(3) as calculated by DFT in
combination with a reaction eld model (P
Open(3)
, right axis) v.s. the dielectric constant of the
solvent (axis scale is arbitrarily chosen). Solvents: 1 cyclohexane, 2 hexane, 3 toluene, 4
diethyl ether, 5 tetrahydrofurane, 6 acetic acid, 7 ethanol, 8 water, 9 formamide.
(Reproduced from ref. 88 with permission)
190 | Catalysis, 2010, 22, 144278
of synthetic modier, pantoyl-naphthylethylamine.
210
The results show a
dramatic inuence of solvents on the ee values. No correlation can be
obtained between ee and relative permittivity (e
r
,) or empirical solvent
parameter (E
N
T
). Surprisingly high ee values were obtained only in halogen
Fig. 17 Eect of solvent on enantiodierentiation of in dierent enantioselective hydrogen-
ation reactions. Dependence of the ee value on empirical parameter E
N
T
(reproduced from
refs. 46,340,352 with permission) A: Pt/Al
2
O
3
-CD and DHCD in EtPy hydrogenation.
46
Solvents: 1
=
cyclohexane, 2
=
toluene, 3
=
chlorobenzene, 4
=
THF, 5
=
dichloromethane,
6
=
propanol, 7
=
1-pentanol, 8
=
ethanol, 9
=
AcOH, 10
=
methanol, 11
=
water; B: Rh/Al
2
O
3
-
b-ICN in KPL hydrogenation.
351
Solvents: 1
=
toluene, 2
=
t-BuMe ether, 3
=
THF,
4
=
dichloromethane, 5
=
DMF, 6
=
t-butanol, 7
=
acetonitrile, 8
=
2-propanol, 9
=
AcOH;
C: Pt/Al
2
O
3
-CD in the hydrogenation of 3,5-bis(triuoromethyl) acetophenone.
340
Table 8 Solvent eect and inuence of acetic acid. (Reproduced from ref. 84 with permission)
No Solvent k
1
, min
1
k
2
, min
1
Optical yield
c
, %
1 Methanol 0.022 0.019 62.2
2 ethanol 0.057 0.034 72.0
3 n-butanol 0.099 k
2
Wk
1
75.0
4 toluene (EtPy)
a
0.057 k
2
Wk
1
86.3
5 MCH (EtPy)
a
0.106 0.106 78.1
6 toluene (AcOEt)
a
0.063 k
2
Wk
1
84.0
7 MCH (AcOEt)
a
0.069 0.060 75.3
8 ethanol AcOH
b
0.074 0.048 91.4
9 toluene AcOH
b
0.120 0.120 93.1
Reaction conditions: T
=
23 1C, P
=
50 bar, [EtPy]
0=
1.0 M, [CD]
=
8.4 10
4
M, CD in-
jection.
a
Ethyl pyruvate or ethyl acetate (1.5 cm
3
) is added to dissolve cinchonidine in these
solvents (8.5 cm
3
).
b
The solvent is mixed with acetic acid; [AcOH]
0=
5.0 M.
c
Measured at
90100% conversion.
Catalysis, 2010, 22, 144278 | 191
containing solvents. Some of these solvents, for instance dichloromethane,
are often called as reactive solvent. A rapid loss of activity of Pt/alumina
was found in this solvent and steady-state conditions could not be reached
in the continuous-ow reactor at 10 bar.
295
In one of the recent publications
352
it was mentioned the use of
dichloromethane should be avoided in hydrogenation reactions. As it was
emphasized dehalogenation of this solvent on Pt, particularly at high
hydrogen pressure, aords HCl, which induces a new set of acid-catalyzed
side reactions. It is a very correct remark what was addressed against the use
of CH
2
Cl
2
at high pressure by an English group.
233
However, we consider also that the use of CH
2
Cl
2
as a solvent by Baikers
group in ATR-FTIR spectroscopic studies
314
can also be criticized. These
ATR-FTIR studies are considered as one of the crucial proves for the
formation of protonated CD in the absence of AcOH. However, as it was
mentioned in ref. 352 HCl can be formed from CH
2
Cl
2
. Consequently, the
use of CH
2
Cl
2
would result in the protonation of CD in the absence of
AcOH and hydrogen.
5.5 Kinetic aspects
5.5.1 Rate acceleration. The rate enhancement of enantioselective hy-
drogenation of activated ketones has been observed by various research
groups. The rst results were published by the Ciba Group.
57,58,63
The
phenomenon was also observed by others.
65,67,289
In all of these studies
using EtPy as a substrate the common observation was that the modied
reaction is 20100 times faster than the unmodied one.
The rate enhancement was also described as ligand acceleration
58
based on the analogous observation in homogeneous catalysis.
353
It was
proposed that a reaction is considered ligand accelerated if there is a slower
unmodied (unselective) cycle and a faster modied (selective) cycle.
58
This term has been used for many years, although its chemical meaning is
quite doubtful or even misleading.
Most of the authors use the term rate acceleration (RA) or rate en-
hancement (RE). Not only cinchona alkaloids, but also other tertiary
amines, such as quinuclidine, triethylamine, etc. can induce RA
63
. This
behaviour was evidenced in various solvents.
73,354
The addition of small
amount of acetic acid into ethanol or toluene resulted in even more pro-
nounced RA
84
. This behaviour is very characteristic for a-keto esters
(Etpy, MePy, KPL
77
) and was observed not only over Pt, but other metals
such as Rh
252,254
and Ir.
355
In ref. 341 it was found that in a-ketoester the
increase of the size of R
1
and R
2
groups resulted in slight alteration in the
extent of RA.
With respect to kinetics studies the reproducibility problems related to
dierent impurities has to be mentioned.
73,84
Dierent batches of ethyl
pyruvate can give completely dierent kinetic results.
84,356
The impurities
alter both the initial rates and the enantioselectivity. When unpuried EtPy
is used in this case the rate of racemic hydrogenation is extremely low.
233
For this reason, kinetic results using the given substrate without any puri-
cation
65,66,227,232
should be treated with great precaution. However, even in
192 | Catalysis, 2010, 22, 144278
this case the addition of cinchona alkaloids as modiers or even dierent
tertiary amines increases the rate signicantly.
The other problem is that initial rates or related kinetic information
are only seldom published. Most authors prefer to provide activity data in
the form of conversion values measured after a given reaction time. It is
especially notable in recent publications.
235,351,357
Consequently, less and
less information is available with respect to the RA phenomena. It has
to be mentioned that RA has been observed only in liquid phase
hydrogenations; in gas phase hydrogenation of MePy no RA was
measured.
288
Direct measurement of the reaction rates by using reaction calorimetry in
a transient experiment provided an unambiguous evidence for the RA
100
.
The results show that upon injection of CD the rate increase is instant-
aneous and the rate increase is in the range of 512 depending on the type of
catalyst used. Similar pronounced RA was observed in other studies over
5% Pt/Al
2
O
3
catalyst using EtPy upon injecting cinchona type modiers or
tertiary amines at higher pressures.
289,307
With respect to the RA one important question can be raised: is any
direct coupling between the reaction rate and the enantioselectivity. This
coupling was rst described by Blaser et al. in their ligand acceleration
model.
58
Although the above coupling was clearly presented recently more
and more evidences have been accumulated that this coupling is not a
prerequisite to obtain high enantioselectivities.
The rst evidences against the direct coupling were obtained in our
studies.
289,358
In ref. 358 it was shown that the modication of Pt/Al
2
O
3
by
Sn(C
2
H
5
)
x
moieties strongly alter the reaction rates, but their eect on the ee
is negligible. Based on the analysis of the form of conversion-selectivity
dependencies in ref. 289 it was stated that, at low concentrations of sub-
strate and modier, contrary to instantaneous rate acceleration, the maximum
ee values are obtained only after a certain time delay. The increase of the rate
of enantioselective hydrogenation with respect to the racemic one was well
documented in ref. 203 upon using four dierent substrates (EtPy, EOG,
EBF, PADA) as shown in Fig. 18.
It should also be mentioned that there is a denite class of substrates that
do not show any RA or even the rate of enantioselective reaction is slower
than the rate of racemic one. In most of these substrates the prochiral keto
group is not activated. These substrates are as follows: acetophenone,
359
3,5-bis(triuoromethyl)acetophone,
340
alkylsubstituted triuoromethyl
ketones.
359,360
Classication of substrates according to their extent of RA and ED was
given recently (see Fig. 1).
72
In addition, the following experimental con-
ditions are not favourable for RA: (i) MePy pyruvate in gas phase;
290
(ii)
EtPy in the presence of a-ICN;
197,361
(iii) EBF in AcOH at 1 bar hydrogen;
56
(iv) non-activated aromatic ketones
359
and non-activated triuoromethyl
derivatives;
363
(v) hydrogenation of EtPy in the presence of CD at very low
substrate concentrations.
234
The appearance and the disappearance of RA acceleration are well
documented in a series of experiments using triuoro acetophenone and
cyclohexyl analog. In the case of the former substrate pronounced rate
Catalysis, 2010, 22, 144278 | 193
acceleration was observed as shown in Fig. 19A. Contrary to that upon
using triuoro cyclohexyl ketone in the presence of modier the rate of
reaction decreased as presented in Fig. 19B.
Further insight on the origin of RA was obtained upon comparing the
hydrogenation of acetophenone and triuoromethyl derivatives of
Fig. 18 Conversionreaction time dependencies in the enantioselective hydrogenations of
activated ketones (standard conditions, DHCD concentration 0.01 mmol l
1
, 0.16 ml; EOG:
diethyl 2-oxoglutarate, EBF: ethyl benzoylformate, PADA: pyruvaldehyde dimethyl acetal, ()
racemic hydrogenations, (v) enantioselective hydrogenations.) (Reproduced from ref. 203 with
permission).
Fig. 19 The eect of CD concentration on the enantioselective hydrogenation of triuoro
compounds. A: Substrate
=
triuoroacetophenone; B: Substrate
=
triuoromethylcyclohexyl
ketone. (Reproduced from refs. 360,363 with permission)
194 | Catalysis, 2010, 22, 144278
acetophenone over Pt/Al
2
O
3
-CD system.
332,362
In these studies both the rate
and the ee values strongly depended on the electronic and steric eect of the
substituents and on the hydrogen-bonding interactions between the qui-
nuclidine N atom of the alkaloid and the carbonyl group of the substrate.
In the hydrogenation of acetophenone and triuoromethylacetophenone
derivatives on CD-modied Pt/Al
2
O
3
, the conversion rates and enantio-
selectivities varied strongly with the nature of the aromatic substitu-
ents.
332,362
Dierent reactivities were attributed to the electronic (and steric)
eect of the substituents and to hydrogen-bonding interactions between the
quinuclidine N atom of the alkaloid and the carbonyl group of the sub-
strate. A linear correlation has been found between the logarithm of the
reaction rate and the highest occupied molecular orbital and lowest un-
occupied molecular orbital stabilization of the carbonyl compounds
(DE
orb
), relative to the reference compound.
359
The by-products are high-molecular weight compounds and are con-
sidered as strong catalyst poisons reducing the number of available Pt sites
resulting in substantial decrease in the reaction rates. Consequently, in
this case the RA is masked by a catalyst poisoning eect. Recently the
RA phenomenon has been questioned by two research groups.
233,234,364
In ref. 232 it was concluded that rate enhancement is now attributed to
reaction occurring at a normal rate at an enhanced number of sites, not (as
previously proposed) to a reaction occurring at an enhanced rate at a
constant number of sites.
The nal conclusion was that the rate enhancement in the presence of an
alkaloid modier is attributed to the inhibition of the pyruvate ester poly-
merization at the Pt surface. In another recent study
365
it was emphasized
that the reaction rate was lower in all chirally modied reactions as
compared to the racemic reaction in the absence of modier.
We believe that in references cited above experimental conditions were
not properly chosen as their ndings strongly contradict to results observed
earlier by several groups. In a recent paper
352
the use of reactive solvent
in ref. 232, such as dichloromethane, was strongly criticized.
Recently, with respect to the RA phenomena an open dispute has been
emerged in Journal of Catalysis.
295,352,366
In a recent study continuousow
experiments were performed providing clear evidence that the rate accel-
eration exists and it was concluded that it is not the suppression of catalyst
deactivation by addition of chiral modier, because under appropriate
conditions catalyst deactivation is negligible in pyruvate hydrogenation.
295
This statement was strongly opposed in ref. 366. Those who favor the role
of deactivation defended their view referring to their earlier results shown in
Fig. 20.
234
This gure shows that the rate acceleration appears only at high
concentration of substrate, while at low concentration the rate of enantio-
selective hydrogenation is lower than that of the racemic one. In this respect
it has to be mentioned that the determination of reaction rate at low sub-
strate concentration is very plausible. We consider that the minor dier-
ences shown in Fig. 20 cannot be considered as a real prove for the lack
of RA.
We have to emphasize again that the decrease of the reaction rate in
enantioselective hydrogenation of EtPy at low substrate concentration
366
Catalysis, 2010, 22, 144278 | 195
can be related to the decreased concentration of substrate-modier com-
plexes formed under condition of catalytic hydrogenation. In this respect it
is irrespective where the above complex has been formed in the liquid phase
or at the Pt surface. The decrease of the concentration of intermediate
complex can result in pronounced rate decrease; similar to the kinetic pat-
terns observed in enzymatic kinetics.
In our recent study transient experiments with injection of CD during
racemic hydrogenation of EtPy were investigated using puried substrates
and a distillation residue. The distillation residue contained 20% of
compound 1a (see Scheme 2 in Section 5). Fig. 21A shows that the increase
in the time delay between the start of racemic hydrogenation and the in-
jection of CD has no inuence on the rate of enantioselective
Fig. 20 Initial hydrogenation rates of enantioselective (D) and racemic hydrogenation (E) of
EtPy and the enantiomeric excess (K). (reproduced from refs. 234 with permission)
0.0
0.2
0.4
0.6
0.8
1.0 A
0 50 100 150
time, min
c
o
n
v
e
r
s
i
o
n
0.0
0.2
0.4
0.6
0.8
1.0
0 50 100 150
time, min
c
o
n
v
e
r
s
i
o
n
Fig. 21 Inuence of the time delay in CD injection during raceme hydrogenation. Kinetic
curves of EtPy hydrogenation upon using puried substrate; [CD]
=
5 10
5
M, T
=
20 1C,
P
H2=
50 bar, catalyst
=
5% Pt/Al
2
O
3
(E 4759), 0.125 g;
7
CD injection at 0 min; & CD
injection at 15 min; CD injection at 30 min; } CD injection at 90 min; () no CD
(racemic hydrogenation); A: [EtPy]
0=
1.0 M (puried by distillation prior to the use); B:
[EtPy]
0=
1.0 M (distillation residue containing dimer 1a in the amount of 20%). (Repro-
duced from ref. 367 with permission)
196 | Catalysis, 2010, 22, 144278
hydrogenation. It means that racemic products formed up to 10% con-
version have no measurable inuence on the reaction rate, consequently the
size of free Pt surface available for enantioselective hydrogenation is not
altered during racemic hydrogenation. When similar series of experiments
were performed in ethanol in the above conversion range slight decrease in
the initial rates was observed.
289
Results given in Fig. 21B clearly show that upon using the distillation
residue the rate of racemic hydrogenation decreases, the decrease in rate is
around eleven-fold compare to puried EtPy. The rate decrease in the ra-
cemic hydrogenation is due to the strong poisoning eect induced by
compound 1a. The poisoning eect can also be observed in enantioselective
hydrogenation, its extent is around three-fold. The introduction of CD
during racemic hydrogenation of distillation residue resulted in also in-
stantaneous rate acceleration in all cases (see Fig. 21B).
Contrary to results obtained in the previous series of experiments upon
increasing the time delay from zero to 90 minutes the rate of enantioselec-
tive hydrogenation decreases. All these results unambiguously show that the
statement given in ref. 232 rate enhancement is now attributed to reaction
occurring at a normal rate at an enhanced number of sites, not (as previ-
ously proposed) to a reaction occurring at an enhanced rate at a constant
number of sites cannot be valid. It is hard to suggest that the addition of
5 10
5
M modier will compete with 0.2 M high molecular weigh product
and can remove their adsorbed forms instantaneously from the Pt surface.
In an analogous series of experiments shown in Fig. 22, upon using
methyl-benzoyl formate (MBF) substrate
367
similar trend in the concen-
tration dependences was obtained as in the case of EtPy (see Fig. 20).
However, the rate of the enantioselective hydrogenation was higher than
that of the racemic one in the whole concentration range.
Results obtained in series of experiments using MBF shows that the RA
eect is maintained in a relatively broad concentration range. It is a good
example for the appearance of RA for the class of substrate with decreased
ability to form by-products. Finaly let us conclude that we completely
y = 0.007Ln(x) + 0.0306
R
2
= 0.9794
y = 0.0007Ln(x) + 0.0053
R
2
= 0.9206
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0 0.2 0.4 0.6
Concentration MBF, M
d
[
R
+
S
]
/
d
t
,

M
/
m
i
n
1
Fig. 22 Initial hydrogenation rates of enantioselective (&) and racemic hydrogenation (}) of
MBF. (Reproduced from ref. 367 with permission)
Catalysis, 2010, 22, 144278 | 197
disagree with the new views advertised in refs. 233, 234. Both our earl-
ier
69,289,307
and recent results
269
show that upon introduction of CD during
racemic hydrogenation of EtPy the RA are instantaneous. This conclusion
has been supported by recent results obtained in continuous ow
reactor.
295,366
5.5.2 Enantioselectivityconversion dependencies. In enantioselective
hydrogenation of EtPy one of the most disputed kinetic pattern is the form of
the enantioselectivityconversion (time) dependencies (ECD). In the hydro-
genation of EtPy monotonic increase (MI) type dependencies were obtained
at low conversion in various studies
83,84,268,289,369
as shown in Fig. 23. The
MI type behaviour is often called as initial transient period (ITP).
195
In rst publications integrated ee values were calculated from actual
concentration of (R) and (S) products according to the general formula
ee = ([R[ [S[)=([R[ [S[):
Further on incremental ee values (ee
incr=
ee
calc
or Dee) were also used.
374
It was calculated using the following formula:
ee
incr
= [c
2
ee
2
c
1
ee
1
[=[c
2
c
1
[
where c is the actual concentration of ethyl lactate and ee is the measured
optical yield. The use of ee
incr
reects the ee values in a given time interval.
It is applied when two dierent types of modiers are added to the reaction
mixture or when the loss of the modier during the enantioselective hydro-
genation is very pronounced. In addition kinetic ee values can also be cal-
culated from the corresponding reactions rates:
ee
kin
= ([r
R
[ [r
S
[)=([r
R
[ [r
S
[):
Fig. 23 Changes in ee observed during the course of EtPy hydrogenation. A: hydrogenation
over a DHCD-Pt catalyst;
369
B: hydrogenation over CD-Pt catalyst
84
(2, ) in toluene,
CD
inj
. [Etpy]
0=
1.0 M, [CD]
0=
8.4 10
4
M, 3.4 10
2
M, respectively; all other experiments
in ethanol, [Etpy]
0=
1.0 M, (B) [CD]
0 =
6.8 10
6
M, (E) [CD]
0inj=
3.4 10
5
M, ()
[CD]
0=
0.4 10
4
M, (CDEtPy)
inj
, (&) [CD]
0=
8.4 10
4
M, (EtPy)
inj
, (CD)
premixed
.
(Reproduced from refs. 84 and 369 with permission)
198 | Catalysis, 2010, 22, 144278
This kind of behaviour was also observed upon using other activated
ketones, such as PADA,
281
MBF
281
and KPL.
53
In earlier studies this be-
haviour was not discovered as no attempt was done to determine the ee
values at low conversion.
Other characteristic feature of ee-conversion (time) dependencies is the
decrease of the ee values at high conversion.
108
This decrease was attributed
to the loss of alkaloid during the enantioselective hydrogenation. The
addition of further amount of alkaloid during the hydrogenation experi-
ment resulted in almost constant ee values even at high conversion.
108
Results shown in Figs 23A and B have one common feature, i.e., the use
of injection method for the introduction of reaction compo-
nents. Fig. 23A shows the ee-time dependencies in EtPy hydrogenation
in ethylacetate injecting the substrate into the mixture containing the
catalyst and the modier. When CD was injected into the reactor
using toluene or ethanol as a solvent MI type enantioselectivity-conversion
dependencies were also observed provided the concentration of CD was
less than 10
4
M (see Fig. 23B). In both solvents the appearance of MI
character was independent whether CD or the substrate was injected. In all
cases the increase part was very pronounced in the rst 1525% of
conversion.
Later on similar behaviour was also described by two other groups in the
hydrogenation of EtPy in ethanol using the premixing technique.
66,82
There
was a very tough dispute between these two groups as they had completely
dierent view on this new kinetic phenomenon.
82,239
Further results clearly indicated
281,350,371
that the appearance of MI type
of enantioselectivity conversion (time) dependencies strongly depends on
the following experimental conditions: (i) concentration of CD, (ii) the
mode of introduction of reaction components, (iii) the purity of substrates,
(iv) the solvent used, and (v) conditions of catalyst pretreatment.
Figs. 24A and B show the ee
calc
-conversion dependencies obtained
in toluene upon using premixing and injection techniques, respectively.
93
Fig. 24 Enantioselectivity (ee
calc
)-conversion dependencies during the hydrogenation of EtPy
in toluene; & [CD]
0=
1 10
4
M; E [CD]
0=
1.2 10
5
M; T
=
23 1C, P
H2=
50 bar,
[Etpy]
0=
1.0 M, catalyst: 5 wt% Pt/Al
2
O
3
(Engelhard, E4759); A: premixing, B: injection.
(Reproduced from ref. 93 with permission.)
Catalysis, 2010, 22, 144278 | 199
The comparison of these two techniques shows that upon using premixing
the MI type behaviour disappears completely and there is only a very slight
increase or decrease of enantioselectivity with conversion. Contrary to that
when the injection technique was used the MI type behaviour was observed
and its character depended strongly on the initial concentration of CD. The
lower the concentration of CD the more pronounced the MI character (see
Fig. 24B). The MI character was completely maintained when ee
kin
values
were used instead of ee
calc
. It has to be emphasized that when similar ex-
periments were performed in ethanol the MI character appeared upon using
both premixing and injection methods.
84
This behaviour was attributed to
the formation of semi-ketal from the substrate and the solvent during the
period of premixing.
Similar experiments were performed in the hydrogenation of 3,5-bis(tri-
uoromethyl)-acetophenone over Pt/Al
2
O
3
in the presence of CD.
306
MI
type dependence was observed under general experimental condition, while
almost constant ee values were obtained after premixing the reaction mix-
ture in nitrogen as shown in Fig. 25A.
53
Consequently, identical observation
was obtained as in the hydrogenation of EtPy.
93
The results clearly indicate
that both surface cleanness and interactions in the liquid phase have their
contribution for the appearance of MI type eeconversion (time)
dependencies.
Dierent aspects of the appearance of initial transient period were dis-
cussed by Barto k upon using various substrates, such as EtPy, PADA,
MBF.
281
One of the most interesting observations was the dependence of
initial transient period on the pre-treatment conditions and the purity of the
substrate as shown in Fig. 25B. After pretreatment in helium ee values are
1520% higher than those without this pre-treatment. This behaviour was
attributed to the of 5 ppm oxygen in helium. It was suggested that the
oxygen can alter the Pt surface, what is more favourable for the interaction
with DHCD or CD.
20
40
60
80
100 B
0 20 40 60 80 100
Conversion (%)
e
e

(
%
)
98% purity / He
98% purity / H
2
99.9% purity / He
99.9% purity / H
2
H
2
He
A
Fig. 25 Eect of catalyst pretreatment on ee-time (conversion) dependencies. A: sub-
strate
=
3,5-bis(triuoromethyl)-acetophenone, catalyst
=
Pt/Al
2
O
3
, chiral modier
=
CD, sol-
vent
=
toluene, p
H2=
1 bar, r.t. a no catalyst pretreatment;
53
b catalyst is prereduced in H
2
at 400 1C; c-catalyst is prereduced in H
2
at 400 1C, and then, the reaction mixture was stirred
under N
2
for 1 h before H
2
was introduced (premixing); B: Pretreatment of re-reduced catalyst
in toluene with H
2
or He in the enantioselective hydrogenation of EtPy. (Reproduced from
ref. 281 with permission.)
200 | Catalysis, 2010, 22, 144278
The inuence of the reuse of the catalyst on the initial transient period
was investigated by the Barto ks group. Typical MI type dependencies are
shown in Fig. 26.
268
The results showed that the expression of MI character
depended on the amount of modier, but it was less pronounced after reuse
of the catalyst. However, in repeated use, i.e. after removal of the reaction
mixture and addition of fresh toluene, EtPy, and modier resulted in
1020% increase in the ee values.
On the basis of these results it was concluded that the the phenomenon
of increase in ee on reuse is an intrinsic feature of the catalyst system used,
i.e. new chiral centers making higher ee possible are formed.
195
In this
respect restructuring of the Pt surface was suggested based on analogous
analysis of results given in refs. 55, 90, 277. It was also supposed that oxygen
plays a denite role in this process.
A sequential introduction of dierent substrates was performed in which
the hydrogenation of MePy was carried out following the initial hydro-
genation of EtPy using Pt/Al
2
O
3
-cinchona catalyst. In these experiments,
the MI type character was obtained in both hydrogenation experiments (see
Fig. 27A). The character of ee-conversion dependencies was maintained
after reversed order of introduction of substrates (see Fig. 27B). The ob-
servation that the initial transient eect is still observed with the sequential
hydrogenation of EtPy and MePy indicates that the phenomenon cannot be
attributed to impurity eects. Consequently, it is more probable that the
reaction-driven equilibrium of the chiral environment play a role in the MI
character of ee-conversion dependencies.
In one of the recent studies three dierent modiers, such as CD, 9O-
phenyl-CD (PhOCD), 9O-pyridil-CD (PyrOCD) were investigated in the
hydrogenation of EtPy.
372
Well-expressed MI type behaviour was obtained
for all three modiers. However, despite all the convincing results presented
20
40
60
80
100
0 20 40 60 80 100
Conversion (%)
e
e

(
%
)
1 2
2r
1r
3
3r
[DHCD]
(mmol/L)
Temp.
(C)
1
1r
2
2r
3
3r
0.01 use
0.01 reuse
0.1 use
0.1 reuse
0.01 use
0.01 reuse
-10
-10
-10
-10
-20
-20
Fig. 26 Repeated use of catalyst in the enantioselective hydrogenation of EtPy: eect of
DHCD concentration and reaction temperature on the ee-conversion dependencies (fresh
DHCD was added for reuse, r
=
reuse). (Reproduced from ref. 268 with permission)
Catalysis, 2010, 22, 144278 | 201
in this section the following statement was done: We assume that the slow
removal of surface impurities is the major reason for this behavior (i.e. the
MI type ee-conversion dependencies). Consequently, there are groups who
do not learn from results obtained by other groups and keeping their old
views as a dogma.
Finally we can summarize the general views with respect to the origin of
the initial transient behaviour of ECD: (i) it is related to impurities or other
experimental artifacts,
82
(ii) it is due to surface induced alterations,
60,82,239
(iii) intrinsic kinetics.
75,195
5.5.3 Non-linear phenomenon. Non-linear eects (NLE) in homo-
geneous asymmetric catalysis have been investigated for many years since
the pioneering work of H.B. Kagan.
373
First the phenomenon was attrib-
uted to the diastereomeric association inside or outside the catalytic
cycle.
374
Later on the approach was extended to the use of mixtures of
diastereomeric ligands.
375
Recently this approach was been extended to the Oritos reaction. It was
suggested that the nonlinear behavior be due to the deviation from the
expected ideal behaviour assuming that the molar ratios of the modiers in
solution and on the metal surface are identical. Consequently, the nonlinear
behavior of mixtures of two diastereoisomers or two completely dierent
chiral modiers has been attributed mainly to their dierent adsorption
strength,
287
however the contribution of the adsorption geometries on the
metallic sites was also emphasized and new term non-linear phenomenon
(NLP) has been introduced.
269
Besides it was also suggested
269
that modi-
ermodier interactions may also be involved in the NLP, but no ex-
perimental evidence has been found yet. It was concluded that the
investigation of NLP behavior of mixtures of two modiers is a powerful
tool in heterogeneous catalysis for characterizing the relative adsorption
strength of modiers under truly in situ conditions.
However, in this respect the controversy between catalytic and spectro-
scopic investigations related to the evaluation of the relative adsorption
Fig. 27 Enantioselectivity-conversion dependencies in sequential hydrogenation experiments.
a: EtPy hydrogenation to 100% conversion prior to addition of MePy; b: MePy hydrogenation
to 100% conversion prior to addition of EtPy; EtPy conversion, K e.e. in (R)-EtLa,
7
MePy conversion, E e.e. in (R)-MeLa. T
=
20 1C, reaction pressure 30 bar H
2
for EtPy
hydrogenation, 50 bar H
2
for MePy introduction. (Reproduced from ref. 371 with permission.)
202 | Catalysis, 2010, 22, 144278
strength of various chiral modiers has to be mentioned.
376378
We have to
admit that this controversy can be attributed to the absence of substrate and
hydrogen in spectroscopic investigations.
In a recent review based on the above results the following statement was
done: An essential conclusion from this study is that, although strong
adsorption is a crucial requirement for an ecient modier, there is no
positive correlation between the adsorption strength (AS) and the enan-
tioselectivity achieved with the modier alone.
53
In a recent study it was emphasized that the NLP can presumably be
interpreted on the basis of dierences in the structure of the substrate-
modier complexes formed and in the adsorption-desorption processes of
the complexes, thus the NLP is not solely dependent on the adsorption of
cinchona alkaloids, as suggested by earlier experimental data.
379
The above view is very close to our one. In one of our study
361
we turned
back to the original idea given by Kagan, namely to the formation of dia-
stereomeric associations between the substrate and dierent competing
chiral entities as modiers in the liquid phase. Consequently, in our inter-
pretation the nonlinear behaviour is due to dierent enantio-dierentiation
ability of two modiers acting simultaneously in the liquid phase resulting
in dierent substrate-modier complexes (associations). Of course the
enantio-dierentiation ability of two modiers is further inuenced by
dierent factors, such as the adsorption-desorption behaviour, the abun-
dance and the reactivity of the formed associates.
It has to be added that kinetically the dierence between the two inter-
pretations (dierent adsorption strengths v.s. dierences in the structure
and stability of substrate-modier complexes) for the NLP cannot be done.
Only careful analysis of the chemical and surface properties can provide
some hints inside the origin of these observations.
Dierent experimental techniques were used to investigate the NLP of
two alkaloids: (i) variation of the initial ratio of two modiers measuring the
ee values at the end of the reaction,
287
(ii) applying a xed initial ratio of two
modiers and following the ee-conversion dependencies,
361
(iii) using
transient method in a batch reactor, where one of the modiers is intro-
duced at t
=
0, while the other one after a given time lap,
269
(iv) using
continuous ow reactors and creating transient conditions by switching
from one modier to another one.
301
The deviation from the expected linear correlation was rst observed in
the hydrogenation of EtPy in the presence of CDCN and QNQD mix-
tures.
287
At mole fraction of 0.5 of these alkaloids the ee value was higher
than zero indicating that the ED ability of CD and QN is higher than that of
the CN and QD, respectively. Similar result was also obtained in other
publications.
60,379
In all of these studies the ndings were attributed to the
dierences in the adsorption strength of the alkaloids.
The most striking NLP behaviour was observed in the hydrogenation
of KPL over Pt/Al
2
O
3
in the presence of CD-PhOCD mixtures (see
Fig. 28A).
238
It is known that PhOCD gives (S)-pantolactone, whereas CD
aords (R)-pantolactone as major enantiomer. The addition of small
amount of CD (X
CD
o0.05) to a reaction mixture containing PhOCD re-
sulted in drastic change from (S)-pantolactone to (R)-pantolactone as the
Catalysis, 2010, 22, 144278 | 203
major product. This non-linear behavior is attributed to the much stronger
adsorption of CD compared to PhOCD. The weaker strengths of ad-
sorption of PhOCD were related to its tilted form of adsorption as shown in
Fig. 28A.
Systematic investigation of NLP was done by two groups.
197,269,378381
Results obtained in a series of experiments using CD, CN, QN and
QD is shown in Fig. 28B.
378
Based on these results the following order was
established for the adsorption strength of cinchona alkaloids: CDW
CNWQNWQD. The above order was also supported by other studies.
269,378
Contrary to that RAIRS measurements of adsorbed alkaloids resulted in a
dierent order for the strength of adsorption: QN,QDWCDWCN.
376
In a
more recent RAIRS experiments the order in the adsorption equilibrium
constants (K
ads
) the following sequence was established: CNWQDW
CDWQN.
377
Probably based on these results in a recent review the fol-
lowing statement was done: An essential conclusion from this study is
that, although strong adsorption is a crucial requirement for an ecient
modier, there is no positive correlation between the adsorption
strength (AS) and the enantioselectivity achieved with the modier
alone.
53
Upon investigating the behaviour of O-alkylated derivatives of CD it was
nicely demonstrated that the adsorption strength of this type of modiers on
Pt decreases in the following order: CDWMeOCDWEtOCDWPhOCDE
TMSOCD.
202
Fig. 28 Non-linear eect in enantioselective hydrogenation reactions over Pt/Al
2
O
3
catalyst.
A: substrate
=
KPL, chiral modier
=
CD-PhOCD mixtures; schematic illustration of the
adsorption of CD and PhOCD on an idealized at Pt surface;
238
B: substrate
=
EtPy,
solvent
=
toluene, chiral modier
=
mixtures of dierent modiers, the 2nd modier was added
at 1020% conversion of EtPy.
380
(Reproduced from refs. 238 and 380 with permission.)
204 | Catalysis, 2010, 22, 144278
A continuous-ow xed-bed reactor was applied in the enantioselective
hydrogenation of EtPy on Pt/Al
2
O
3
using the principle of chiral switch.
301
These time on stream experiment start with the introduction of one of the
modiers and a given moment this modier is switched to another one. The
QD-CD and CD-QD switch is shown in the Fig. 29A and B.
295
The results
clearly show that the enantio-dierentiation ability of CD is stronger than
that of the QD. All of the above results strongly support the general view
that NLP and the adsorption strength of the modiers are coupled. How-
ever, there are experimental ndings indicating that the origin of NLP has
more complex basis.
In this respect let us refer to a series of transient experiments performed in
a batch reactor. Fig. 28B shows the inuence of solvents when CD was
added to the reaction mixture containing QN. In the opposite situation
when QN was added to the reaction mixture containing CD only minor
changes in the ee values were observed. The most interesting nding is that
the rate of replacement of QN by CD shows strong solvent dependency.
No real explanation was given for this nding, although the possibility for
the involvement of solvent polarity and the formation of an alkaloidacid
ion pair has been mentioned. Our view is that these experimental ndings
indicate that not only the dierence in the adsorption strength controls
NLP. Even more striking results related to NLP were observed when the
amount of modiers was varied in the above experiments. These results are
shown in Figs. 30 AC.
269
When CD was added to the reaction mixture
containing QD the direction of the enantioselectivity was immediately
altered. The time period required to reach the maximum Dee showed
strong concentration dependence, what was attributed to the fast hydro-
genation of the quinoline ring of QN in the rst 30 minutes at low con-
centration of modiers. In the opposite situation, i.e. when QD was added
to CD (see Fig. 30C) the decrease part was also explained by the fast
hydrogenation of CD, however no acceptable explanation was given for the
increase part.
Fig. 29 Appearance of chiral switch. A: Chiral switch induced by replacing CN with CD (lled
circles) and vice versa (lled squares). The conversion is shown with open symbols (open
squares are barely seen due to overlapping). The second modier reached the catalyst after
about 45 min (vertical dashed line); B: Inuence of the modier concentration on the dynamics
of the chiral switch. Conditions: 0.226 mM CD, 0.226 mM QD concentration for 1:1 ratio of
CD and QD (lled circles and squares) and 2.26 mM for the 10 fold amount of QD relative to
CD (open triangles) 100% conversion. (Reproduced from ref. 295 with permission)
Catalysis, 2010, 22, 144278 | 205
The mixing of two dierent alkaloids was also applied to study the
anomalous behaviour of both ICN. The results shown in Fig. 31A and B
indicate that the addition of a-ICN to CD, CN and b-ICN has no inuence
on the enantio-dierentiation ability of these alkaloids.
361
Based on these
results it was suggested that the origin of enantio-dierentiation ability of
a-ICN is dierent than that of for CD, CN and b-ICN.
Results shown in Fig. 31B indicate also that in the presence of CN the
addition of a-ICN resulted in less loss of ee at high conversions. It is due to
the suppression of the hydrogenation of the quinoline ring of CN in the
presence of a-ICN. Consequently, a-ICN should be strongly adsorbed on
the Pt surface.
The rst attempt to compare the behaviour of two substrates (EtPy and
KPL) in NLP under identical conditions using CN and QN was done in a
recent study. The investigations were performed in two solvents (toluene
and AcOH).
379
Three dierent methods were applied. Here we show results
obtained in a batch reactor using conventional and transient experiments.
According to results given in Fig. 32A, in the hydrogenation of EtPy the
direction of enantio-selection changes almost linearly with the concen-
trations of the two modiers. On the contrary, in the hydrogenation of KPL
the direction of enantio-selection is aected to a much higher extent by CN
Fig. 30 Hydrogenation of EtPy over Pt/Al
2
O
3
; A: Solvent eect on the exchange of QD by
CD. Addition of one equivalent CD after a 30-min reaction time; B: Inuence of modier
concentration on the transient behaviour. Addition of one molar equivalent CD after a 30-min
reaction carried out in the presence of QD; C: Addition of one molar equivalent QD after a 30-
min reaction carried out in the presence of CD. Standard conditions; acetic acid; amounts of
the modiers: 1.7, 0.17, and 0.017 mm. (Reproduced from ref. 269 with permission)
206 | Catalysis, 2010, 22, 144278
Fig. 31 Enantioselectivity-conversion dependencies in the presence of mixtures of a-ICN and
exible alkaloids. T
=
20 1C, p
H2=
50 bar, injection method, 500 rpm, reaction time
=
90 min;
A: 1.2 10
5
MCD; & 1.2 10
5
MCD1.2 10
5
Ma-ICN; K 1.210
5
Mb-
ICD;

1.2 10
5
Ma-ICN1.2 10
5
Mb-ICN; B: 1.2 10
5
Ma-ICN;
7
1.2
10
5
MCN; D 1.2 10
5
MCN1.2 10
5
Ma-ICN. (Reproduced from ref. 361 with
permission)
Fig. 32 Comparing the behavior of EtPy (EP) and KPL in NLP. A: QN-CN modier mixture,
total modiers concentration: 0.1 mM, solvent: toluene/AcOH
=
9/1; B: QN-CN modiers;
C: CN-QN modiers. In B and C concentration of each modier
=
0.05 mM, rst abbreviation-
modier used rst, second abbreviation-modier added afterwards; solvent
=
toluene (T) and
AcOH; modiers. (Reproduced from ref. 379 with permission)
Catalysis, 2010, 22, 144278 | 207
than by QN. This might indicate that in the presence of EtPy the adsorption
strengths are identical, while in the presence of KPL the adsorption strength
of CN is higher than that of QN. Based on results shown in Fig. 32B, i.e.
when QN was used as a rst modier, the following conclusions can be
drawn: (i) CN desorbs QN more readily in the hydrogenation of KPL than
in the hydrogenation EtPy, (ii) in the case of EtPy, CN cannot fully desorb
QN from the surface; (iii) in the hydrogenation of KPL CN can nearly fully
desorb QN. Based on these ndings the order of adsorption strength in
these two substrates is dierent, namely in EtPy CNBQN, while in KPL
CNWQN. When CN was used as the rst chiral modier (see Fig. 32C), in
the hydrogenation of EtPy CN cannot be desorbed by QN, while in the
hydrogenation of KPL under identical conditions CN acted as if QN was
not present at all. Consequently, the order of the adsorption strength of the
two cinchonas is dierent in these to substrates, in case of EtPy CNBQN,
while in case of KPL CNWWQN. These ndings are similar as those ob-
served in ref. 361, where CD, CN and b-ICN acted as if a-ICN was not
present at all. Such observation was also made in another earlier study in
transient experiments using CN and QN.
197
Summing up all investigations related to the elucidation of the origin of
NLP we accept the conclusions given in a recent study that the NLP de-
pends not only on the chiral modier but also on the substrate to be hy-
drogenated. This observation can presumably be interpreted on the basis of
dierences in the structure of the substrate-modier complexes formed and
in the adsorption-desorption processes of the complexes, thus the NLP is
not solely dependent on the adsorption of cinchona alkaloids, as suggested
by earlier experimental data.
197
The statement is in full agreement with our
view related to the importance of the formation of substrate-modier
complexes.
5.5.4 Inversion of enantioselectivity. To nd relationship between
the conguration of chiral centers of the modier and the chirality of the
product was one of the early tasks. It has been generally accepted that the
conguration of C8 or C8 and C9 atoms of the cinchona alkaloid molecule
determines the product distribution.
57,192
Changes in the sense of enantio-
selection were rst observed by Augustine et al. in 1993. Upon varying the
DHCD/ catalyst ratio in the hydrogenation of EtPy over Pt/Al
2
O
3
catalyst
(S)-ethyl lactate formed at low modier concentrations and (R)-enantiomer
at higher modier levels.
67
However, the extent of inversion is within the
experimental error. The other intriguing fact is that the ee values are ex-
tremely low. It is unprecedented that in this reaction the ee values are less
than 20%.
Analogous observation was found in gas phase hydrogenation of EtPy
over Pt/SiO
2
catalyst pre-modied with a series of C9 cinchona derivatives
299
i.e., the sense of enantioselectivity has changed as a function of the modier
concentration. The inversion of ee was found to be dependent on the nature
of the substituent at C9.
382
The appearance of inversion of enantioselectivity
was observed due to the changes in the modier structure,
192,202,205,238
variation of the solvent
44,56,216,238,340
changes of the modier concen-
tration
206
and even changes of the substrate.
210
Inversion has been reported
208 | Catalysis, 2010, 22, 144278
both on Pt
56,202
and Rh
254,256,351
catalysts. Summary of recent results was
given in ref. 383. Certain C9 substituted derivatives of cinchonas such 9O-
alky,
202
-aryl
192,202,238
and -silyl
202,206,238
derivatives of cinchonidine and
Sharpless-ligands,
192,206
furthermore b-isocinchonine
56,197,384
(the rigid de-
rivative of CN) have resulted in product with the opposite sense of ee than
the underivatized alkaloid. Fig. 33 shows both the diminished enantio-
selectivity and its inversion with increasing bulkiness of the ether function of
the modiers.
202
Upon using b-isocinchonine-Pt/Al
2
O
3
catalyst system in the hydrogen-
ation of EtPy ee decreases continuously and turn to opposite value with
decreasing of pH (see Fig. 34). Investigation of unexpected inversion has
given a new possibility for mechanistic studies.
In the hydrogenation of ethyl-4,4,4-triuoroacetoacetate over O-methyl-
cinchonidine-Pt/Al
2
O
3
catalyst system a signicant variation of ee value was
observed with the conversion in the presence of even trace amounts of water
or catalytic amounts of a strong acid.
349,385
This issue has been discussed in
Section 5.1. The explanation for the inversion of enantioselectivity is not
completely clear at the molecular level. It is obvious that the inversion of ee
can be related to increasing bulkiness of the substituent at C9 and the in-
creased rigidity of the alkaloid molecule. However, these factors alone give
not sucient answer why O-pyridoxy derivative
372
of CD does not lead to
inversion in spite of the fact that O-phenyl and O-pyridyl moieties have
almost identical van der Waals volumes. Further arguments are necessary to
explain why a-ICN
197
and a-isoquinine
385
owning similar rigid structure as
b-ICN shows no inversion.
To understand the origin of inversion dierent physical chemical methods
have been applied. HPLC-MS and GC-MS measurements have shown that
Fig. 33 Hydrogenation of EtPy over Pt/Al
2
O
3
in toluene, at p
H2=
1 bar. CD: cinchonidine,
MeOCD: 9-O-methyl-cinchonidine, EtOCD: 9-O-ethyl-cinchonidine, TMSOCD: 9-O-tri-
methylsylil-cinchonidine, PhOCD: 9-O-phenyl-cinchonidine, XylOCD: 9-O-(3,5-dimethylphe-
nyl)-cinchonidine, HFXylOCD: 9-O-[3,5-bis(triuoromethyl) phenyl]-cinchonidine,
NaphOCD: 9-O-naphthyl-cinchonidine. (Reproduced from ref. 202 with permission)
Catalysis, 2010, 22, 144278 | 209
b-isocinchonine modier keeps its inner ether structure during the enan-
tioselective hydrogenation.
386
NMR measurements have proved that the
hydrogenation of phenyl group in 9O-phenyl-CD (PhOCD) is not re-
sponsible for inversion.
202
From ATR-FTIR spectroscopic measurements
and DFT calculations it has been concluded that the shape of the chiral
space formed by the adsorption of PhOCD onto the metal is altered com-
pared to that formed by CD
238,387
(see Fig. 28). The phenyl group has a
complex interaction with platinum; it can adsorb via its p system inuencing
the strength of adsorption of the modier. However, at the same time it can
generate steric repulsion in the proximity of the chiral site.
388
The presence
of the phenyl group in (PhOCD) can also hurt the eciency of the shielding
eect (see Section 8.3).
Chiral pocket
389
has been dened as a physical space that is able to
accommodate, via bonding and repulsive interactions, a pro-chiral ad-
sorbate, and that is able to discriminate between its enantiomers. It was
suggested that although CD and PhOCD display similar adsorption modes,
the dierent adsorption strengths and the change of the chiral pocket are
sucient to induce the inversion of enantioselectivity.
387
The dierent role
of the bulky ether groups i.e. repulsion by the phenoxy and attraction by the
2-pyridoxy group explains the dierent behaviour of these derivatives.
372
Based on results obtained in the hydrogenation of EtPy
197
and keto-
pantolactone in the presence of b-ICN
381
in toluene interactions responsible
for the inversion were proposed.
The conformational rigidity of both the chiral modier and the reactant
may inhibit the geometrical t of the three components (modier, reactant,
and Pt), consequently the formation of the adsorbed intermediate respon-
sible for enantio-selection is hindered. Beside the interaction between the
nucleophilic N atom of the quinuclidine skeleton and the electrophilic
C atom of the keto group of KPL or EtPy, H-bonded interaction veried by
McBreen are also suggested.
72
It is proposed that the sense of enantio-
selection is controlled by the conformation of the adsorbed reactantchiral
Fig. 34 Hydrogenation of EtPy to (R)- and (S)-ethyl lactate on b-isocinchonine modied
platinum in toluene and AcOH mixtures. (Reproduced from ref. 56 with permission)
210 | Catalysis, 2010, 22, 144278
modier (1:1) complex which can be inuenced by the solvent.
384
It has been
concluded that the adsorption mode and conformation of the modier
during interaction with the substrate play the crucial importance in the
change of the sense of enantio-selection.
53
In a recent study the inversion of enantioselectivity was investigated in the
hydrogenation of of 1-phenyl-1,2-propanedione (PPD) using dierent
O-ether derivatives of CD.
391
The data conrmed that the origin of inversion
is related to depletion of the H-bonding interaction between the modier
OH-group and the carbonyl group of the reactant rather than to a decreased
population of the Open(3) conformation in the solutions of O-ether de-
rivatives when compared with the solution behavior of the parent alkaloid.
In another recent study dierent O-ethers of CD and CN were used in
both the enantioselective hydrogenation of PPD and the kinetic resolution
of the 1-hydroxyketones formed over Pt catalysts
390
Characteristic results
for PPD are shown in Fig. 35. As emerges from these results all O-ethers
showed inversion of enantioselectivity. Similar trend was also observed in
the kinetic resolution of 1-hydroxyketones. These results are dierent from
that obtained in the enantioselective hydrogenation of EtPy, where in-
version was observed only in case of large substituents. Another important
nding is that in the presence of AcOH the above modiers showed only
very low enantio-dierentiation ability (eeo5%).
Inversion of enantioselectivity has also been observed by Garland et al.
using a continuous-ow three-phase reactor.
299
5.6 Addition of other components
Several papers are devoted to the investigation of the inuence of various
additives on the behaviour of Pt/cinchona catalyst. These additives can be
considered as modiers either of the platinum or the support.
Fig. 35 Enantioselectivities of PPD hydrogenation in toluene over Pt/Al
2
O
3
catalysts modied
with: (K) CD; (

) CN; () MeOCD; (&) MeOCN; (

7
) PhOCD; (D) PhOCN; (E)
TMSOCD; (
}
) TMSOCN. (Reproduced from ref. 390 with permission.)
Catalysis, 2010, 22, 144278 | 211
5.6.1 Modication of Pt by tin tetraethyl. In one of our earlier studies
the Pt sites in a Pt/Al
2
O
3
catalyst were modied by Sn(C
2
H
5
)
4
.
358
This
modication is a two step anchoring type surface reaction.
392
PtH
a
Sn(C
2
H
5
)
4
PtSn(C
2
H
5
)
(4x)
xC
2
H
6
(PSC) (1)
PtSn(C
2
H
5
)
(4x)
H
2
PtSn (n x)C
2
H
6
(SBA) (2)
In reaction (1) primary surface complexes (PSC) are formed. After tin
anchoring the surface of Pt is covered by surface organometallic complexes
with general formula of Pt-SnR
3
or Pt-SnR
2
. These PSCs are stable at room
temperature. Upon heating in a hydrogen atmosphere (see reaction (2)) they
decompose with the formation of alkanes and stabilized bimetallic alloy
(SBA) type surface species, i.e., supported Pt-Sn alloys are formed.
393
Further details on this kind of modication of Pt can be found elsewhere.
394
Results in the enantioselective hydrogenation using tin modied catalysts
are summarized in Table 9. As emerges from this Table the modications
resulted in both PSC and SBA forms of Pt-Sn/Al
2
O
3
catalysts with dierent
Sn
anch
/Pt
s
ratios. The activity of modied catalyst was strongly altered by
the amount and the type of surface species. However, over catalysts con-
taining PSC (see Exps. 5, 13, 14, 15, 16 in Table 9) the ee values were almost
constant, i.e. they were not aected by modication of Pt (ee
=
8689%).
Striking observation was that upon using PSC the hydrogenation re-
action was completely blocked at relatively small Sn
anch
/Pt
s
ratios. This was
attributed to the selective blocking of kink and corner sites responsible for
Table 9 Enantioselective hydrogenation using tin modied catalysts (Reproduced from ref.
358 with permission)
Exp. No
Catalyst
Code No
Temperature of
H
2
treatment, 1C Sn/Pt
s
, g
Rate of
hydrogenation,
mol (kg
cat
sec)
1
Optical
yield, %
1 Pt no 0.000 0.83 64
2 Pt 150 0.000 1.70 82
3 Pt 200 0.000 1.66 87
4 Pt 400 0.000 2.00 88
5 PtSn-1 no 0.025 3.00 89
6 PtSn-1 100 0.025 2.60 84
7 PtSn-1 200 0.025 2.12 80
8 PtSn-1 200 0.025 2.17 86
9 PtSn-1 400 0.025 1.15 85
10 PtSn-2 200 0.036 1.06 72
11 PtSn-2 400 0.036 1.08 81
10 PtSn-3 200 0.056 0.02 72
11 PtSn-3 400 0.056 0.74 81
13 PtSn-4 no 0.030 1.77 86
14 PtSn-4 no 0.030 1.55 86
15 PtSn-5 no 0.008 2.00 89
16 PtSn-5 no 0.008 1.77 88
212 | Catalysis, 2010, 22, 144278
hydrogen activation by Sn(R)
(4 x)
moieties. The highest rates in the
enantioselective hydrogenation were obtained upon using modied catalysts
containing PSC. This nding was attributed to the suppression of the poi-
soning eect induced by byproducts formed.
There is one interesting remark: in a related study it was conrmed that in
this kind of surface modication of Pt at low tin coverage tin prefers kink
and corner sites.
395
Based in this old results it can be concluded that the
involvement of kink and corner sites of Pt in the ED step, as it has been
suggested by dierent authors,
233,369,396
is highly questionable. In addition
the above results can be considered as a rst real hint that the reaction rates
and the ee values are not well correlated, i.e. relatively high ee values can be
obtained even when the reaction rate is strongly suppressed. Unfortunately,
this result was almost forgotten, as its conclusion did not t into the concept
of ligand acceleration model . This model a priori suggests a denite re-
lationship between reaction rate and enantioselectivity.
5.6.2 Addition of achiral amines. Based on the use of dierent experi-
mental methods
182,189191,397,398
it has been suggested that cinchona alkal-
oids can form dimers. As far as any dimer would decrease the virtual
concentration of CD in the liquid phase attempts were done to use dierent
achiral tertiary amines (ATAs) with the aim to shift the equilibrium between
the dimer and the monomer form of CD as shown in the following scheme:
[CD[
2
2[CD[ (4)
[CD[
2
ATA [CD ATA[ CD (5)
This concept has been tested in the enantioselective hydrogenation of
EtPy and hexanedione.
93,399401
It is suggested that the modier in the form
of a dimer is a spectator in the asymmetric hydrogenation reaction.
Results in the presence of various ATAs at dierent experimental con-
ditions are summarized in Tables 10 and 11. These results clearly show the
Table 10 Inuence of dierent added achiral tertiary amines on the enantioselective hydro-
genation of EtPy in the presence of CD-Pt/Al
2
O
3
catalyst system. (Reproduced from ref. 93
with permission)
Achiral tertiary
amines added
Concentration of
achiral amines (M)
Rate constant,
k
1
(min
1
)
Rate constant,
k
2
(min
1
)
Enantioselectivity
(ee
max
)
No 0.0352 0.0465 0.750 (0.714)
b
TEA 1.2 10
5
0.0407 0.0676 0.841 (0.793)
b
DABCO 1.2 10
5
0.0886 0.1588 0.915
b
QND 1.2 10
5
0.1289 0.1645 0.898
b
QND 1.2 10
5
0.1297 0.1757 0.909
b
QND
c
1.2 10
5
0.0832 0.1346 0.926
b
QND
c
6.0 10
5
0.1267 n.m.
d
0.936
b
QND
c
1.2 10
4
0.1219 n.m.
d
0.946
b
a
Reaction conditions, solvent: toluene; reaction temperature: 23 1C; hydrogen pressure: 50 bar;
[Etpy]
0=
1.0M, [CD]
0=
1.2 10
5
M, TEA triethylamine; DABCO 1,4-diazabicyclo-
[2.2.2]octane; QND quinuclidine.
b
ee values measured at the end of reaction.
c
reactions
carried out at 10 1C.
d
n.m.: not measurable.
Catalysis, 2010, 22, 144278 | 213
strong eect of ATAs in toluene, however no eect has been observed in
EtOH and AcOH. In the presence of quinuclidine unprecedented high ee
values were obtained at low CD concentration (1.2 10
5
). The ee value
equal to 0.946 is close to those obtained in pure AcOH.
Further evidence with respect to the involvement of alkaloids dimers in
the ATA eect was obtained upon comparison of CD with 9-methoxy-CD
(CH
3
OCD) in the hydrogenation of EtPy. As far as at C-9 position the OH
group is replaced by a methoxy one, (CH
3
OCD) cannot interact with ATA.
It is the reason that no increase in the ee is observed in case of
(CH
3
OCD).
400
Results of kinetic studies were supported by results of circular dichroism
spectroscopy. In table 12 the intensities of the Cotton shift around 237 nm
are shown in the presence of various ATAs. This Cotton shift has been
ascribed to the dimer form.
192
In case of CH
3
OCD no similar Cotton shift is
observed. The calculated De values well correlated with the ability of ATAs
to increase the reaction rate and ee values. These results suggest that the
ATA added into the solution of CD be involved in new type of solutesolute
interaction.
Summing up the ATA eect the following conclusions can be drawn: (i)
ATA eect appears only at low concentration of CD; (ii) no ATA eect in
EtOH and AcOH; (iii) the ATA eect depends on its concentration; (iv)
ATAs containing bulky substituents show more pronounced eect; (v) the
OH group of CD is involved in the interaction with ATAs.
5.6.3 Addition of nitrogen containing aromatic and condensed aromatic
compounds. In our recent study
402
the inuence of the addition of various
nitrogen containing aromatic and condensed aromatic compounds was
studied. The aim of these studies was testing of the validity of the
Table 11 Inuence of dierent tertiary amines on the reaction rate and enantiomeric excess in
the enantioselective hydrogenation of EtPy. (Reproduced from ref. 400 with permission)
No ATAs k
1
, min
1
k
2
, min
1
ee
max
ee
end
1 No
a
0.0045 0.0068
2 No 0.0236 0.0747 0.838 0.819
3 quinuclidine
a
0.0077 0.0109
4 quinuclidine 0.0482 0.0997 0.901 0.882
5 Dabco 0.0486 0.1267 0.909 0.905
6 MPD 0.0322 0.0989 0.895 0.872
7 TEA 0.0300 0.0905 0.849 0.843
8 Edcha 0.0220 0.0735 0.850 0.785
9 Edipa 0.0243 0.1280 0.824 0.796
10 3-quinuclidinol 0.0468 0.0867 0.888 0.870
11 No
b
0.0409 0.1268 0.945 0.945
12 quinuclidine
b
0.0699 0.1518 0.946 0.946
[EtPy]
0=
1.0 M, [CD]
=
1.2 10
5
M, ATA
=
6 10
5
M, T
=
20 1C, p
H2=
50 bar, solvent
=
toluene, coinjection of ATA, Dabco:1,4-diazabicyclo-[2.2.2]octane, MPD: 1-methylpiperidine,
TEA: triethylamine, Edcha: N-ethyldicyclohexylamine, Edipa: N-ethyldiisopropylamine.
k
1
, k
2
: rst order rate constants calculated from experimental points measured in the rst 10
minutes and between 2560 minutes, respectively.
a
in the absence of cinchonidine.
b
solvent
=
1 M acetic acid in toluene.
214 | Catalysis, 2010, 22, 144278
surface model. The surface model assumes that CD adsorbs by its
aromatic quinoline ring almost parallel to the Pt surface.
The condensed ring system has been considered as the anchoring site (AS)
of the modier.
46
Based on this view it was suggested if condition of com-
petitive adsorption between CD and condensed aromatic compounds can be
established, the number of chirally modied sites should decrease re-
sulting in denite loss of enantioselectivity.
Table 13 shows the inuence of added quinoline (Q) on the reaction
kinetic and ee values. These results unambiguously show that the addition
of quinoline increases both the rate and the ee values. The eect of quinoline
is very pronounced at low concentration of CD, while upon increasing the
Table 12 Eect of ATA on the circular dichroism data of cinchonidine (Reproduced from ref.
400 with permission)
No ATA added
Concentration
of ATA
( 10
3
M)
ATA-CD
molar
ratio solvent De (M
1
cm
1
)
1 no ethanol
2 no CH
2
Cl
2
0.94
3 quinuclidine 0.4 1 CH
2
Cl
2
0.91
4 quinuclidine 0.8 2 CH
2
Cl
2
0.74
5 quinuclidine 2.0 5 CH
2
Cl
2
0.70
6 quinuclidine 4.0 10 CH
2
Cl
2
0.61
7 quinuclidine 8.0 20 CH
2
Cl
2
0.49
8 Dabco 2 5 CH
2
Cl
2
0.92
9 Dabco 4 10 CH
2
Cl
2
0.69
10 Dabco 8 20 CH
2
Cl
2
0.39
11 TEA 2 5 CH
2
Cl
2
0.94
12 TEA 4 10 CH
2
Cl
2
0.90
13 TEA 8 20 CH
2
Cl
2
0.79
[CD]
=
4 10
1
M, T: 25 1C, cell length: 0.2 cm, time mode detection, wavelength: 237.6 nm,
Dabco: 1,4-diazabicyclo-[2.2.2]octane, TEA: triethylamine.
Table 13 Eect of Q on the reaction rate and enantioselectivity in the enantioselective
hydrogenation of EtPy. (Reproduced from ref. 402 with permission)
No [CD], 10
5
M [QN], 10
5
M k
1
, min
1
k
2
, min
1
ee
max
ee
end
1 0.6 no 0.027 0.015 0.573 0.235
2 0.6 6.0 0.040 0.069 0.832 0.699
3 0.9 no 0.032 0.058 0.719 0.575
4 0.9 6.0 0.045 0.090 0.867 0.813
5
a
1.2 no 0.034 0.073 0.830 0.798
6 1.2 1.2 0.054 0.114 0.880 0.847
7 1.2 6.0 0.056 0.118 0.874 0.860
8 1.2 12.0 0.059 0.123 0.880 0.869
9 6.0 no 0.065 0.187 0.894 0.894
10 6.0 6.0 0.060 0.140 0.898 0.898
[EtPy]
0=
1 M, t
react=
90 min, catalyst: 0.125 g, 5 wt% Pt/Al
2
O
3
, solvent: toluene, mode of
introduction: Pr-I for Q followed by Inj-I of CD, conversionW99%.
a
average of ve parallel
experiments.
Catalysis, 2010, 22, 144278 | 215
concentration of CD the eect disappears. Due to the presence of quinoline
unusually high ee values were obtained in toluene at [CD]
0=
1.2 10
5
M.
Figure 36AC shows the ee-conversion dependencies at dierent CD
concentration. Characteristic feature of these dependencies is that at low
CD concentration ee decreases at high conversion (see Fig. 36A). The loss of
ee at high conversion is attributed to the loss of CD due to the hydrogen-
ation of its quinoline ring. However, this decrease is strongly suppressed by
the addition of quinoline; consequently the results indicate that quinoline
replaces CD from the Pt surface. This replacement reduces the chance of CD
to be hydrogenated by its quinoline ring.
Table 14 shows the inuence of various nitrogen containing and con-
densed aromatic compound on the rate and enantioselectivity. These results
were obtained on highly dispersed Pt/SiO
2
catalysts. Over this catalyst the
ring hydrogenation of the quinoline ring was relatively fast. It is the reason
that over this catalyst the ee decreases with conversion. It is reected by the
low value of ee
end
/ee
max
.
The results show that none of the additives used (see Table 14) resulted in
measurable rate decrease. However, substantial rate increase was observed
A B C
0.0
0.2
0.4
0.6
0.8
1.0
0.0 0.2 0.4 0.6 0.8 1.0
Conversion
0.0 0.2 0.4 0.6 0.8 1.0
Conversion
0.0 0.2 0.4 0.6 0.8 1.0
Conversion
0.0
0.2
0.4
0.6
0.8
1.0
0.0
0.2
0.4
0.6
0.8
1.0
e
e
Fig. 36 Inuence of CD concentration on the hydrogenation of EtPy in the presence of Q.
[EtPy]
0=
1.0 M, P
H
2
=
50 bar, solvent: toluene, 500 rpm, catalyst: 0.125 g, 5 wt.% Pt/Al
2
O
3
(Engelhard 4759), mode of introduction: Pr-I for Q followed by Inj-I of CD; A:
[CD]
0=
0.6 10
5
M; B: [CD]
0=
1.2 10
5
M; C: [CD]
0=
6.0 10
5
M, E no Q; &
6 10
5
M Q. (Reproduced from ref. 402 with permission)
Table 14 Hydrogenation of EtPy over cinchona-Pt/SiO
2
catalyst system in the presence of
condensed aromatic compounds and aromatic nitrogen bases. (Reproduced from ref. 402 with
permission)
N
o
Additives k
1
, min
1
k
2
, min
1
conv
end
, % ee
max
ee
end
ee
end
/ee
max
1 0.031 0.053 98.8 0.666 0.343 0.515
2 Acridine 0.045 0.047 98.4 0.690 0.434 0.629
3 Quinoline 0.048 0.078 99.0 0.686 0.468 0.682
4 Pyridine 0.078 0.069 99.4 0.585 0.446 0.762
5 4-Picoline 0.042 0.059 99.5 0.575 0.447 0.780
6 Naphthalene 0.037 0.044 97.7 0.625 0.323 0.517
7 Antracene 0.033 0.049 98.3 0.620 0.323 0.521
8 Pyrene 0.039 0.048 98.4 0.619 0.337 0.544
[EtPy]
0=
1 M, [CD]
=
1.2 10
5
M, [Additive]
=
1 10
4
M, t
react=
90 min, catalyst: 0.07 g
2.7 wt% Pt/SiO
2
, solvent: toluene, mode of introduction: Pr-I for additives followed by Inj-I of
CD.
216 | Catalysis, 2010, 22, 144278
in the presence of acridine, quinoline and pyridine. Two classes of con-
densed aromatic compounds can be dierentiated: (i) nitrogen containing
one resulting in increased ee
end
/ee
max
values and (ii) condensed aromatic
compounds having no inuence on the ee
end
/ee
max
values.
Summing up these results it was concluded that in the enantioselective
hydrogenation of EtPy achiral condensed aromatic N-bases, as additives,
are able to increase both the enantioselectivity and the reaction rate.
Based on the concept of chirally modied sites the co-presence of CD
and quinoline over Pt sites can be considered as a competition. The
consequence of this competition is the decrease of the number of sites in-
volved in ED. Therefore, one would expect a decrease in the ee values.
However, it is not the case, the ee increases when the CD/quinoline
ratio is properly chosen and the CD concentration is low. The observed
eect appeared both on alumina and silica supported Pt catalysts and was
found to be strongly concentration dependent. However, according to the
Surface model the co-adsorption of these compounds should result in a
decrease in the enantioselectivity, what is not observed in our study. Con-
sequently, our results might indicate that the surface model needs some
corrections.
5.6.4 Modication of the support. There are only scarce data on the
modication of the support. In one of our studies the inuence of the
modication of alumina support by alkyl silanes was investigated. After
dehydroxilation of the support at 400 1C it was modied by dierent alkyl
silanes resulting in anchored Si(CH
3
)
3
, or Si(CH
3
)
2
C
8
H
17
moieties
274
. The
rate of this anchoring type surface reaction can be controlled by the con-
centration of the modier, the temperature of anchoring reactions and the
length of the R group in the alkyl silanes.
Catalysts modied in this way were used in the enantioselective hydro-
genation of EtPy in the presence of CD. The above modication was not
benecial for the above reaction as the modied catalysts showed pro-
nounced decrease in reaction rates and slight loss in enantioselectivities
compared to the unmodied Pt/Al
2
O
3
. These results are shown in Figs. 37A
and B. The catalytic performance of these modied catalysts was
Fig. 37 The eect of the surface coverage of CH
3
(CH
2
)
7
Si(CH
3
)
3
moieties on the reaction rate
(A) and the enantioselectivity (B). (Reproduced from ref. 274 with permission)
Catalysis, 2010, 22, 144278 | 217
signicantly altered upon using various pre-activation procedures as shown
in Table 15. The removal of the anchored OSi(CH
3
)
2
R moieties the ori-
ginal activity and enantioselectivity was restored completely.
The catalytic performance of these modied catalysts was signicantly
altered upon using various pre-activation procedures as shown in Table 15.
The removal of the anchored OSi(CH
3
)
2
R moieties the original activity
and enantioselectivity was restored completely. The behaviour of this
type of modied catalysts was explained by the following phenomena:
(i) partitioning or retention of CD or the [substrate-CD] complex by an-
chored Si(CH
3
)
2
R moieties, and (ii) decreasing the mobility of CD or the
[substrate-CD] complex in the boundary layer.
We believe that the results obtained in the above study provided further
indirect evidences that interactions in the liquid phase play a very important
role. Results obtained in this study strongly indicate that in this enantio-
selective hydrogenation reaction the enantio-dierentiation cannot be at-
tributed exclusively to the interaction between the half-hydrogenated
substrate and CD on the Pt surface.
5.6.5 Modication of Pt by other components. These studies were per-
formed by English groups. These groups use the classical aerobic Pre-
modication procedure (see Section 4.4), In the enantioselective
hydrogenation of MePy or butane-2,3-dione in the presence of cinchoni-
dine-modied platinum catalysts it was shown that at the catalyst prepar-
ation stage, the co-adsorption of the alkaloid with a strong co-adsorbate has
a strong positive eect.
278
One of these coadsorbates was oxygen or air
dissolved in reactant and solvent. In addition acetylene, methyl acetylene
and butadiene appeared to be eective co-adsorbates. It was suggested that
in the absence of a strong co-adsorbate the surface is poisoned by
cinchonidine.
It has been shown that the modication under methylacetylene provides
reaction rates and ee values excess under standard conditions (10 bar,
293 K) that are comparable to, or higher than those obtained with normal
aerobic modication.
The importance of surface morphology of small supported Pt particles
was conrmed in refs. 233, 403. In these studies Pt/C and Pt/SiO
2
catalysts
Table 15 Inuence of the catalytic performance of modied catalysts as a function of the
temperature of pre-activation. (Reproduced from ref. 274 with permission)
Experiment No. Temperature of preactivation (1C) Rate constant, k
1
(min
1
) ee (%)
1 150 o0.001 58.3
2 250 0.012 77.2
3 400 0.020 84.7
4 400, blank
a
0.044 85.0
5 400
b
0.054 84.3
6 400, parent 0.057 86.3
Catalyst tested: No.10 (see Table 1 in Ref. 274);
a
Catalyst No. 1 (see Table 1 in Ref.
274).
b
Modied catalyst treated in air at 300 1C prior its preactivation in a hydrogen atmo-
sphere.
c
Catalyst without modication.
218 | Catalysis, 2010, 22, 144278
modied by bismuth and sulphur and were characterized by electrochemical
methods.
404
Their key ndings are summarized in Table 16.
The authors main results and conclusions were as follows:
v
A cyclic voltametric analysis indicated that in poisoning by Bi king
sites, while in poisoning by sulfur terrace sites are involved
v
The reaction rates increased in bismuth modied catalysts; while de-
creased in sulfur modied one.
v
The formation of polymeric residues were strongly reduced over Bi
modied catalysts.
v
Both the enantioselective hydrogenation and the formation of poly-
meric residues are formed on king sites.
v
RE is now attributed to reaction occurring at a normal rate at an
enhanced number of sites, not (as previously proposed) to a reaction oc-
curring at an enhanced rate at a constant number of sites.
It has to be stressed out that in this study EtPy was used without any
purication. It is the reason for extremely low rates in the racemic hydro-
genation (see Table 16).
This fact strongly questions both the results and the conclusions. There is
an additional serious drawback, i.e., the lack of information on racemic
hydrogenation over catalysts modied by Bi. In this respect it has to
mention that the adsorption of Bi on the Pt can give dierent species, in-
cluding metallic and ionic one.
405
We suggest the rate increase and the
decrease of the ee over Bi modied catalysts is due to the acceleration eect
in the racemic hydrogenation by bismuth cations created over the Pt
surface.
In this respect we should like to revert to our results on tin modied
catalysts (see Section 5.6.1). This method clearly indicated that the in-
volvement of kink sites in the ee is excluded as tin is located on the kink site
and ee was independent on the amount of tin anchored to the platinum,
while the rate showed a strong dependence.
Table 16 Variation of activity (r
max
), enantiomeric excess (ee) and HMMP yield in reactions
over Pt/graphite, PtBi/graphite and PtS/graphite modied by cinchonidine (CD) and
quinuclidine (QND). (Reproduced from ref. 232 with permission)
Surface Alkaloid modier r
max
(mmol h
1
g
cat
1
) ee (%(R)) HMMP yield
Pt None
b
0 2
c
Pt CD 850 41 100
Pt QND 440 0 40
Pt 1:1 CD:QND 1205 37
Pt-Bi ((Y
Bi
)
ch=
0.35) CD 1350 35 49
Pt-Bi ((Y
Bi
)
ch=
0.35) QND 1710 0 36
Pt-Bi ((Y
Bi
)
ch=
0.35) 1:1 CD:QND 4600 15
Pt-S ((Y
S
)
ch=
0.19) CD 440 52 109
Pt-S ((Y
S
)
ch=
0.19) QND 310 0
Pt-S ((Y
S
)
ch=
0.19) 1:1 CD:QND 645 51
a
Conditions: 65 mmol ethyl pyruvate, 0.17 mmol CD and/or 0.17 mmol QND, 0.25 g catalyst,
12.5 ml dichloromethane, 30 bar hydrogen, 293 K, 1000 rpm.
b
For this reaction
r
initial=
24 mmol h
1
g
cat
1
.
c
ConversionW20%.
Catalysis, 2010, 22, 144278 | 219
6. Spectroscopic investigations
6.1 NMR
NMR techniques related to substrates, reaction products and chiral modi-
ers have widely been used in the investigation of enantioselective hydro-
genation of activated ketones. It has also been applied for the determination
of by-products, alternative reaction routes and intermediate complexes and
attempts were also made to use NMR for elucidation of dierent hypo-
thetical reaction-mechanisms.
To study the directing eect of ester group
338
or triuoromethyl group
235
of the substrate a series of new compound were prepared and identied by
NMR. It was also applied as a tool to check the purity of substrate.
82
In
many cases NMR gives an opportunity for identication of reaction
products.
203,210,235,331,336,338,406
It is known long before that cinchona alkaloids are extremely active chiral
modiers in various organic reactions. Mapping the role of dierent
structural elements of cinchonas in the enantio-selection several derivatives,
especially C9 substituted cinchonas,
202
inner ethers,
407
N-alkyl deriva-
tives
314
have been prepared and checked by NMR,
44,238,256,408
Upon
identication of the structure of ether derivatives of cinchonidine such as
9O-phenyl-
202,206
9O-pyridyl-,
372
9O-sylil-cinchonidine
202
etc. NMR was
an indispensable tool. Beside of the aforementioned chiral modiers, the
structure of several cinchona analogues, i.e. amines and amino alcohols
44,378
and aryl alcohols
226
prepared for chiral template in the Oritos reaction has
also been conrmed by NMR.
Chiral modiers itself very often suer changes during the enantioselec-
tive hydrogenation. To follow the conversion of 9O-pyrydil-cinchoni-
dine
372
and the saturation of naphthalene ring of 1-naphthyl ethylamine
derivatives
208,212
NMR was applied as well as to check the resistance of
phenyl group in 9O-phenyl-cinchonidine
203
and the stability of methoxy-
cinchonidine
372
and isocinchonines.
351
NMR analysis of the reaction
mixture showed that 1-naphthyl ethylamine derivatives is quantitatively
consumed during the hydrogenation reaction and converted to the sec-
ondary amine.
212
It has been shown by NMR that quaternary ammonium
derivatives of CD as new chiral modiers remained stable during hydro-
genation.
200
Formation and structure of hexahydro-cinchonidines and
hexahydro-cinchonines has been investigated by NMR.
271,409
According to
NMR analysis, at 36% saturation of the quinoline rings of CD in acetic acid
the ratio of homoaromatic and heteroaromatic hydrogenation products was
2.5 to 1.
269
Upon hydrogenation of b-triuoro ketones the sense of enantioselectivity
changes when the polarity of the solvent changes. The phenomenon was
explained by the shift of keto-enol equilibrium conrmed by NMR.
44,385
In
alcoholic solvent ethyl-4,4,4-triuoroacetoacetate has shown a reaction
route via semi-ketal.
348
Semi-ketal was also detected by use of NMR in
other cases.
331,410
IR and NMR experiments have revealed that the enan-
tioselective hydrogenation of EtPy in nonacidic solvents is complicated by
the simultaneously occurring self-condensation (aldol reaction) of the
reactant.
82
In the hydrogenation of ketopantolactone GC and NMR results
220 | Catalysis, 2010, 22, 144278
has shown that no by-product formation appears.
76
The reaction pathways
were followed by NMR in the enantioselective reduction of isatin deriva-
tives over cinchonidine modied Pt/alumina.
411
In the study of hydrogenation of 1,1,1-triuoro-2,4-diketones strong
acid-base interaction has been revealed by NMR. The high chemo- and
enantioselectivities in the above reaction were attributed to the formation of
an ion pair involving the protonated quinuclidine part of the chiral modier
and the enolate form of the substrate.
406
In the hydrogenation of KPL the
formation of dimer was conrmed by NMR.
209,323
Recently a mechanistic model involving nucleophilic catalysis and zwitter-
ionic adduct formation between a cinchona alkaloid and activated ketone has
been suggested.
412
Upon investigation of hydrogenation of ouoroketones the
formation of the ionic species in the solution was studied by
13
C-NMR
spectroscopy. Triuoromethylcyclohexyl ketone was used as a strong elec-
trophile agent and the complex was created by the addition of excess tertiary
amine quinuclidine. The adduct formation was studied in two dierent solvent
systems such as deuterated chloroform and acetone but the formation of the
zwitterionic species was observed only in acetone.
216 13
C-NMR conrmed the
existence of other adducts of the zwitterionic type.
360
However an NMR study
has indicated that the zwitterions model is probably based on erroneous
interpretation of the experimental data; the NMR spectra that had been
reported for zwitterion formation may arise from an aldol addition the a,a,a-
triuoromethyl ketone and the solvent acetone, and the reaction is catalyzed
by the tertiary amine used as a model for the chiral amine modier.
413
Upon using NMR technique it was veried that the enol form of EtPy is
not the reacting species, but under condition of enantioselective hydro-
genation deuterium exchange takes place not only at the quinoline ring, but
at C9 carbon atom, too.
414
6.1.1 Conformation analysis of the modier. The study of the con-
formation of cinchona alkaloids investigated by NMR has been briey
mentioned in Section 2.3. The question of which conformer of cinchonidine
is involved in the enantio-dierentiation step is regarded as a key issue.
Baiker el al. have used ab initio calculations and NMR measurements to
investigate the conformers of (dihydro)cinchonidine in dierent solvent
(such as benzene, toluene, ethyl ether, acetone, etc.).
88
The existence of a
given conformer has been rendered by nuclear Overhauser enhancement
spectroscopy. NOESY experiments have suggested that Open (3) and
Closed (1) and Closed (2) conformers appears. This observation is in
qualitative agreement with their calculations. The dihedral angles for dif-
ferent conformers have been calculated by ab initio methods. The measured
coupling constants (
13
JH
8
H
9(exp)
) and the dihedral angles by applying the
Karplus equation
415
have given possibility for calculation of coupling
constants of dierent conformers (
13
JH
8
H
9(i)
). The above method is limited
to the determination of only two conformers from one coupling constants
measured, however the dihedral angle has been found very similar for the
two closed conformers of CD, so the population of Open (3) and the sum of
populations of closed conformers has been possible to calculate. The results
are represented in Table 17.
Catalysis, 2010, 22, 144278 | 221
According to the above approach the conformer Open (3) has been found
the most stable one.
88
Based on parallel solvent dependence of ee and popu-
lation of Open (3) it has been suggested that Open (3) conformer plays crucial
role in the asymmetric induction. In case of 9-deoxy-CD derivatives similar
method has been used.
416
The coupling constants of 2-phenyl-9-deoxy-10,11-
dihydrocinchonidine (
13
JH
9
H
8a
(5.0 Hz);
13
JH
9
H
8b
(9.3 Hz)) is similar to that
of 9-deoxy-10,11-dihydrocinchonidine (5.5 and 8.5 Hz) in CDCl
3
indicating
that the relative stability of conformers is also similar. NMR experiments and
ab initio calculations revealed that conformer Closed (1) is stabilized relative
to Open (3) when going from CD to 9-deoxy-10,11-dihydrocinchonidine.
In a recent study the eect of the protonation on the conformation of CD
was investigated.
417
It was shown that protonation strongly hinders the
rotation around the C4
/
C9 and C9C8 bond. Structures and conforma-
tional behaviour of several cinchona alkaloid O-ethers in solution (NMR
and DFT) were also investigated.
391
It was demonstrated that the con-
formation found to be abundant in the liquid phase has no direct correl-
ation with the enantioselectivity of the PPD hydrogenation reaction. The
authors concluded that the driving force for production of one of the en-
antiomers in excess is due to the specic adsorption of the modier on the
catalyst surface, a phenomenon that does not correlate with the population
of the conformers in the liquid phase.
6.1.2 Substrate-modier interaction. In an early work NMR measure-
ments have already shown an interaction between CD and EtPy in the liquid
phase.
84
It was shown that in CD
3
OD in the presence of 0.15 M MePy the
characteristic doublet of CD at 5.65 ppm was shifted to 5.85 ppm and a new
small singlet was observed at 6.0 ppm. Upon increasing the concentration
of MePy to 0.6 or 1.0 M the doublet vanished and only the new singlet
at 6.0 ppm was found. More noticeable shift of the C(9) proton, up to
6.36.4 ppm with a formation of a singlet was observed in neat CD
3
COOD
or if small amount of CD
3
COOD was added into the solution of CD in
C
6
D
6
. These NMR results suggested that the torsional angle between the
hydrogen atoms at C(8) and C(9) carbon atom of CD has been changed
resulting in a new conformer of CD.
Table 17 Vicinal
3
JH
8
H
9
coupling constants for cinchonidine and derived population of
conformer open (3) in dierent solvents. (Reproduced from ref. 88 with permission)
Solvent h
T
3
JH
8
H
9
P
open (3)
P
Closed
benzene 2,28 5.0 0.58 0.42
toluene 2,34 4,1 0,7 0,3
ethylether 4,3 4 0,71 0,29
tetrahydrofurane 7,6 4,7 0,62 0,38
acetone 20,7 6,4 0,4 0,6
dimethylfomamide 36,7 7 0,33 0,67
dimethylsulfoxide 40 7,5 0,27 0,73
water 78,5 7,2 0,3 0,7
ethanol 24,3 3,5 0,77 0,23
a
For open(3)
3
JH
8
H
9
is calculated as 1.7 Hz. For Closed (1) and Closed (2), respectively,
3
JH
8
H
9
is calculated as 9.6 and 4 Hz. In this determination of P closed a value of 9.6 was used.
222 | Catalysis, 2010, 22, 144278
In Pt-catalysed hydrogenation of 1,1,1-triuoro-2,4-diketones the com-
bined catalytic, NMR and FTIR spectroscopic, and theoretical study re-
vealed that high chemo- and enantioselectivities are attributed to the
formation of an ion pair involving the protonated amine function of the
chiral modier and the enolate form of the substrate.
406
On the basis of NOE studies and theoretical calculations related to the
hydrogenation of ketopantolactone in the presence of the (R,R) and (R,S)
diastereomers of a new chiral modier, pantoyl-naphthylethylamine, dier-
ent properties of the above diastereomers were investigated, in particular the
eect of acid on the modier structure.
209
The results indicated that in case of
the (R,R)-diastereomer in apolar solvent, a loose, extended structure changes
to a compact one via an additional intra-molecular hydrogen bond, resulting
in a more suitable chiral pocket available for the reactant on the Pt surface.
Standard 2D NMR spectroscopic methods and diusion-ordered NMR
spectroscopy combined with theoretical calculations has been used to verify
the formation of supramolecular complexes between the pairs O-methyl-
cinchonineketopantolactone (KPL) and b-isocinchonineKPL.
418
When
O-methyl-cinchonine or b-isocinchonine and KPL were mixed in dry deu-
terobenzene solution, time-dependent chemical shift changes for the cin-
chonas and new signals for KPL bound to the modier have been detected.
The spatial pattern of the chemical shift dierences and the conformations
of the modiers determined by NOESY demonstrated that the substrate
binding occurs at the quinuclidine N atom, H9, and the quinoline H5
/
re-
gion for O-methyl-cinchonine (H8 and H5
/
for b-isocinchonine. Based on
diusion measurements hydrodynamic radii has been estimated which has
proved the co-diusion of the cinchonas and KPL in a complex. The results
have shown that not only 1:1, but also 2:1 cinchona-KPL complexes must
be taken into account. NMR evidences has also been found for the cor-
relation between the solution-state concentration of the nucleophilic 1:1
modier-substrate complex and the ee on enantioselective hydrogenation of
KPL using Ptb-isocinchonine chiral catalyst.
418,419
6.2 Circular dichroism
Vibrational circular dichroism (VCD) is a useful tool to determine the ab-
solute conguration of the enantiomer produced in excess in an enantio-
selective reaction when reference data on the enantiomer are not available.
The absolute congurations of the enantiomers can be obtained by com-
paring the theoretically calculated VCD spectrum of one enantiomer with
the experimental VCD spectrum of the product of the asymmetric reaction.
It is important to know that VCD signal is about three orders of magnitude
less intensive than the corresponding signal in the ordinary transmission
spectrum.
235
This method has been successfully applied for the determin-
ation of product alcohols in the studies related to the directing eect of
triuoromethyl group
235
or ester group
338
of the substrates. It was also used
upon investigating CD modied Rh/alumina catalyst
420
in the hydrogen-
ation of various aromatic ketones possessing an a-hydroxy or a-methoxy
group and, in case of the enantioselective reduction of isatin derivatives over
CD modied Pt/alumina.
411
Catalysis, 2010, 22, 144278 | 223
Theoretical (DFT) and VCD spectroscopy study has been applied for the
conformational analysis of the synthetic chiral modier 9-O-phenyl-CD.
421
According to these results 9-O-phenyl-cinchonidine behaves similarly to
CD and shows four main conformers, denoted as Closed (1), Closed (2),
Open (3), and Open (4). A combined theoretical-experimental VCD spec-
troscopy approach has given possibility to increase the spectroscopic sen-
sitivity toward changes in the distribution of conformers upon changing the
solvent polarity. The VCD spectra conrm that Open (3) is the most stable
conformation in CCl
4
. Changing from CCl
4
to CDCl
3
the equilibrium be-
tween the conformers does not change signicantly. Upon increasing solv-
ent polarity besides similar non-coordinating properties the fraction of
Closed (2) species increases considerably.
Relating the conformational results to the enantio-dierentiation shown
by this modier (9-O-phenyl-CD) in the platinum-catalysed asymmetric
hydrogenation of KPL the inversion of the sense of enantio-dierentiation
observed cannot be traced to the conformational behaviour.
421
HPLC and UV-vis/circular dichroism
299
has been used to assess con-
version and selectivity in chiral xed bed reactor for stereoselective het-
erogeneous catalysis.
422
The UV-CD method and the HPLC-CD method
have been used to simultaneously determine ee values and concentration of
each enantiomer.
423
Tungler and coworkers have described that the circular dichroism spec-
trum of dihydrovinpocetine changes upon addition of both isophorone as
well as EtPy indicating interactions between these two substrates and the
chiral modier.
68
The similar method has been applied in case of (S)-proline
based chiral modiers.
224
The circular dichroism spectra of CD in toluene
has been found to change by addition of EtPy as shown in Fig. 38.
93
Add-
ition of EtPy to cinchonidine in chloroform has also resulted in changes in
the circular dichroism spectra of cinchonidine, although these changes were
less pronounced than those in toluene. The above results strongly indicate
that there is an interaction between CD and EtPy in the liquid phase.
The results of circular dichroism spectroscopy
401
have provided further
proof for dimer formation of CD in liquid phase. These results are related to
the addition of ATAs discussed in Section 5.6.2.
Fig. 38 The circular dichroism spectra of cinchonidine in toluene and its change by addition of
EtPy. (from ref. 93 with permission)
224 | Catalysis, 2010, 22, 144278
The Cotton shift of CD was measured at dierent [CD]
0
/[QN]
0
ratios.
The corresponding circular dichroism spectra are shown in Fig. 39. The
Cotton shift around 235 nm appeared to be very sensitive to the amount of
quinuclidine added. This Cotton shift is related to the dimer form of
CD.
191,400
Analogous results using MeO-CD have shown that this alkaloid
cannot form a dimer.
6.3 Characterization of the solid and the solid-liquid interface
6.3.1 Introduction. Various surface science techniques were used so far
to investigate the interaction of substrates and modiers or the substrate-
modier complex with the Pt surface. Most of these methods are using
conditions (often high-vacuum) far from those applied in catalytic hydro-
genations. For this reason, although some important details of the ad-
sorption behaviour of CD and substrates have been revealed, the results
have to be treated with certain precaution.
Surface characterization methods applied so far are as follows: (i) near-
edge absorption ne structure spectroscopy (NEXAFS),
91
(ii) X-ray photo-
electron spectroscopy
424,425
(XPS), (iii) low-energy electron diraction
(LEED,
425
(iv) scanning tunnelling microscopy (STM),
425427
(v) reection-
absorption infrared spectroscopy (RAIRS),
428,429
(vi) surface-enhanced
Raman spectroscopy (SERS),
92,430
(vii) attenuated total reection infrared
(ATR-IR) spectroscopy,
301,431,432
and (viii) electrochemical polarization.
241
It had to be emphasized that only ATR-IR spectroscopic method
240,232
and its combination with modulation excitation spectroscopy (MES) in a
ow-through cell
433
can be considered as appropriate methods approaching
almost real in situ conditions. It has to be emphasized that above two
techniques have the advantage to obtain information about adsorption
processes at the solid-liquid interface. In this respect it is important to
mention that exact vibrational assignments for adsorbed CD on Pt surface
using combination of experimental vibrational spectroscopic measurements
and ab initio computational methods were also reported.
92,434,435
Recently a
Fig. 39 Circular dichroism spectra of cinchonidine in the presence of dierent amount of
quinuclidine [CD]
0=
1.2 10
5
M. (from ref. 93 with permission)
Catalysis, 2010, 22, 144278 | 225
new method for in situ spectroscopic investigation of heterogeneous cata-
lysts and reaction media at high pressure have been developed.
436
6.3.2 Investigation of the substrates. The adsorption of EtPy on Pt(111)
at low temperature was investigated by XP and UP spectroscopy.
424
The
results indicated that EtPy adsorbed strongly to the Pt. The ketone carbonyl
is more strongly involved in the chemisorption bond than the carboxyl one.
Further analysis showed that EtPy is predominantly adsorbed in a tilted
rather than a completely at mode.
The behaviour of EtPy during adsorption on alumina-supported plat-
inum lms and on a commercial 5 wt% Pt/ Al
2
O
3
catalyst has been studied
in the absence and presence of coadsorbed CD.
91
The in situ ATR-IR study
at room temperature using hydrogen-saturated CH
2
Cl
2
as solvent demon-
strated that upon adsorption on the Pt EtPy decomposes with the formation
of strongly adsorbed CO and other organic residues. The presence of CD
(10
4
M) strongly decrease the rate of decomposition of EtPy.
Upon using STM method self-condensation of MePy over Pt surface was
observed.
308
This reaction took place in the absence of cinchona modier at
low hydrogen coverages. Based on this nding new set of side reactions with
the involvement of MePy was proposed and conditions to avoid the by-
product formation was discussed (see Section 5.1).
Side reactions of EtPy during enantioselective hydrogenation on Pt/
Al
2
O
3
have been investigated using in situ ATR-IR and ex situ DRIFT.
309
The studies revealed that EtPy can decomposed and polymerize (aldol
condensation) under conditions of hydrogenation. These side reactions take
place both on the Pt site and the Al
2
O
3
support.
Based on analysis of the RAIRS spectra of MePy it has been shown that
on Pt(111) at room temperature MePy undergoes surface mediated enol
formation leading to an assembly of H-bonded superstructures.
310
The
decrease of the temperature and the use of low background hydrogen
pressure suppress these surface reactions.
In a recent study adsorption and reaction of EtPy on Pt/g-Al
2
O
3
was
studied by IR spectroscopy.
311
Several side reactions of EtPy were detected.
These results were discussed in Section 5.1.
The adsorption mode of MePy and EtPy was studied under ultra-high
vacuum conditions on Pt single-crystal surfaces using X-ray and UV
photoelectron spectroscopies (XPS and UPS),
424
NEXAFS,
96
and
(RAIRS).
437
The results indicated that alkyl pyruvates adsorbs via lone
pair-metal interaction of both carbonyl groups, i.e., in cis conformation
with their plane oriented normal or tilted with respect to the surface. At
high coverage, a minority species was assigned to an Z
1
-trans
conguration.
437
The coadsorption of hydrogen resulted in signicant inuence on the
adsorption of alkyl pyruvates by lowering the tilting angle of the adsorbed
species
438
and suppressing surface polymerization of the adsorbed enedio-
late species observed earleir.
308
6.3.3 Investigation of the modiers. Adsorbed forms of cinchona al-
kaloids display dierent IR spectra from each other and from the solution
form of the alkaloids. This fact makes vibrational spectroscopy a suitable
226 | Catalysis, 2010, 22, 144278
method to investigate the adsorption of cinchona alkaloids on metal sur-
faces. Although this method seems to be very powerful it could not answer
the key question, namely, which of these species interacts with the substrate
in the enantio-dierentiating step.
The rst information that the mode of adsorption of CD on Pt depends
on its coverage was obtained by using in situ ATR-IR spectroscopy.
240
At
low coverage the at mode, while at high one the tilted mode prevails.
Further study revealed that abstraction of hydrogen form the quinoline ring
can also take place resulting in a so called a-H abstracted form.
431
Study on
Pt/Al
2
O
3
in the presence of an organic solvent and hydrogen revealed three
dierent adsorption modes of CD as shown in Fig. 40.
Infrared spectroscopy (IR), Raman spectroscopy, surface-enhanced
Raman scattering (SERS) and reectionadsorption infrared spectra
(RAIRS) studies
428,431,434
ratify the results discussed above (Fig. 40).
The adsorption of CD on Rh/Al
2
O
3
has also been investigated using
ATR-IR spectroscopy. The adsorption appears to be more complex than
that observed on Pt and Pd. Strongly adsorbed at form was observed on
Rh when adsorption was performed in the absence of dissolved hydrogen.
This form is responsible for the fast hydrogenation of the quinoline ring and
does not allow the detection of the at form in the presence of dissolved
hydrogen.
270
Contrary to Pt it has been discovered that on Rh hydrogen-
ation of the heteroaromatic part of the quinoline ring takes place. Adsorbed
CD in the at geometry is the intermediate of the hydrogenation reaction,
Fig. 40 Suggested adsorption mechanism of cinchonidine on Pt/Al
2
O
3
at 283 K based on ATR
experiments; y represents the surface coverage. Species 1: p-bonded, 2: a-H abstracted and 3: N
lone pair bonded (tilted). (Reproduced from ref. 431 with permission)
Catalysis, 2010, 22, 144278 | 227
Zaera and coworkers investigated the adsorption of CD at Pt using in situ
RAIRS technique.
428
Good correlation has been found between the surface
concentration of at lying CD and the enantioselectivity in EtPy
hydrogenation.
In another study it was found that the oxygen present in most CD so-
lutions from dissolved air blocks the surface toward any CD uptake, pre-
sumably via its dissociation to atomic surface oxygen atoms (and maybe by
partial oxidation of the platinum surface), while Ar, N
2
, or CO
2
has no
inuence on the adsorption of CD. Hydrogen plays a unique role, initially
facilitating the uptake of CD.
90
Non-linear eects (see Section 5.5.3) has also been characterized by
in situ ATR-IR spectroscopy comparing the behaviour of CD and
PhOCD.
435
It was shown that both alkaloids are adsorbed via the quinoline
ring and that the spatial arrangement of the quinuclidine ring is crucial for
the chiral recognition. The result helped to elucidate the role of the phenyl
group played in the creation of the chiral space responsible for the inversion
of ED.
Surface-enhanced Raman spectroscopy has been applied to investigate
the adsorption of CD on polycrystalline Pt.
92
The eects of liquid-phase
concentration in ethanol and that of co-adsorbed hydrogen were studied.
It was found that CD is strongly and irreversibly adsorbed through its
quinoline ring via p-bonding. Stronger adsorption of DHCD compared
with CD was also suggested.
The room-temperature adsorption of four cinchona alkaloids and three
reference quinoline-based compounds from CCl
4
solutions onto a poly-
crystalline Pt surface was characterized by in situ RAIRS.
377
The results are
shown in Fig. 41. Data show Langmuir type adsorption kinetics. The
Fig. 41 Adsorption uptakes for all the quinoline-derived compounds from CCl
4
solutions
onto Pt as a function of concentration. (Reproduced from ref. 377 with permission)
228 | Catalysis, 2010, 22, 144278
calculated adsorption equilibrium constants (K
ads
) are given in Table 18
and were found to follow the sequence CNWQDWCDWQNW6methoxy-
quinolineWlepidineWquinoline. Some of this ordering can be explained by
dierences in solubility, but QD displays a much larger K
ads
than expected
on the basis of its large relative solubility.
Results indicated also that each alkaloid binds dierently on Pt at sat-
uration coverages. At low concentrations all alkaloids adsorb with their
quinoline ring at on the surface and then tilt abruptly upon increasing
coverages, but the switch-over takes place at signicantly dierent solution
concentrations in each case. CD tilts mainly along its quinoline long axis,
whereas CN does it along the short one. CN has also larger degree of ring
distortion. The most surprising result is the fact that CN shows a higher
K
ads
than CD, QN, or QD. In this respect results obtained in an earlier
study has to be mentioned. As shown in Fig. 42 when in sequential intro-
duction of CCl
4
solutions of CN, CD, and back to CN was applied CN was
replaced by CD, while CN cannot replace CD.
376
Similar conclusions can be
obtained from other studies using the chiral switch technique.
238,379
The
dierence in the adsorption mode of CD and CN was investigated in a
recent study.
439
The main message from these studies is that the solvent has to be taken
into consideration in the formation of the above discussed adsorbed forms
of alkaloids.
The adsorption of 1-(1-naphthyl)ethylamine (NEA) on platinum surfaces
has also been characterized by RAIRS and temperature-programmed de-
sorption (TPD) both under ultra-high vacuum and in situ from liquid
solutions.
440
ATR-IR spectroscopy was also used to prove the exibility of the qui-
nuclidine moiety resulting in surface quinuclidine bound CD. It was done by
comparison of the ATR-IR spectra of CD and PhOCD adsorbed on
Pt.
98,435
The dierence in the intensity of the signal at 1458 cm
1
(d(CH)
deformation modes of the quinuclidine skeleton) was attributed to the
possible interaction of the quinuclidine moiety of CD with the Pt surface.
Based on the comparison of the ATR-IR spectra of CD and CD hydro-
chloride adsorbed on Pt under similar condition the authors came to the
conclusion that at the Pt the quinuclidine moiety of CD has identical
structure as in the protonated quinuclidine of CD hydrochloride.
98
This
nding was considered as an additional evidence that CD can be protonated
Table 18 Adsorption equilibrium constants (estimated from the data given in Fig. 41 and
expressed as K
ads
1
) and solubilities in CCl
4
for the quinoline-derived compounds. (Repro-
duced from ref. 377 with permission)
Compounds K
ads
1
mM Solubility in CCl
4
, mM K
ads
1
/solubility
Quinoline 30 innite
lepidine 11 innite
6-methoxyquinoline 6.5 innite
QN 0.65 8.63 0.075
CD 0.5 1.56 0.32
QD 0.25 16.3 0.015
CN 0.1 0.30 0.33
Catalysis, 2010, 22, 144278 | 229
by chemisorbed hydrogen in aprotic solvent. However, the authors admit
that this conclusion is tempting, further studies are needed to conrm its
validity. Doubts may arise from the presence of HCl originating from
CH
2
Cl
2
solvent decomposition on Pt.
327
We also have serious doubt with
respect to these interpretations.
ATR-IR method was also used to give some new information about the
formation of quinuclidine bonded form of alkaloids. However, these results
are quite dubious. In this respect in a recent study the following information
was given:
270
Recent results indicate that the quinuclidine moiety is also
involved in adsorption on Pt.
98,441
At low coverage, the energetically fa-
voured geometry exhibits the aromatic ring parallel to the surface and the
quinuclidine moiety oriented toward the metal surface in a geometry that
has been named surface quinuclidine bound (SQB).
442
However, the careful analysis of references given above clearly indicates
that there is no experimental evidence for the above statement. In ref. 441
upon using molecular dynamics simulation CD was found to adsorb with
the quinoline ring oriented largely parallel (ao61) to the surface. CD sur-
face attachment was found to be through both p- bonding of the aromatic
group and adsorption of the C
Q
C double bond of the vinyl group. It was
also mentioned that we found that CD conformation at the surface was
not only aected by the ethanol solvent, but also by the cinchonidine
cinchonidine steric interactions and their competition for surface sites.
However, no words were given related to the involvement of the
Fig. 42 In-situ RAIRS from experiments: sequential introduction of CCl
4
solutions of CN,
CD, and back to CN (from top to bottom). (Reproduced from ref. 429 with permission)
230 | Catalysis, 2010, 22, 144278
quinuclidine moiety in the adsorption. In ref. 98 only computational results
were given, while ref. 442 contains scientic speculations and not real evi-
dences. Consequently, there is no exact experimental evidence for the for-
mation of surface quinuclidine bound CD.
The adsorption of CD and CN on Pt(111) and Pd(111) single crystals has
been investigated by means of time-lapse STM in an ultra-high vacuum
system.
443
CD and CN showed similar adsorption modes and diusion
behaviour on Pt(111). The only exception is that the atly adsorbed CN
molecules were signicantly more mobile than CD.
NEXAFS and corresponding STEX calculations have been applied
to investigate the orientation of DHCD on Pt(111) at 298 and 323 K.
91
The results indicate that at 298 K the quinoline ring is almost parallel
to the Pt surface but is tilted up from the surface by 60 101. However, the
results show that at higher temperatures the alkaloid dissociates to
quinoline.
Various techniques, such as NEXAFS, XPS, STM, and temperature
programmed reaction was applied to investigate at 320 K the molecular
orientation, spatial distribution, and thermal behaviour of the powerful
chiral modier precursor (S)-naphthylethylamine adsorbed on Pt(111)
427
No formation of ordered arrays was observed in the presence or the absence
of coadsorbed hydrogen. Based on high resolution STM images some
speculation was done related to the formation of 1:1 docking complex be-
tween MePy reactant and the chiral modier.
NEXAFS revealed that the quinoline ring of 10,11-dihydrocinchonidine
is orientated parallel to the surface at 298 K, whereas at 323K the orien-
tation is tilted about 601 to the surface.
91
von Arx et al. used STM to reveal
that the cinchonidine molecules are randomly distributed on the Pt (111)
surface.
444
Attard and co-workers studied the inuene of surface structure and
surface chirality on the adsorption rate of several modiers.
445
However,
probably due to the large adsorption energy of these systems, no dierence
in the adsorption rate was observed. It was also observed that in a hydro-
gen-saturated solution, the alkaloid dihydrocinchonine is partially desorbed
from a kinked, chiral Pt surface.
The adsorption of CD on polycrystalline Pt surfaces in H
2
SO
4
was in-
vestigated by cyclic voltammetry.
241
The adsorption was found to be ir-
reversible. The results indicated that at maximum coverage, 50% of the Pt
atoms were still accessible for hydrogen adsorption. They calculated also
the site requirement for CD equal to 1314 Pt atoms. In another study it was
calculated that in the surface modication model each enantioselective site
requires 25 or so Pt atoms to achieve simultaneous adsorption of modier,
reactant, and hydrogen.
446
The adsorption of quinoline and CN on Pt (111), Pt (332) and poly-
crystalline Pt electrode has been studied by dierential electrochemical mass
spectrometry (DEMS). It was shown that benzene is even able to displace
some of the alkaloid.
447
Electrochemical method was applied to investigate the introduction of
cinchona alkaloids with R- and S-kink sites of the Pt(643) surface.
447
No
interaction was evidenced.
Catalysis, 2010, 22, 144278 | 231
6.3.4 Substrate modier interactions. Interaction of KPL with CD was
investigated by ATRIR concentration modulation spectroscopy using
CH
2
Cl
2
as a solvent.
314
The results showed that in the presence of CD and
KPL a new band appeared at 2580 cm
1
as shown in Figs. 43 and 44.
This band was attributed to the formation of protonated quinuclidine by
chemisorbed hydrogen. This experimental results is considered as a key
prove for the support of authors general view with respect to the reaction
mechanism (see more details in Section 8), In this respect the use of CH
2
Cl
2
solvent has to mentioned. Due to its use it is not excluded that the observed
protonation is simple an artefact.
Recently the formation of a surface complex between adsorbed
cis-EtPy and protonated CD has been suggested using ATR-IR method
during asymmetric platinum catalysed hydrogenation of EtPy in super-
critical ethane solvent.
448
These results are shown in Fig. 45. Based
on the shifts in the 12001300 cm
1
region preferential adsorption of
EtPy as cis-conformer was suggested. The appearance of the band at
1660 cm
1
was tentatively be attributed to carbonyl stretching vibrations
of EtPy.
Fig. 43 Demodulated ATR spectra of dierent concentration modulation experiments. The
KPL concentration was modulated (modulation period T (184 s) between 0 and 5 10
2
mol/L
in CH
2
Cl
2
. Spectrum a: clean, uncoated Ge internal reection element; spectrum b: a Pt/Al
2
O
3
lm in the absence of CD; spectrum ce were recorded on a Pt/Al
2
O
3
lm in the presence of CD
(5 10
4
mol/L). Before the modulation experiments were started (ce), the Pt/Al
2
O
3
lms
were dierently treated: (c) 30 min N
2
saturated CH
2
Cl
2
only; (d) pretreatment with 5 min H
2
saturated KPL solution; (e) directly contacted with modulation solutions. (Reproduced from
ref. 314 with permission)
232 | Catalysis, 2010, 22, 144278
The above shift to lower wave-numbers occurs due to hydrogen bonding
between the quinuclidine nitrogen and the keto oxygen atom of EtPy.
However, in this respect it is necessary to mention the authors following
statement: This interpretation is in line with our recently reported study on
Fig. 44 Comparison between two KPL concentration modulation ATR experiments. The
KPL concentration was modulated (modulation period T 184 s) between 0 and 5 10
2
mol/L
in CH
2
Cl
2
. Use of modiers: (a) N-Methyl CD (5 10
4
mol/L), (b) CD (5 10
4
mol/L).
(Reproduced from ref. 314 with permission)
Fig. 45 ATR-IR spectra of adsorption/reaction of EP in supercritical ethane on (1) Al
2
O
3
in absence of H
2
; (2) CD-premodied Pt-black; (3) unmodied Pt/Al
2
O
3
, but CD dissolved in
EP; (4) CD-premodied Pt/Al
2
O
3
. Conditions in all experiments were 40 1C, and 95 bar. Molar
ratio EP:H
2
: ethane
=
1:5:200. (Reproduced from ref. 448 with permission)
Catalysis, 2010, 22, 144278 | 233
KPL adsorption on a CD-modied Pt/Al
2
O
3
thin lm.
431
However, in the
above reference there is no words related to the assignment of any bands
around 1660 cm
1
.
The conformational exibility of the quinuclidine moiety was investigated
by ATRIR experiments under nearly in situ conditions, by comparing the
adsorption behaviour of CD and O-phenyl-CD on platinum.
98,435
It was
concluded that the tertiary nitrogen of the quinuclidine moiety can par-
ticipate in the anchoring of the alkaloid and can be protonated by surface
hydrogen. This study is related to the mechanism proposed by Baikers
group whereby the tertiary nitrogen can promote charge polarization of
hydrogen and its transfer to the substrate (see more details in Section 8).
There is one more comment on these results. Even if we accept results
shown in Figures 4345 one question still remains: What is the proof that
surface species assigned to the [CD-H

-substrate] complex is really in-

volved in the ED?
6.3.5 HPLC-MS and HPLC-ESI-MS investigations. These studies were
related to the investigation of the products formed from dierent alkaloids
during enantioselective hydrogenation reactions. Upon investigation of the
eect of a-ICN it was demonstrated by HPLCESMS measurements that
the cyclic ether structure of the alkaloid remained unchanged.
449
In another
study the product of isomerization of b-ICN, b-isocinchonicine (b-ICNN),
was hydrogenated using supported Pt and Pd catalysts. The products were
analyzed using HPLC-ESI-ion-trap MS measurements.
450
Combined HPLC and ESI-MS method was used to investigate cinchona
alkaloid derivatives formed in the hydrogenation of a-ICN and b-ICN.
197
The products of reaction are shown in Fig. 46. The hydrogenated com-
pounds were identied as 1
/
,2
/
,3
/
,4
/
- tetrahydro-a-ICN (A) and 1
/
,2
//
,3
//
,4
//
-
tetrahydro-b-ICN (B) and decahydro-a-ICN (C).
Upon investigating C9-O-substituted cinchona alkaloids in the enantio-
selective hydrogenation of EtPy ESI-MSD-ion-trap method was applied to
follow and identify the hydrogenated derivatives of these cinchona
derivatives.
206
HPLC-MS method was used to investigate products of HD exchange
measurements of dierent alkaloids.
451
As revealed by these measurements,
iso-alkaloids are not converted back to CN or QD; (v) in all alkaloids
studied, HD exchange takes place on the quinoline skeleton as well as on
carbon atom C9; (vi) HD exchange on the quinuclidine skeleton appears
signicant only in the case of CN and a-ICN.
230
Deuterium exchange in CD
was also studied in ref. 48.
Fig. 46 Cinchona alkaloid derivatives formed by hydrogenation of a-ICN and b-ICN.
234 | Catalysis, 2010, 22, 144278
Potential products of hydrogenation of a-ICN were investigated in an-
other study. The aim of this work was identifying hydrogenated cinchonas
formed during enantioselective hydrogenation of EtPy. The target com-
pound was DHCN which might possibly be formed from a-ICN. The results
obtained by HPLC/ESI-MS measurements showed that of DHCN was not
formed.
385
7. Theoretical calculations
7.1 Introduction and rst attempts
The proposed mechanisms for the asymmetric hydrogenation of activated
ketones over cinchona-platinum catalyst system that leads to the observed
ED require supports using dierent theoretical-computational studies.
These studies are related to the conformational analysis of both substrates
and modiers, adsorption of both substrates and modiers into Pt and
energetic calculations for the whole complex system Pt-modier-substrate.
It is generally accepted that the CD or its natural or synthetic analogue
forms a 1:1 complex, what is hydrogenated on the metal surface. The
question is where the chiral discrimination takes place on the Pt surface or
in the liquid phase.
Both the structure and the conformational complexity of cinchona al-
kaloids generate several possible interactions with the substrates. As a re-
sults a chiral pocket is created for the ED either on the Pt surface or in the
liquid phase.
The way to explore these properties one has to investigate or model
theoretically the characteristic features of substrate molecules and the cin-
chona alkaloids. Based on this knowledge, the modier-Pt and the sub-
strate-modier and substrate-modier-Pt interactions can be investigated.
It is useful to extend all these calculations with solvent eect.
Various computational methods have been used so far, such as molecular
mechanics
452
and quantum chemical calculations.
453
Molecular geometries
can be optimized on MMFF94 molecular mechanic level. Relatively
accurate energies (mainly for energy dierences) can be obtained e.g. on
HF-SCF/631G* or B3LYP/631G* level single point energy calculations.
The involvement of metal in these calculations requires the use DFT
methods.
In the next sub-sections we shall review most of the relevant results re-
lated to the computation on substrates, modiers. Calculations related to
the substrate-modier interactions and possible interactions of all these
components with Pt surface will be discussed in Section 8 related to the
reaction mechanism.
7.2 Characteristic features of substrate molecules
Among the substrates, for which the cinchona-Pt catalytic system yields
high ee values, the following groups of molecules are in the focus of ex-
periments and computations: (i) pyruvate esters, (ii) ketopantolactone
(KPL), (ii) diketones (PPD), (iii) triuoro acetophenone (TFA), and (iv)
triuorodiketones. In addition, the uor substituted derivatives of the rst
Catalysis, 2010, 22, 144278 | 235
and third groups of compounds were also included into computational
studies.
It was also shown that s-trans conformer of MePy is more stable in the gas
phase by 12 kcal/mol, but the relative stability could be strongly inuenced
by the metal surface, especially because the s-cis conformer has a consider-
ably larger dipole moment.
454
With respect to the formation of substrate CD
complex the two conformers of MePy were compared,
455
and it was found
that the complex yielding (R)-methyl lactate upon hydrogenation was
more stable than the corresponding pro-(S) complex by 1.8 kcal/mol
(corresponds to an enantiomeric excess of 92%, in good agreement with
experiment), however, for the analogous complexes of s-cis-methyl pyruvate
the energy dierence is only 0.2 kcal/mol in favour of pro-(R), corresponding
to 17% ee value. The relation between the electronic structure of
a-substituted ketones and their reactivity
456
in the racemic and enantiose-
lective Pt-catalysed hydrogenation was also investigated. A correlation be-
tween the keto carbonyl orbital energy and the hydrogenation rate was
found, which rationalizes the eect of the substituent on the rate of hydro-
genation (the often observed rate acceleration).
The rst model calculations indicated that in the complex responsible for
the enantio-dierentiation the a-keto ester existed in trans-conformation.
457
Further studies revailed that in the enantio-dierentiation complex the
a-keto ester can also exist in its cis conformation.
455
The fact that in the
hydrogenation of KPL to (R)-PL high enantioselectivites were obtained
indicated that the rigid cis conformation has no inuence on the enantio-
dierentiation step.
Generally speaking, the number of substrate molecules with high ee is in a
relatively narrow
59,370
range: This strong substrate specicity has not been
answered yet, neither by theory nor with computation. a-keto esters were
modelled in dierent studies.
49,74,456,458
The trans conformer is more stable
than the cis one, the carbon atom in the keto group is partially positively
charged, while the oxygen part is negatively.
In the hydrogenation of acetophenone and TFA derivatives on CD-
modied Pt/Al
2
O
3
, the rates and ee values varied strongly with the nature of
the aromatic substituents.
332,363
The dierent reactivities were attributed to
the electronic (and steric) eect of the substituents and to hydrogen-bonding
interactions between the quinuclidine N atom of the alkaloid and the car-
bonyl group of the substrate.
359,456
Theoretical calculations revealed a linear
correlation between the logarithm of the reaction rate and the highest
occupied molecular orbital and lowest unoccupied molecular orbital stabili-
zation DE
orb
of the carbonyl compounds, relative to the reference com-
pound (see Fig. 47.).
53
The relative orbital stabilization is dened as the sum
of two numbers: the dierence between the energy of the anti-bonding or-
bital of the reference compound acetophenone and that of the substituted
acetophenone, and the corresponding energy dierence for the bonding
orbitals. The more stabilized the orbitals of the substituted acetophenone
are, the larger DE
orb
and the reactivity of the molecule are. According to
these calculations (where the metal surface was not involved), the origin of
ligand acceleration is the lowering of the p-orbitals in the diastereomeric
complex of the substrate and modier. In the pro(R) and pro(S) complexes,
236 | Catalysis, 2010, 22, 144278
the carbonyl -orbitals are dierently stabilized, which results in dierent
intrinsic rates in the formation of the two enantiomers. It remains, however,
to be proven that the concept can be extended to other substrates and
reaction types.
The proton anities of seven dierent ketones, vicinal diketones, and
a-keto esters (acetophenone, TFA, 2,3-butanedione, PPD, MePy, EBF and
KPL) have been evaluated theoretically using the conventional ab initio HF
and several post-HF methods (MP2, MP4, CCSD), density functional
methods with the B3LYP hybrid functional, as well as some ab initio model
chemistries [CBS-4M, G2(MP2), and G3(MP2)//B3LYP].
459
In the most stable protonated species, the proton is bound to one
of the carbonyl oxygens in the molecule. The preferred site depends on the
molecule. In two a-keto esters (MePy and KPL) the carbonyl oxygen
of the ester group is protonated. In the case of EBF and the asym-
metric vicinal diketone, PPD it is the carbonyl oxygen next to the phenyl
group, which forms a more stable bond with the proton. These pheno-
mena can be understood in terms of resonance stabilization of the
resulting cations. It was shown that the protonation of both the modier
and the reactant in acidic solvent hinders the formation of a reactant
modier complex, which is believed to be crucial for enantio-discrimination,
consequently in these cases the ee decreases. This decrease of ee
was observed in case of butanedione (14% vs. 47%), KPL (35% vs. 79%)
and PPD (6% vs. 65%) comparing results in AcOH and toluene,
respectively.
It is known that triuoro beta-diketones can also exist in enol form. The
adsorption of both the keto and enol forms of 1,1,1-triuoro-2,4-diketone
into Pt(111) was modelled and calculated
406
DFT calculations including the
simulation of the interaction of a protonated amine with the enolate
Fig. 47 Linear correlation between the logarithm of the hydrogenation rate (mmol h
1
) of
acetophenone and TFA derivatives and the relative orbital stabilization DE
orb.
(Reproduced
from ref. 53 with permission)
Catalysis, 2010, 22, 144278 | 237
adsorbed on Pt revealed that only the CO bond next to the CF
3
group of
the substrate is in direct contact with Pt and can be hydrogenated.
7.3 Characteristic features of cinchona alkaloids
Characteristic features of cinchona alkaloids have already been discussed in
Sections 2 and 3. For this reason, we shall refer to information given in these
sections. In the next sub-section we shall focus mainly on the conforma-
tional analysis of cinchona alkaloids and their analogues.
7.3.1 Conformational behaviour of cinchonidine. Among the eective
chiral modiers used for enantioselective hydrogenation of activated ke-
tones over Pt/Al
2
O
3
catalysts the most eective and widely used one is CD.
The characteristic feature of this alkaloid is shown in Figs. 2 and 3.
It has already been mentioned earlier cinchona alkaloids were intensively
investigated by NMR methods
176,186
as described in Section 2. Conforma-
tional behaviour of cinchonidine was calculated independently by dierent
groups.
83,88,460,461
Most of these results are in accordance with earlier results
discussed in Section 2.
176,183
In our rst study,
84
the conformational analysis
was done by using rigid quinoline and quinuclidine moieties. As a result,
four stable conformations have been found. In our subsequent study,
461
all
of these calculations were repeated in such a way that only the phi and psi
torsion angles were forced to be constant, while all other freedom of the
molecule were left to relax. The conformational analysis indicated that
CD might exist at least in nine dierent forms, however only four of them
are relatively stable (two open (A1 and A2) and two closed (C1 and C2)
conformers). These results are shown in Fig. 48. The solid line in this
gure gives the contour of the possible forms of CD within 8 kcal/mol
energy range. For CD the 2D NOE spectra indicate
446
that the major
conformation in solution is conformation A2, this is close to that adopted
by the molecules in the solid state.
179
Thus, the conformational analysis
strongly indicates that CD can exist both in open and closed forms and both
forms of CD can be involved in the formation of substratemodier
complex.
Detailed conformational analysis of CD in solutions using NMR tech-
niques as well as theoretical calculations was done in ref. 88. Three con-
formers of CD are shown to be stable at room temperature, cl(1), cl(2), and
op(3), with the latter being the most stable in apolar solvents. The stability
of the closed conformers relative to that of open(3), however, increased with
solvent polarity. In polar solvents the three conformers have similar energy
(Fig. 48).
Structures and relative energies in kcal/mol of low energy CD conform-
ations were calculated using hybrid density functional (B3LYP/631 G*/
PCM B3LYP) and AMBER* optimization (AMBER*/GB/SA).
416
The
relative stability of the conformers is as follows: op(3)Wcl(1)Wcl(2)Wop(4).
The eect of protonation on the conformation of CD was investigated in
a recent study.
417
It was shown that the protonation of cinchonidine ap-
pears to hinder the rotation around the C4
/
C9 and C9C8 bonds and to
favour only a narrow range of the conformational space of the molecule. In
terms of the behaviour of CD and CN molecules in solution, 2D NMR
238 | Catalysis, 2010, 22, 144278
experiments indicate a somewhat more restricted rotational conformation
space for cinchonine than for cinchonidine.
462
Protonation of cinchonidine
also signicantly restricts its rotational conformation space.
417
7.3.2 Conformational behaviour of cinchona derivatives. Detailed NMR
analysis and ab initio quantum chemical calculations were performed on
1
/
,2
/
,3
/
,4
/
,10,11-hexahydroderivatives of CD.
409
The rotation around the
C4
/
C9 and C9C8 bonds led to conformers of close energies, providing
evidence on the possible presence of other stable conformers in the solution
of these cinchonidine derivatives.
The conformational analysis of the synthetic chiral modier O-phenyl-
cinchonidine in vacuum has been performed at semi-empirical level and at
DFT level with a medium-size basis set for energetics related to the parent
alkaloid cinchonidine.
421
The O-phenyl-cinchonidine behaves similarly to
cinchonidine and owns the same main stable conformers as mentioned
above in vacuum and in CH
2
Cl
2
and CCl
4
solvents. Based on combined
theoreticalexperimental results, the open(3) appears to be the most
populated in these solvents, but indication was found that an excess
cl(2) conformer has to be also expected in CD
2
Cl
2
in comparison to CD.
The authors suggest that the sterical constraints imposed by insertion
of O-phenyl at the C9 position shows its eect when the substituted CD
adsorbs on the surface via its quinoline part.
Isocinchonines belongs to the class of rigid alkaloids (see Section 3.2).
In these molecules the rotation of the quinuclidine ring is restricted (see
Fig. 6). b-ICN was investigated in a recent study and its conformational
analysis was performed. The results conrmed that the numerous con-
formational changes possible for CD and CN are reduced to a single degree
of freedom, namely rotation around C(4
/
)-C(9).
463
Fig. 48 Conformational analysis of cinchonidine. The calculated energy map has been ob-
tained by changing the torsion angles phi ((C3
/
)(C4
/
)(C9)(C8)) and psi ((C4
/
)(C9)(C8)
(C7)). The contours are given in steps 0.5 kcal/mol. (Reproduced from ref. 461 with
permission)
Catalysis, 2010, 22, 144278 | 239
Recently detailed NMR, DFT, and X-ray investigation of some cinchona
alkaloid O-ethers related to the determination of their structure and con-
formations was published.
391
7.3.3 Other calculations. Conformational analysis of synthetic
modiers, such as (R)-2-1-pyrrolidinyl)-1-1-naphthyl)ethanol, (R)-2-1-
pyrrolidinyl)-1-2-naphthyl)ethanol, and (R)-2-1-pyrrolidinyl)-1-1-8-methyl-
naphthyl)]ethanol was also performed. Open(3) conformers appeared to be
the most stable. Minimum energy structures of the pro-(R) and pro-(S)
interaction complexes between (R)-2-1-pyrrolidinyl)-1-1-naphthyl)ethanol
and trans ethyl pyruvate were also performed. Good quantitative agreement
between calculated and experimental ee values has been found for the
enantioselective hydrogenation of EtPy over Pt catalyst chirally modied by
synthetic pyrrolidinyl naphthylethanol modiers, assuming that EtPy
exists in the trans conformation in the adsorbed enantio-dierentiating
complex. The destabilising repulsive interaction between EtPy and the an-
choring aromatic moiety within the pro-(S) complex has been identied to
be important for ED.
85
7.4 Substrate-Pt interaction
The adsorption of ketones on transition metals has been the topic of various
studies.
464466
In general, ketones adsorb on transition metal surfaces via two
dierent bonding mode: as Z
1
(O) in an end-on adsorption conguration in
which the oxygen atom is bonded by its lone pair orbital to the metal surface,
or as Z
2
(C, O), with both the carbon and the oxygen atoms of the keto-group
p-bonded to the metal and the C
Q
O moiety lying parallel to the surface.
The bonding interaction between an adsorbate and a surface is a very
complex process.
467
To perform rst principle calculation on the adsorption
of substrate molecule
97
on a reasonably large (about 2040 atom) Pt (or Pd)
surface or cluster has become feasible only recently, however these results
should be handle cautiously. For example a drawback of using metal
clusters of this size is that the Pt cluster is strongly paramagnetic (high spin
states) in the result of the computation,
98
while experimentally it is not
magnetic.
The interaction of various ketones with Pt surface was investigated in
details.
97
Fig. 49 shows the adsorption geometries of EtPy for both the cis
and in the trans conformations. The cis Z
2
adsorption appeared to be the
most stable one (see Fig. 49a) In the Z
1
adsorption mode only the trans
conformation showed an energy minimum (see Fig. 49c), whereas the cis
conformer was not stable when Z
1
adsorbed. When adsorbed Z
2
the main
interaction the keto-carbonyl moiety interacts with the metal. Once the
preferred keto-carbonyl adsorption had taken place, the ester group inter-
acts only weekly with the Pt surface.
The adsorption EBF and its derivatives onto Pt surface was also modelled
and calculated.
468
The results showed that the introduction of two o-sub-
stituents into the aromatic ring completely eliminated the reactivity of the
ketone. The dramatic dierence between EBF and ethyl mesithylglyoxylate (5)
is their mode of adsorption. The o-substitution suppresses adsorption
240 | Catalysis, 2010, 22, 144278
modes where the keto-carbonyl group is bound to the metal in Z
2
(C,O) mode
involved in the hydrogenation reaction.
In a recent study the interaction of PPD with Pt surface was investigated
by DRIFT spectroscopic method and DFT calculations.
469
Seven dierent
adsorption forms were suggested as shown in Fig. 50. The calculated ad-
sorption energies are given in Table 19. DFT calculations demonstrated that
Z
1
-(O2) conguration is the most stable end-on adsorption mode of PPD.
Tilted p-bonded adsorption mode of cinchonidine was revealed on the
platinum catalyst at higher concentration of CD.
7.5 Modier-Pt interaction
The interaction of CD with Pt(111) both in ultrahigh vacuum (UHV) and in
ethanol solvent has been studied using molecular dynamics (MD) simu-
lation. In UHV at low coverage (0.0125 molecules/Pt atom) and 298.15 K
the CD was found to adsorb with the quinoline ring oriented largely parallel
(a
=
61) to the surface.
441
Cinchonidine surface attachment was found to be
through both p bonding of the aromatic group and adsorption of the C
Q
C
double bond of the vinyl group. The interactions between ethanol solutions
of CD (0.129 and 1.035 M) and the platinum surface were also simulated.
For the less concentrated solution (0.129 M) two dierent equilibrium
conformations were found, one in which only part of the quinoline is at-
tached to the surface, and another slightly more stable conformation. In the
latter one the quinoline group is adsorbed parallel to the platinum surface.
Fig. 49 Adsorption modes of EtPy on Pt: (a) Z
2
-cis, (b) Z
2
-trans, (c) Z
1
-trans, and (d)
semi-hydrogenated Z
7.3
-cis. (Reproduced from ref. 97 with permission)
Catalysis, 2010, 22, 144278 | 241
It was also observed that that CD conformation at the surface was aected
both by the ethanol solvent and the CD-CD interactions and their com-
petition for surface sites.
The conformations of CD adsorbed on a Pt(111) surface were also in-
vestigated.
442
Eight conformationally dierent adsorption states due to
dierent degrees of rotation around the t1 and t2 degrees of freedom were
identied. The possible role of these conformations in the formation of
chiral surface sites relevant to enantioselective hydrogenation was also in-
vestigated. The comparison of the conformational behaviour of CD in so-
lution and on Pt has revealed the eect of the metal surface on the internal
mobility of the alkaloid. In the study the role of the adsorbed op(3) con-
former, the observed conformational exibility on the Pt surface revealed
the possibility that other conformers of CD also might be involved in ED.
Closed conformations of CD are found to play an important role in the
Fig. 50 PPD adsorption modes. (Reproduced from ref. 469 with permission)
Table 19 Adsorption Energies for Dierent Adsorption Modes of 1-Phenyl-1,2-propanedione
(Reproduced from ref. 469 with permission)
adsorption conguration DE (kJ mol
1
)
Z
1
(O1) 19
a
Z
1
(O2) 36
pseudo- n
1
(O1) 55
di- n
1
(O1, O2) 3
a
Z
2
(C1, O1) 88
b
Z
2
(C2, O2) 38
a
Z
3
(C1, O1, O2) 59
a
Taken from ref. 470.
b
Phenyl ring only partly adsorbed.
242 | Catalysis, 2010, 22, 144278
conformational equilibria on the surface due to their stability and are
identied as precursors of the less stable, but probably more active, open
conformers. Although the open and closed conformers are closely related to
the correspondent ones found in solution, surface species that are also ad-
sorbed via quinuclidine moiety have been identied also as possible forms of
metalmodier interaction and can be involved in ED.
In a recent study the possible forms of adsorbed CD was given as shown
in Fig. 51.
469
Density functional theory (DFT) at the B3LYP/T(ON)DZP
level was used to model one-to-one reactant-modier interactions relevant
to the enantioselective hydrogenation of PPD and MP over platinum
catalysts In an other study
205
DFT calculations revealed that protonated
cinchonidine and 10,11-dihydrocinchonidine are more stable on Pt when
adopting the so-called QA-Open(4) conformation rather than the Open-(3)
conformation. Thus, the QA-Open conformations may have some role in
the enantioselective hydrogenation over modied Pt catalysts. The results of
these calculations are shown in Fig. 52.
8. Reaction mechanisms and related calculations
8.1 Introduction
In the rst approaches related to the enantioselective hydrogenation of
activated ketones over Pt-cinchona catalytic system mechanistic views de-
veloped earlier for Ni-tartaric acid catalyst system.
471
It also means that the
rst models were proposed without any solid knowledge about the reaction
mechanism, i.e., the proposed reaction mechanism and schemes were based
on pure presumption related to the knowledge accumulated in studies
over the Ni-tartaric acid system.
However, careful analysis of these two enantioselective hydrogenation
reactions shows denite dierences as follows: (i) mode of introduction of
the modier, (ii) amount of modiers, (iii) reaction rate, and (iv) reaction
temperature
In Ni/tartrate system the catalyst requires pre-modication under con-
ditions dierent from those used in the hydrogenation reaction. Contrary
to that the Pt/cinchona system the introduction of the chiral modier
Fig. 51 The adsorption modes of cinchonidine: (a) parallel p-bonded; (b) tilted p -bonded; (c)
a-H-abstracted quinolyl; (d) quinoline-N-lone pair. (Reproduced from ref. 469 with
permission)
Catalysis, 2010, 22, 144278 | 243
into the reaction mixture during racemic hydrogenation instantaneously
induces ED.
In the Pt/cinchona system the substrate/modier ratio is very high (in case
of KPL it is 276 000), but the optimum substrate/modier ratio strongly
depends on the type of substrate. In Ni/tartrate system this value is several
order lower.
In the Pt/cinchona system as it has already been discussed the cinchona
alkaloid induces not only enantio-dierentiation but a well-pronounced rate
acceleration. Contrary to that in the Ni/tartrate system the modier de-
creases the reactions rate. It has to be emphasized that the rate acceleration
eect has also been observed in homogeneous catalytic reactions in the
presence of cinchona alkaloids.
353
In Ni/tartrate system the reaction takes place at moderate temperature
above 60 1C, while the enantioselective hydrogenation of prochiral ketones
requires low temperature around 010 1C. High temperatures above 40 1C
are not favourable to get high ee values.
As it has been mentioned in a recent publication
301
two types of
mechanisms-modied catalyst,
58,265,455,472
and shielding eect
74
have been
proposed. Unfortunately, not all of the authors consider this way. Those
who accepted the modied catalyst model (we shall call it surface
Fig. 52 Side and top views of the RI-BP86/SV(P) optimized Open(3) and QA-Open(4) con-
formations of cinchonidine, 10,11-dihydrocinchonidine, and their protonated counterparts on
the Pt38 cluster. The adsorption energies as dened in the text are given in parentheses (in
kJ mol
1
) (Reproduced from ref. 205 with permission)
244 | Catalysis, 2010, 22, 144278
modication model) did an enormous eort using various spectroscopic
methods and computational tools aimed to demonstrate that in fact only
one reaction scheme is working, i.e., both in aprotic and protic reaction
media the enantioselective hydrogenation reaction proceeds via the proto-
nated form of cinchonidine and the surface entities responsible for the
enantio-dierentiation step has a NH

O bond.
53
It also means that all
key events, i.e., the rate acceleration and enantio-dierentiation are ex-
clusively surface related phenomena.
Of course, the surface of Pt has a crucial role in this reaction. First or all
Pt provides landing sites for all participants in the given reaction, i.e., both
actors and spectators can land and react on the Pt sites. The question is
what of these surface induced interactions shall have a direct contribution
into the rate acceleration and enantio-dierentiation steps.
8.2 The surface modication model
The surface modication concept was rst suggested in early nineties, when
the number of publications in this area was very scarce. The distinction
between modied and unmodied sites over platinum was done by
Blaser and coworkers.
63
These terms have been widely accepted and used by
those who believe in the surface modication concept. The above dis-
tinction was formulated into a kinetic equation describing the ligand ac-
celeration phenomenon.
58
It has to be mentioned that in the above study
no mechanistic views were given just a very simple reaction scheme. Ac-
cording to this scheme enantioselective hydrogenation takes place over
modied sites, while racemic hydrogenation over unmodied sites.
This model gives a relatively good correlation between rate and ee values,
but it does not explain the variation of the ee values with the concentration
of the substrate.
The rst mechanistic view or scheme was given by Wells and coworkers in
early nineties (template model).
65,228
According to this the enantio-dif-
ferentiating sites are created by an ordered layer of the alkaloid with the
formation of a chiral pocket, i.e., a free room between adsorbed chiral
entities, where the enantio-dierentiation can take place. However, their
concept was not supported by surface spectroscopic methods
446
and the
original idea was withdrawn
45
very soon and a new idea based on the in-
volvement of the half-hydrogenated form of a-keto ester in the enantio-dif-
ferentiation step was proposed by the same research group.
472
It has to be
emphasized again that this new idea was suggested without any experi-
mental prove or evidence.
The fact that in acetic acid the enantioselective hydrogenation of alkyl
pyruvates takes place with higher rates and higher enantioselectivity than in
aprotic solvents the original idea given by Wells and coworkers was further
extended to the involvement of the protonated form of cinchonidine.
49
In
this model the quinuclidine nitrogen atom is protonated and the substrate is
still in its original state, maintaining the double bond character of the
carbonyl group. Later on this model was accepted as a general one even in
the absence of acids.
53
Baiker and coworkers have published several
experimental
85,97
and theoretical papers
314,430,442
trying to convince the
Catalysis, 2010, 22, 144278 | 245
readers that in the presence of cinchona alkaloids the atomic hydrogen is
spontaneously ionized with the formation protonated form of alkaloid.
There is a general view that the hydrogen-bonding interactions can trigger
for rate acceleration.
359,456
8.3 Shielding eect model
83
8.3.1 The principle of chemical shielding.
183
The basis for this approach
is the shielding eect (SE) known in organic chemistry. If a prochiral moiety
is preferentially shielded its further reaction can take place only from its
unshielded site resulting in an ED. A chiral template molecule can induce
SE in a similar way, i.e. it preferentially interacts with one of the prochiral
sites of the substrate leaving the unshielded site free for the reaction.
Intramolecular steric shielding of an aketo ester moiety has been ob-
served resulting in enantio-dierentiation in the hydrogenation of the
a-keto group.
473
ED was observed only in the presence of large aromatic
substituent, such as naphthyl, and it was completely lost if it was substituted
for a phenyl one. Based on this nding the ED was attributed to the SE
induced by the large aromatic moiety. Similar phenomena was also de-
scribed for the hydrogenation of an a,b- unsaturated ester moiety.
474
The
above two examples are shown in Fig. 53. Additional examples for chemical
shielding can be found elsewhere.
475,476
8.3.2 Application of the principle of chemical shielding to the Oritos
reaction.
83,183
Both reacting groups shown in Fig. 53 have a common fea-
ture, namely a conjugated double bond system. This feature is also char-
acteristic for most of the substrates what can enantio-selectively be
hydrogenated in the presence of cinchona-Pt or cinchona- Pd catalyst
477
systems.
On the other hand it was also shown that in the hydrogenation of EtPy
over Pt/Al
2
O
3
catalyst in the presence of new types of modiers (derivatives
of 2-1-pyrrolidinyl)-1-naphthyl)ethanol) the ED was completely lost if the
naphthyl ring was replaced by phenyl or pyridyl one.
60
It should also be
mentioned that in the hydrogenation of a-keto esters over CD-Pt/Al
2
O
3
R = Me, Et, Ph
OAc
O O
O R
O
CO
2
Me
O
CH
2
O
O
OAc
O O
R
CO
2
Me
Fig. 53 Intermolecular chemical shielding in the involvement of a-keto ester and a,b-un-
saturated ester. (Reproduced from refs. 475 and 476 with permission)
246 | Catalysis, 2010, 22, 144278
catalysts the ED was partially or fully lost if the quinoline ring of CD was
partially or fully hydrogenated.
64
If the key pp interactions given in Fig. 53 are compared with results
obtained in the enantioselective heterogeneous hydrogenation experiments
using cinchona-Pt systems the following very important elements of simi-
larity can be found: (i) ED can only be observed in the presence of large
aromatic shielding groups; (ii) the reactive prochiral group (both the keto
carbonyl and the C
Q
C double bond) is activated by an electron with-
drawing carbonyl group; (iii) the prochiral keto carbonyl group in most of
the activated ketones is in a conjugation with the adjacent carbonyl group
(or with the aromatic ring in TFA as it was shown earlier).
461
As emerges from these comparisons the presence of a large aromatic
substituents in the modier and a conjugated double bond system in the
substrate should play an important role to induce ED in these asymmetric
hydrogenation reactions, i.e. these are the key elements responsible for the
substrate specicity.
It has to be added that the shielding eect model suggest that substrate
modier interactions responsible for the ED take place in the liquid phase
and not on the Pt sites. The term substrate-modier interaction in liquid
phase was also mentioned by other authors. The substrate-modier
interaction exists, according to circular dichroism, in solution, probably in
the form of aggregates.
68
Similar views were given in another study.
221
It
has also been suggested that for some substrates, the solvent is involved in
the substratemodier interaction.
478
It has been suggested that the OH
group of the alkaloid should be involved in the substratemodier inter-
action which more likely occurs in the liquid phase.
479
8.4 Character of substrate modier interaction
In a recent review it has been admitted that in the absence of reliable ex-
perimental evidence, most mechanistic ideas are based on assumptions and
(at best) calculations. In most cases, the models assume two interactions
between the amine type modier and the ketone: an NHO
52,77,458,480,481
or N-C type attractive interaction
67,412,482
and a second attractive or re-
pulsive interaction that directs the adsorption of the ketone on Pt.
52,483
In the following section we shall follow the above consideration, i.e., we
shall distinguish electrophilic and nucleophilic interactions between the
substrate and the modier. It has to be emphasized that all existing models
postulate 1:1 type interactions between CD and the substrate. Barto k et al.
451
and Augustine et al.
371
proposed that not only the quinuclidine N, but also
the OH function of CD would be involved in the interactions. However this
view can be questioned as neither the methylation nor the removal of the OH
group in CD hinders the enantio-selection in the hydrogenation of EtPy.
57
The rst attempt aimed to elucidate the character of substrate-modier
interactions was done in an early study
458
related to the investigation of
interaction between MePy with NH
3
and NH
4

. In this study the ammonia

part represented the quinuclidine nitrogen of CD. The results indicated that
MePy can interact with both NH
3
and NH
4

and the electrophilic inter-

action is more favourable than the nucleophilic one. However, the
Catalysis, 2010, 22, 144278 | 247
nucleophilic interaction provided interesting result, namely the reaction
pocket of MePy is located between the two carbonyl groups. This nding
indicated that under condition of enantioselective hydrogenation both
carbonyl groups are activated. Consequently, if the enantioselective hy-
drogenation of EtPy is performed in methanol trans-esterication reaction
can take place. This has been proved experimentally.
307
In the next approaches two types of interactions were modelled, namely the
Baikers group focused on the electrophilic interaction between the half-
hydrogenated substrate and CD.
53,74,457,484
In our group, based on kinetic
results over cinchonidine-Pt/Al
2
O
3
, and the proposed shielding eect model
the nucleophilic interaction between the modier and substrate was favored.
69
8.4.1 Electrophilic interaction. In the rst theoretical study related to the
substrate-modier interaction the formation of a week complex between
protonated CD and MePy methyl pyruvate was investigated.
74
In this study
molecular mechanics and AM1 semi-empirical methods were used. The cal-
culated surface complex bifurcated electrophilic interaction between the pro-
tonated quinuclidine and the keto carbonyl group was considered. The results
revealed that adsorption of the complex leading to (R)-methyl lactate is more
favorable than that of the corresponding system yielding (S)-methyl lactate.
In another study ab initio calculations were used to study the interaction
between protonated amines (NH
3
, (CH
3
)
3
N and quinuclidine) and methyl
pyruvate (MP), as well as between protonated MP and these amines.
481
Based on results it has been suggested that interactions mediated by a
proton between the MP and the alkaloid are the main driving force leading
to enantiodierentiation in the hydrogenation of a-ketoesters. MP interacts
with protonated amines preferentially in the s-cis conformation, with a
proton making two hydrogen bonds to the carbonyl oxygens. This proton
may be transferred to MP, forming a new complex in which the amines are
bonded to the protonated MP. The last complex is approximately
10 kcal mol
1
less stable than the rst one. However, this energy dierence
decreases to approximately 5 kcal mol
1
when solvent eects are included.
Characteristic feature of these models is that both in the absence and
presence of acid in the key reaction intermediate the electrophilic interaction
prevails with the involvement of NHO or NH

O bonds. This interaction

can be either monodentate or bidentate (bifurcated) as shown in Figs. 54.
Fig. 54 Schematic representation of mechanistic models suggested by Baiker and co-workers;
A: monodentate interaction;
49,98
B: monodentate interaction;
338
C: bidentate interaction.
338
(Reproduced from refs. 49, 98, 338 with permission)
248 | Catalysis, 2010, 22, 144278
The key issue in this model the adsorption of the chrial modier with its
quinoline ring parallel to the Pt surface as it has already been discussed in
Section 6. Several adsorbed conformations of CD were calculated.
442
Sequence of events on the Pt surface related to the protonation of qui-
nuclidine nitrogen is shown in Fig. 55, 56, while the calculated substrate-
modier complex and its interaction with the Pt surface are given in Fig. 57.
In this respect the waging motion of the quinuclidine part has been em-
phasized. The overall route for proton transfer from protonated CD to
adsorbed substrate supported by DFT calculations and in situ ATR-IR
spectroscopy is shown in Fig. 55. It has to be added that in the recent
publication of this group it was found that the most stable intermediate
complex forms without adsorption of the substrate.
103
We have serious objection against the exclusiveness of the electrophilic
interaction in the Oritos reaction. Assuming the scheme given in Fig. 55 one
would suggest that not only the quinuclidine nitrogen of the cinchona al-
kaloid can be involved in the transformation of atomic hydrogen formed on
the Pt site to a protonated nitrogen base. All tertiary nitrogen bases should
have similar ability. Consequently, the hydrogen transfer in the presence of
an achiral tertiary amines (ATA) should result in a racemic product. Thus,
Fig. 55 Simplied scheme for the interaction of the quinuclidine N atom with the Pt-H system
and the subsequent transfer of the H to the adsorbed ketone. (Reproduced from ref. 372 with
permission)
Fig. 56 Hydrogen uptake of CD from a platinum surface. (Reproduced from ref. 98 with
permission)
Catalysis, 2010, 22, 144278 | 249
the simultaneous addition of cinchona alkaloids and ATAs should result in
a decrease in the ee values. However, our results discussed in Section 5.7.2
showed a completely opposite eect.
According to Figs. 5557 the key issues in the surface modication
model are as follows: (i) adsorption of the modier with its condensed
aromatic ring parallel to the Pt surface, (ii) stabilization of the modier in its
open form, (iii) adsorption of the substrate via its both carbonyl bonds in
re-phase, (iv) formation of a hydrogen bond between protonated alkaloid
and the substrate and (v) transfer of the proton to the substrate. The con-
densed aromatic ring is often called as anchoring site.
As it has already be mentioned earlier the chiral C8 and C9 carbon atoms
of the alkaloid play a vital role in the enantio-dierentiation, i.e. their
conformation determines the position of the chiral pocket located in
the neighbourhood of quinuclidine nitrogen. In addition the mode of
adsorption of the chiral modier (at or tilted) has a decisive role in
the ED step as it has been shown in the series of O-substituted derivatives of
CD.
435
In a recent study the role of the modier structure in the reactant-modier
interactions relevant to the heterogeneous enantioselective hydrogenation
of PPD and MePy) was studied using DFT calculations.
205
Two protonated
modiers, CD and MeOCD, in dierent conformations were considered.
So-called bifurcated and cyclic hydrogen-bonded reactant-modier inter-
action modes were investigated. The results showed that only the bifurcated
reactant-modier(Open3) complexes were found to be relevant in the de-
termination of enantioselectivity. Analysis of the orbital stabilization im-
plies a notable decrease in the enantiomeric excess of the main
hydrogenation product of PPD when CD is replaced with MeOCD. On the
other hand, according to the theoretical calculations the hydrogenation of
MP over modied Pt is expected to yield an equal ee values in the presence
Fig. 57 Proposed relative surface structures of adsorbed CD and MePy on a Pt31 cluster
(DFT calculations), which allow an H-bonding interaction (not shown). (Reproduced from ref.
389 with permission)
250 | Catalysis, 2010, 22, 144278
of both modiers. DFT calculations revealed that protonated CD and
DHCD are more stable on Pt when adopting the so-called QA-Open (4)
conformation rather than the Open (3) conformation. These conformations
are shown in Fig. 58. Thus, the QA-Open conformations may have some
role in the enantioselective hydrogenation over modied Pt catalysts. The
QA-Open (4) conformation of a modier is adsorbed on the surface via both
its quinoline and quinuclidine moieties, and a reactant may interact sim-
ultaneously with the protonated quinuclidine nitrogen and the functional
group at the C(9) position of the modier.
The interaction between KPL (Pro-(R) conformation) and adsorbed
o-PyOCD over Pt surface was also modelled.
372
In this case both the qui-
nuclidine and pyridine moieties in o-PyOCD were protonated. At the end of
the simulation the hydrogen was transferred to the keto-carbonyl group of
ketopantolactone, therefore forming a semi-hydrogenated surface species,
while protonated o-pyridyl group coordinated to the ester carbonyl group
as shown in Fig. 59.
Modelling studies revealed also that there is no mode of docking of any
low energy conformation of epiquinidine with pyruvate ester that could lead
to selective enantioface adsorption of the latter.
485
Fig. 58 Calculated stabilized structure of CD over Pt in Open (3) and QA-Open (4). (Re-
produced from ref. 204 with permission)
Fig. 59 Interaction of adsorbed o-PyOCD in the most stable position of the o-pyridoxy
moiety, with KPL adsorbed in a Pro-(R) conformation. (Reproduced from ref. 372 with
permission)
Catalysis, 2010, 22, 144278 | 251
Recently a new idea was suggested assuming a H-bond between the
quinuclidine N of CD and the ester carbonyl or triuoromethyl group of the
substrate and a second, monodentate or bidentate H-bond involving two or
one aromatic H atoms of the modier at 5
/
- and 6
/
-positions and the O atom
of the ketocarbonyl group.
72,316,483
In addition, it was suggested that similar interactions might exist for all
activated ketones. General principles of this type of interactions are shown
in Fig. 60.
This type of interactions has also been proposed in recent studies by the
Barto ks goup
384,486
(see Fig. 61). However, in this case the character of
substrate modier interaction is nucleophilic.
However, these models strongly contradicts to experimental ndings as
ring-substituted cinchona derivatives, such as QN and QD containing a
methoxy group in the 6
/
-position, are highly eective modiers in the hy-
drogenation of activated ketones (see Section 3.1). Consequently, the
interaction of the substrate molecule with the proton of the quinoline ring is
not a prerequisite for enantio-dierentiation.
In addition, the proposed interaction of the keto group with the aromatic
hydrogen (see Fig. 60 cannot give any reasonable explanation for the ac-
tivation of the keto group resulting in rate acceleration.
Based on ESI-MS spectra of EtPy, DHCD and EtPy-DHCD mixtures
interesting equilibria (see Fig. 62) were suggested by Barto k et al.
195
In this
respect it interesting to note that the semi-ketal formed between the CD and
EtPy was also evidenced in another study.
109
Fig. 60 Two-point H-bonding model suggested by McBreen et al. A: interaction between
protonated CD and MePy, B: interaction between protonated CD and triuoroacetophenone
(TFA). (Reproduced from refs. 316 and 483 with permission)
Fig. 61 Hydrogen bounded substrate modier complex. (Reproduced from ref. 487 with
permission)
252 | Catalysis, 2010, 22, 144278
8.4.2 Nucleophilic interaction. Nucleophilic interaction between
the substrate and the modier has been suggested by dierent
authors.
83,84,369,412,458,488
In an early mechanistic view
67
it was proposed
that the hydrogenation of pyruvate over either modied or unmodied
platinum takes place on the more coordinatively unsaturated corner
atoms or adatoms on the platinum surface. In their further study
369
it was suggested that the substrate-modier complex (association) in-
corporates some interaction between the quinuclidine nitrogen and the
ketone carbonyl group of the pyruvate. One such interaction is between
the electron pair on the nitrogen and the electron decient carbon atom
of the carbonyl group, which, as discussed above would account for the
observed increase in hydrogenation rate in these reactions. The involve-
ment of coordinatively unsaturated platinum was also suggested by the
Barto ks group.
486,487
The shielding eect model is also based on the nucleophilic inter-
actions. The key issue of this model is the involvement of closed conformer
of CD in the substrate modier interaction. The character of these inter-
actions will be discussed in the next section. Upon investigating enantio-
selective hydrogenation of KPL in the presence of b-ICN Barto k an
coworkers suggested two possible forms of surface complex representing
either electrophilic or nucleophilic interaction as shown in the next scheme
(see Fig. 63.) The inversion of the ee was attributed to the change of the
reaction mechanism from nucleophilic to electrophilic one.
It was also suggested that in the hydrogenation of activated ketones in the
presence of cinchona-Pt catalysts proceeds through nucleophilic addition
of a cinchona alkaloid to the ketone to form a zwitterionic adduct, which is
then hydrogenolyzed with inversion of conguration. The enantioselectivity
of the reaction is determined by the relative stabilities of the diastereomeric
adducts adsorbed on platinum.
412
However, this mechanism has been
ruled out as it was pointed out that this approach does not take into account
steric hindrance against the interaction of the amine modier with cyclic
ketones and further critical point is the regioselectivity of the hydro-
genolysis of the hypothetical zwitterionic intermediate.
413
+
N
H
OH
N
C
COOEt
OH
Me
+
N
H
OH
N
H
C
C
OEt
Me
O
O
N
O
H
C COOEt
Me
OH
N
H
+
Fig. 62 Possible form of adducts between DHCH and EtPy (Reproduced from ref. 195 with
permission)
Catalysis, 2010, 22, 144278 | 253
When the inversion of enantioselectivity in the presence of b-ICNs was
investigated the formation of dierent nucleophilic adducts was proposed as
shown in Fig. 64.
8.4.3 Character of interactions in the shielding eect model. Cinchona
alkaloids (CA) have two rotational axises, which allow to rotate either the
quinoline ring around the C(1)
/
-C(9) axis or the quinuclidine ring around
the C(9)-C(8) axis (see Sections 2.1 and 3.1). Molecular mechanics and
ab initio calculations performed by dierent groups that in liquid phase CA
can exist at least in three dierent stable forms. We suggest that the closed
form of the modier is required both for the RA and the ED. Only the
closed form of CA can provide the cooperative required for ED.
The possible arrangements of the substrate and the modier in the shiel-
ded complex are shown in Fig. 65. In the hydrogenation of pyruvate esters
the complex shown in Fig. 65A would result in the expected (R)-lactate
ester, while the complex given in Fig. 65B would give the corresponding
(S)-product. The major dierence between the (R) and (S) complexes is the
mode of interaction between the lone pair of electrons of the quinuclidine
Fig. 63 Enantioselective hydrogenation of KPL in the presence of b-ICN. (Reproduced from
ref. 419 with permission)
Fig. 64 The proposed structures of adduct complexes of b-ICN (B) and CD (C) with esters of
phenylglyoxylic acids. (Reproduced from ref. 486 with permission)
254 | Catalysis, 2010, 22, 144278
nitrogen and the keto carbonyl group. In complex (R), the directionality
489
of the nucleophilic attack by quinuclidine nitrogen towards the keto car-
bonyl group is very favourable to increase the reactivity of the keto carbonyl
group because the electron- rich quinuclidine nitrogen and the keto-oxygen
of the substrate are on the opposite sides of the keto carbon atom. According
to the orbital steering theory,
490
a proper reaction window or reaction cone
can result in perturbation of the reacting group.
In our case the proper reaction window is determined by the relative
position of the quinuclidine N1, pyruvate C2 and O3 atoms, i.e., by direct
N1C2 interaction as shown in Fig. 66. In case of proper reaction window
the overall reactivity of the keto group should increase. We suggest that the
above perturbation leads to a pronounced rate increase both in the hy-
drogenation reaction and the formation of by-products, such as semi-ketal,
transesterication and deuterium exchange products
84,289,307
Thus, in
complex (R), the favourable directionality promotes the perturbation of the
keto carbonyl group, resulting in the observed RA. Contrary to that in
complex (S), due to the misalignment of the interacting groups, i.e., due to
the lack of direct N1C2 interaction, no RA can be expected, consequently,
the hydrogenation of (S). complex is not accelerated.
Those who favour the modier-surface or modier-metal interactions
suggest that the quinoline ring is involved in the adsorption of the modier
to the metal.
45,82,214
Contrary to that we suggest that the quinoline ring is
involved in the p-p interaction with the substrate via p-p stacking.
83,84
We
suggest that the RA is a cooperative eect with the involvement of both the
quinuclidine nitrogen and the quinoline ring (Fig. 66).
Monte-Carlo simulation method was used to investigate the interaction
of the [methyl pyruvate CD]
closed
complex with Pt (111). surface. The result
shown in Fig. 67 indicates that the shielded complex retains its entity even
after adsorption.
The above gure gives a good presentation of the SE provided by the
large aromatic moiety. With respect to the explanation related to the use of
small Pt colloids we should like to refer to results of our calculations (Monte
Carlo simulation). These results given in Fig. 68 shows that the closed
[substrate modier] complex can be accommodated at the Pt(111) face
even of a small Pt nanocluster.
244
When the shielding eect model was proposed it was also mentioned
that in the enantioselective hydrogenation of activated ketones cinchona
alkaloids behave like an enzyme.
93
This view has recently been emphasized
without reference to our original idea.
103
Fig. 65 Shielded [methyl pyruvate-CDclosed] complexes. A favourable alignment;
B unfavorable alignment. (Reproduced from ref. 461 with permission)
Catalysis, 2010, 22, 144278 | 255
8.5 Pros and contras related to existing models
8.5.1 Surface modication model. The surface modication model
has been strongly altered since the introduction of the rst concept, i.e., the
division of Pt surface into modied and unmodied sites. According to the
generalized view the key issues in this model are as follows: (i) adsorption of
CD in its open (3) conformation via its quinoline ring parallel to the Pt
surface, (ii) conformational changes at the Pt surface to form quinuclidine
bonded CD, (iii) formation of protonated quinuclidine moiety, (iv) trans-
formation of the proton to the substrate to form half hydrogenated surface
species, and (v) direct addition of the second hydrogen form the Pt surface
to get the chiral keto-alcohol (see Fig. 57).
However, based on the discussion in this contribution we can emphasize
that this model was not able to give appropriate answer to the following
Fig. 66 A Simplied scheme for the [MePyCD
closed
] complex; B the reaction window for
the substratemodier interaction in [MePyCD
closed
] complex. (Reproduced from ref. 461
with permission)
Fig. 67 Monte-Carlo simulation of the adsorption of the [MePyCD]
closed
complex onto Pt
(111) surface. (Reproduced from ref. 83 with permission)
256 | Catalysis, 2010, 22, 144278
important observations: (i) rate acceleration (see Section 5.5.1), (ii) the
appearance of the initial transient period in the conversion-selectivity de-
pendencies (see Section 5.5.2); (iii) the inuence of ATAs (see Section 5.6.2),
(iv) the inuence of compounds with large aromatic ring (see Section 5.6.3),
(v) the inuence of the modiers of the Pt and support (see Section 5.6.3),
(vi) the stability of nucleophilic [substrate modier] complex (see Section
6.1.1) in the presence of AcOH, (vii) high enantioselectivities over very small
Pt nano-colloids (see Section 4.2.2).
Even if scheme shown in Fig. 55 is valid a simple question can be
raised? Why the adsorption and subsequent strong distortion of the
alkaloid at Pt surface is needed to pick up a proton from the Pt surface if it
could also be done without any preadsorption via quinuclidine N-Pt
interaction. Would not be it more logical and energetically more
favourable?
In this respect we have to address literature data related to the proto-
nation of pyridine and its analogs observed under high vacuum and low
temperatures.
491,492
These references were cited in several papers as a direct
proof related to surface reactions given in Fig. 55. However, it has to be
pointed out that none of the authors referred to experimental conditions
used in these earlier studies. It has to be emphasized that in refs. 492,493
results obtained under ultra-high vacuum were presented. The key experi-
ments were performed over Pt(110) surface under base pressure between
5 10
11
and 1 10
10
Torr and the temperature was kept between
100180 K. The intensities of the 3450 cm
1
EELS peak characteristic of
cation formation showed strong temperature dependence and above 180 K
it was hardly detected.
Consequently, there are many speculations related to this model. Finally,
it has to be added that this model does not take into account one of the
important issues that these alkaloids are used by organic chemist for many
years to induce ED or chiral separation.
Fig. 68 Monte-Carlo simulation of the adsorption of the [MePyCD]
closed
complex onto the
Pt(111) surface of small Pt colloid. (Reproduced from ref. 244 with permission)
Catalysis, 2010, 22, 144278 | 257
8.5.2 Shielding eect model (SEM). The shielding eect model can
explain the following experimental ndings:
74,83
(i) substrate specicity), (ii)
inversion of enantioselectivity for enantiopairs CD-CN, QN-QD, (iii) rate
acceleration, (iv) the MI character of the ee-conversion dependencies (v) the
loss of ee in case of replacing the quinoline ring for pyridyl or phenyl, (vi)
formation of transesterication and deuterium exchange products; (vii) ef-
fectiveness of very small Pt colloids, (viii) the role of achiral tertiary
amines, (viii) the need for of large aromatic moieties in cinchona alkaloids
to induce ED.
The reaction network derived form the shielding eect model provided
kinetic equations what can describe the following kinetic events:
83
(i) rate
acceleration, (ii) increase the reaction rate at the initial period of the re-
action,
66
(iii) the the MI character of the ee-conversion dependencies.
The strongest conict with shielding eect model is the nding that
ICNs can also induce enantio-dierentiation. However, in this respect the
anomalous behaviour of these rigid alkaloids
361
has to be mentioned. The
behaviour of these alkaloids needs further elucidation and probably the use
of more pure alkaloids. In this respect the lack of rate acceleration in the
presence of a-ICN and the inversion of ee in the presence of b-ICN have to
be mentioned. Another unclear issue is that shielding eect model requires
nucleophilic interaction between the substrate and the modier, while in the
presence of AcOH electrophilic interactions interaction prevails. Although
in this relation recent NMR results has to be emphasized, what clearly in-
dicated that in case of KPL even in the presence of AcOH the nucleophilic
substrate-modier adduct can be formed.
419
Finally, we have to admit that the shielding eect model was not
supported by the scientic community in the eld of heterogeneous cata-
lysis. This fact can be attributed to the deciency of the model. However, it
cannot be excluded that due to the strong inuence of those who favour the
surface modication model, the scientic community just simple followed
the main stream without any criticism.
9. Conclusions
In this review an attempt was done to give a retrospective overview about
methods, approaches and results obtained in the last three decades in the
area of enantioselective hydrogenation of activated ketones. Both practical
and theoretical aspects were discussed. Characteristic feature of this review
is that the term chirally modied surface was not really used.
Although tremendous eort has been done so far to elucidate the pecu-
liarities of this reaction there are still several open questions related to the
substrate-modier and substrate-modier-platinum interactions involved in
the enantio-dierentiation step.
It seems to us that starting from the beginning of early nineties there is a
permanent desire to demonstrate and prove that in the presence of cin-
chona-Pt catalyst system all interactions responsible for ED take place on
the Pt surface. In addition, last years the mainstream concentrated to prove
that the protonated quinuclidine moiety is involved in the rst step of
hydrogen transfer, with the involvement of adsorbed form of the alkaloid by
258 | Catalysis, 2010, 22, 144278
its quinuclidine moiety and adsorbed hydrogen, i.e., the key mechanism in
aprotic and protic solvents is the same. We consider that this mechanistic
view is too general and in addition it is articial and far-fetched. This view
neglects series of experimental evidences obtained by dierent research
groups. Let us remind the reader only three of these neglecting facts:
Use of Pt colloid. As it was mentioned in Section 4.2.2 high rates and high
enantioselectivities were obtained upon using very small Pt colloids. In none
of the reviews published so far by catalytic scientists this anomalous ndings
were not really discussed. However, in a recent review written by organic
chemists it was emphasized that upon using Pt colloids in enantioselective
hydrogenation of MePy in the presence of CD the smallest Pt clusters gave
the best results despite having no at surface large enough for the adsorption
of cinchonidine.
493
Addition of quinoline. In this respect one of the earlier results has also to
be mentioned.
345
In this study it was shown that the addition of quinoline to
the reaction mixture at very low concentration (0.1 g/L) increased both the
rate and the ee values. The authors attributed this observation to some sort
of base eect. Unfortunately, due to the dominance of the general view, i.e.
the formation of chirally modied surfaces this result has completely been
forgotten and in the last eighteen years it was only very seldom cited. In this
respect we should like to refer to our results discussed in Section 5.6.2).
These results clearly indicated that the addition of quinoline has no negative
eect either on the reaction rate and the ee values. Based on these ndings
the scheme shown in Fig. 69 has been suggested.
Fig. 69 shows four dierent situations described in ref. 402. A represents
the racemic hydrogenation in the absence of any additive, where due to the
poisoning eects of by-products the rate is controlled by free Pt sites left. B
corresponds to the situation when quinoline is added prior to the addition
of hydrogen. In this case the poisoning eect of by-products decreased re-
sulting in a rate increase in racemic hydrogenation. C represents the
enantioselective hydrogenation upon injecting CD, where the initial surface
coverages are identical to those established in case A.
Fig. 69 Surface coverages in the presence of quinoline added to the reaction mixture.
(Reproduced from ref. 402 with permission)
Catalysis, 2010, 22, 144278 | 259
After injection of CD instantaneous RA and MI type the ee conversion
dependencies are evidenced. D corresponds to the situation when cincho-
nidine is injected to surface B containing preadsorbed quinoline. In case D,
due to the established competition between CD and quinoline the Pt sites
are covered by both CD and quinoline. However, the net results are un-
expected, i.e., increased rate and increased ee. Consequently, these results
might indicate that the general view that strongly bonded to the platinum
CD via its quinoline ring needs some corrections.
Spectroscopic results in liquid phase. Both NMR
83,84,418,419
and Circular
Dichorism
68,93
spectroscopic results clearly indicated that there is a complex
formation between the substrates and cinchona alkaloids in the liquid
phase. These facts were completely neglected by the scientic community. In
this respect let us refer to a very recent results indicating that the nucleophilic
complex between KPL and b-ICN can exist even in the presence of AcOH.
The authors showed a nice dependence between the solution concentration
of the 1:1 substrate-modier complex and the enantioselectivity as shown in
Fig. 70. In addition it was shown that there is an excellent correlation be-
tween the ee values, the concentration of the 1:1 substrate/modier complex
and the amount of AcOH added as shown in Fig. 71.
It is known that in the enantioselective hydrogenation of KPL all polar
solvents have a negative eect.
76
Results presented in ref. 419 (see Figs. 2
and 3) denitely show the importance of the complex formation in the liquid
phase. However, even in the light of these unambiguous evidences the
authors of this study were not brave enough as they made the following
remark: we did not doubt the role of the protonated cinchona despite the
fact that the spectroscopy data published previously, obtained under the
conditions of the Orito reaction in toluene, are not totally convincing in
terms of protonation of the N atom of quinuclidine.
We believe that in the near future further high quality and unambiguous
experimental data will be obtained related to the character of substrate-
modier interactions as well to the formation of substrate-modier complex
at the Pt surface. We also hope that those who have dierent views on the
mechanism of Oritos reaction in the future will get more wide open plat-
forms to publish their results and ideas.
Fig. 70 Dependence of the ee of the concentration of substrate-modier complex in the liquid
phase. (Reproduced from ref. 419 with permission)
260 | Catalysis, 2010, 22, 144278
Abbreviations used
AcOH acetic acid
AS anchoring sites
ATA achiral tertiary amine
ATR-IR attenuated total reection infrared (spectroscopy)
CD cinchonidine
CI chiral induction
CN cinchonine
De diastereomeric excess
DHCD 10,11-dihydrocinchonidine
DHCN 10,11-dihydrocinchonine
DRIFT diuse reectance FT infrared
EBF ethyl benzoylformate
ECD enantioselectivityconversion dependencies
ED enantio-dierentiation
ee enantiomeric excess (%)
EOG diethyl 2-oxoglutarate
EOPB ethyl-2-oxo-4-phenyl butirate
Et ethyl
EtLa ethyl lactate
Etpy ethyl pyruvate
HHCD hexahydrocinchonidine
HRTEM high-resolution transmission electron microscopy
ICN isocinchonine
IR infrared spectroscopy
ITP initial transient period
KPL ketopantolactone
M metal
M/S modiersubstrate molar ratio
MBF methyl benzoylformate
Me methyl
MeLa methyl lactate
Fig. 71 Comparison of the total concentration of the 1:1 b-ICNKPL complexes measured by
NMR (circles) with the enantioselectivities (diamonds) obtained at identical AcOH
(CD
3
COOD for the NMR) concentrations (logarithmic scale). (Reproduced from ref. 419 with
permission)
Catalysis, 2010, 22, 144278 | 261
MeOCD O-methyl-cinchonidine
MeODHCD O-methyl-10,11-dihydrocinchonidine
MePy methyl pyruvate
MI monotonic increase
NED 1-naphthyl-1,2-ethanediol
NLP non-linear phenomena
PADA pyruvaldehyde dimethyl acetal
Ph phenyl
PhOCD O-phenyl-cinchonidine
PNEA pantoylnaphthylethylamine
PPD 1-phenyl-1,2-propanedione
PSC primary surface complex
Q quinoline
QD quinidine
QN quinine
QND quinuclidine
RA rate acceleration
RAIRS reection absorption infrared spectroscopy
RAIRS reection adsorption infrared spectra
RE rate enhancement
SBA stabilized bimetallic alloy
SERS surface-enhanced Raman scattering
STM scanning tunnelling microscopy
TEA triethylamine
TFA triuoroacetic acid
TFAP triuroacetophenone
TMS trimethylsilane
TOF turnover frequency (h
1
)
Y yield (%)
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100, 2159.
278 | Catalysis, 2010, 22, 144278
Gold catalysis in organic synthesis and
material science
Cristina Della Pina,
a
Ermelinda Falletta
a
and Michele Rossi
a
DOI: 10.1039/9781847559630-00279
1. Introduction
One of the most exciting and unforeseen developments of the chemical
research has been the recent application of gold in catalysis. In fact, this
metal has become an important tool in organic synthesis several years after
the rst reports on ethyne hydrochlorination and CO oxidation and now it
is widely employed in many fundamental catalytic processes as oxidation,
hydrogenation and coupling reactions.
14
New applications of gold have
been also proposed for commercial syntheses by academic and industrial
researchers.
58
An ultimate project concerns an inorganic reaction, that is
the direct synthesis of hydrogen peroxide which has been developed by the
impressive work of Hutchings group.
13
Strategic application of gold is the selective transformation of renewable
biological resources, a key importance task for balancing the CO
2
cycle. In
particular, valuable oxygenated compounds can be produced as new
building blocks for further transformation.
The catalytic conversion of carbohydrates and alcohols to the corres-
ponding carbonylic or carboxylic compounds still maintains an attracting
power, being the products employed as chemical intermediates and high
value components for perfumery, food and pharmaceutical industry.
18
Selective oxidations using the eco-friendly air or pure dioxygen, as the
oxidant, and supported metals as catalysts, are earning a general praise:
they represent the promising response to the environmental restrictions for
the progressive shutdown of the traditional methods, causing undesired and
toxic by-products. Gold catalysis enjoyed an important progress owing to
the rapid advancement of nanotechnology and nanoscience, thus resulting
in new applications for commercial syntheses by both academic and
industrial research worlds.
912
The strong scientic appeal towards the
precious metal can be easily realized considering its peculiar property to
discriminate inside chemical groups and geometrical positions,
1315
and its
chemical stability, strictly related to the unique features of gold itself. The
kinetic studies clearly show how much the activity is highly dependent on
the size of metallic gold particles. In particular, many investigations on the
liquid-phase oxidation of polyols, alcohols, carbohydrates demonstrate that
only small gold particles are catalytically active,
16,17
which is in line with the
behaviour of gold particles employed in the gas-phase oxidation of carbon
monoxide.
1
a
Department of Chimica Inorganica, Metallorganica e Analitica L. Malatesta e ISTM-CNR,
Universita` degli Studi di Milano, Via Venezian 21 20133, Milano, Italy
Catalysis, 2010, 22, 279317 | 279
c
The Royal Society of Chemistry 2010
2. Gold catalysis in organic synthesis
2.1 Selective oxidation of alcohols
The reason why the oxidation of alcohols represents an attractive topic
mainly lies in the wide diusion of hydroxy-compounds, their easy avail-
ability from renewable sources and the protable employment of their de-
rivatives as chemicals for organic synthesis. A great number of recent
reviews deals with the catalytic oxidation of the COH group, outlining the
evolution of the catalytic system from conventional Pt and Pd to more
sophisticated Pt-Pd-Bi polymetallic systems, in order to increase selectivity
and drop the deactivation process.
18,19
A novel generation of catalysts for alcohols and polyols oxidation is
represented by supported gold: its application leads to a dramatic im-
provement in selectivity and stability, thus fomenting an exciting com-
petition among ruthenium, platinum, palladium catalysts.
13,20
Corma and
Hutchings research groups are quite active in this eld, resulting in fun-
damental achievements which have added a key progress in this topic.
2,3
In
particular, Hutchings et al.
21
have shown the advantage in using continuous
ow reactors for the oxidation of glycerol under mild conditions: both
monolith and meso-scale structured downow slurry bubble column designs
lead to an increment in the reaction rate and selectivity towards glyceric acid
over autoclave.
An ultimate method has now been proposed,
22
based on a gold-immo-
bilized microchannel ow reactor for the oxidation of alcohols with mo-
lecular oxygen: Kobayashi and co-workers have shown how the oxidation
of various alcohols proceeded easily to give the corresponding aldehydes
and ketones in good to excellent yields. No leaching of gold was observed
and the gold-immobilized capillary column could be continuously used for
at least four days without loss of activity. Probably, it is the rst example of
a microreactor that allowed full conversion of alcohols by aerobic oxidation
of alcohols in microchannels.
However, the rst systematic study on gold catalysis for selective
liquid phase oxidation has been performed at Milan University, with the
ambitious aim to nd a substitute for palladium, platinum and, particularly,
copper in the aerobic oxidation of the alcoholic group. The most chal-
lenging drawbacks to be overcome were metal leaching and scarce
selectivity of the traditional catalysts. The early experiments for testing
the activity of metal gold were disheartening: whereas bulk copper
quickly reacted with O
2
and ethane-1,2-diol in basic solution to produce
oxoethanoate- and formate-derivatives,
23
gold powder resulted totally inert
towards any transformation of the glycol. The high chemical stability of
bulk gold was overcome by discovering the new peculiarities of gold
nanoparticles and the logic of Scheme 1 was soon adopted also by
other dierent research groups for liquid and gas phase applications.
The favourite methods for preparing catalysts were co-precipitation, de-
position-precipitation and colloidal particles immobilisation. In our case,
nely dispersed gold supported on carbon by metal sol immobilisation
allowed to achieve an active and selective catalyst for liquid phase
oxidation.
280 | Catalysis, 2010, 22, 279317
2.2 Catalyst preparation
Ecient, carbon-supported gold catalysts for liquid phase oxidation can be
prepared starting from colloidal dispersions containing metallic gold (sol).
Dierently sized gold particles, in the range 210 nm, could be obtained by
reducing chloroauric acid with NaBH
4
in the presence of stabilizing agents as
polyvinylalcohol (PVA), polyvinylpyrrolidone (PVP) and tetrahydroxymethyl-
phosphonium chloride (THMP), glucose. Au (III) concentration is a key
factor for tuning particle size. Either high resolution electron transmission
microscopy (HR-TEM) or X-ray diraction (XRD) techniques are applied for
particle size determination after immobilisation of the sol on a useful sup-
porting material, as copper grid and carbon powder. TEM shows the direct
image of the metal particles, whereas Scherrer equation allows the calculation
of the mean diameter from the half height width of the XRD pattern.
Colloidal gold nanoparticles were generally collected on two types of
activated carbons: for catalytic tests, Au was immobilised on a coconut
derived carbon powder (A
S
=1300 m
2
g
1
from Camel) at a level of 0.2
0.8% (w/w), which was chosen for the low sulphur content, while for XRD
determination 12% Au (w/w) was contacted with a pyrolytic carbon
powder (A
S
=254 m
2
g
1
from Cabot), which was selected for its fast ad-
sorption property. The modulation of gold clusters size was achieved using
initial solutions ranging from 25 mg L
1
(small particles) to 500 mg L
1
(large particles) of gold.
2.3 Oxidation of diols
Aliphatic 1,2 diols can be oxidised to the corresponding monocarboxylates
with O
2
under low pressure (13 bar) in the presence of the stoichiometric
Kinetics, Mechanism, Models Nanotechnologies
High dispersion
Particle size
Metal-support interaction
Nature and role of the support
Gold
Long life but low activity metal
Scheme 1 Tailoring ecient gold catalysts.
Catalysis, 2010, 22, 279317 | 281
amount of NaOH. Supported gold particles were shown to be the best
catalytic system, by comparing with Pd and Pt metals (Table 1).
13,24
Developing the sol immobilisation technique and improving our ability in
preparing small colloidal gold particles, gold catalyst activity could be
grown from a few hundred TOF units up to 3500 h
1
in the case of gly-
colate and 2000 h
1
for lactate. Selectivity at 100% conversion was raised
to surprisingly high values, dierently from the lower performance of Pd
and Pt catalysts.
Regarding phenylethane-1,2-diol oxidation, however, a worse selectivity
scenario appeared, probably due to a strong induction eect of the phenyl
group: two abundant by-products, namely benzoate and phenylglyoxylate,
were detected together with the expected mandelate, in basic conditions
(Scheme 2).
An accurate comprehension of the experimental results can not set aside
the alkali catalysed keto-enolic equilibrium c and internal Cannizzaro-type
reaction f, reported in Scheme 3.
The original gold selectivity could be evaluated by dropping the reaction
pH to the value 7 when reactions c and f, together with the overoxidation of
mandelate, were inhibited.
Table 1 Catalytic activity and selectivity of carbon dispersed metals in the oxidation of vicinal
diols
HO
OH
Au/C Pd/C Pt/C
TOF (h
1
) 3500 500 475
Selectivity (%) 98 77 71
OH
OH
Au/C Pd/C Pt/C
TOF (h
1
) 2000 720 650
Selectivity (%) 99 90 89
+ O
2
Au/C
NaOH
+
By-products
COO
OH
OH
OH
-
By-products
COO
O
COO
+
-
-
Scheme 2 Reaction products detected during the oxidation of phenylethane-1,2-diol (P) with
Au/C catalyst. [P]=0.4 M; P/Au=500; P/NaOH=1; T=343 K.
282 | Catalysis, 2010, 22, 279317
Scheme 4 shows that the formation of mandelate supports path a, due to
the oxidation at the terminal carbon atom, while phenylglyoxylate and
benzoate underpin path b favouring the oxidation at the internal carbon.
The oxidation observed under these conditions concerned mainly the
secondary alcoholic function, 62.5%, followed by the primary one, 45%.
The selectivity towards mandelate can be increased by promoting reactions
c and f. Table 2 visualizes how we were able to improve the selectivity from
45 to 83% by increasing alkali concentration and temperature.
25
Non-vicinal glycols can also undergo selective oxidation: however, Table 3
shows the worse reactivity of 1,3 propanediol and diethyleneglycol oxidation
OH
OH
O
OH
OH
O
O
O
OH
O
O
O
O
O
-
-
O
O
-
a
b
Scheme 4 Reaction pathway of phenylethane-1,2-diol oxidation at pH 7.
OH
OH
O
OH
OH
O
O
O
OH
O
O
O
O
O
-
-
O
O
-
a
b
+
HCO
3
-
c
e
d
f
g
h
Scheme 3 Reaction pathway of phenylethane-1,2-diol oxidation in basic solution.
Table 2 Optimization of phenylethane-1,2-diol (PED) oxidation for
producing mandelate with Au/C catalyst
NaOH/PED T (K) Conversion % Selectivity %
1 343 52 45
2 343 100 60
2 363 100 70
4 363 100 83
Catalysis, 2010, 22, 279317 | 283
with respect to vicinal diols reported in Table 1, while the selectivity to
monocarboxylates maintains always high values.
The great interest in the synthesis of dicarboxylic acids has suggested a
thorough study on the oxidation of diethyleneglycol, in order to force the
reaction towards the double oxidation, by changing the amount of alkali,
nature of catalyst and temperature. The optimization of the experimental
conditions at O
2
pressure 3 bar and substrate: Au ratio 1000 led to the
production of monocarboxylate by gold on carbon, whereas gold on titania
resulted in 45% of the diacarboxylate in the presence of 2 mol of NaOH at
363 K (Table 4). Other by-products were absent.
26
In the case of Au/TiO
2
catalyst, a positive metal-support interaction was therefore outlined.
2.4 Oxidation of other polyols
2.4.1 Glycerol. The huge and easy availability of glycerol as a by-
product of biodiesel has recently prompted research to transform this cheap
compound into valuable chemicals.
27,28
The application of gold catalysis in
glycerol oxidation under mild conditions has been experimented mainly by
two Groups. In spite of the variety of potential reaction products, origin-
ated by the general oxidative pathway reported in Scheme 5, Hutch-
ingsgroup has underlined the high selectivity of gold: using graphite as a
Table 3 Oxidation of isolated diols with gold catalysts. Substrate=0.4M; substrate/Au=100;
T=343 K; pO
2
=3 bar; pH=9.5
O H
OH
Au/C Au/TiO
2
TOF (h
1
) 430 490
Selectivity (%) 100 95
HO
O
OH
Au/C Au/TiO
2
TOF (h
1
) 240 240
Selectivity (%) 99 98
Table 4 Inuence of catalyst and experimental conditions on the oxidation of di-
ethyleneglycol to mono- and dicarboxylates
Catalyst NaOH/Substrate T (K) T (h) Conv % Monoacid% Diacid%
1%Au/C 1 343 4 96 99 1
1%Au/C 2 343 4 80 97 3
1%Au/C 2 363 1 83 98 2
1%Au/TiO
2
1 343 4 95 98 2
1%Au/TiO
2
1 363 2 95 96 4
1%Au/TiO
2
2 343 3 94 70 30
1%Au/TiO
2
2 363 6 100 55 45
284 | Catalysis, 2010, 22, 279317
support, in water solution at 333 K and in the presence of NaOH, 100%
selectivity to sodium glycerate could be readily achieved at 5060%
conversion.
29
Another thorough investigation on glycerol oxidation has been carried
out by Prati et al. in Milano. In a rst study, the relationship between
catalyst morphology and selectivity was explored at total conversion: it has
been found that larger gold particles (20 nm), supported on suitable car-
bons, show low TOFs but favour glycerate formation under mild conditions
(303 K, 3 bar), thus allowing yields up to 92%.
30
Exciting results were
achieved by the Authors using bimetallic nanoparticles as supported cata-
lyst.
31
Two important points were highlighted: a) the activity can be im-
proved by using the bimetallic Au-Pt and Au-Pd systems, thus
demonstrating a synergistic eect between the metals; b) the selectivity to
the desired product can be aected by the nature of the catalyst (particle
size, alloyed phases and support) and experimental conditions. A smart use
of the metals allowed a precise modulation of selectivity, whereas pure gold
promotes glyceric acid formation, Pd addition favours further transfor-
mation to tartronic acid and Pt addition leads to carbon-carbon bond s-
sion resulting in glycolic acid. Also in this case, the best performance was
recorded with smaller particle size catalysts. Another important parameter
is the atomic ratio of the metals in (Au
x
Pd
y
)/C catalyst, which deeply in-
uences activity and selectivity, as well as the supporting materials (Carbon,
Graphite, TiO
2
, Ti/SiO
2
, SiO
2
).
2.4.2 Sorbitol. Supported gold catalysts have been employed in sorbitol
oxidation (Scheme 6) and a comparison with Pd and Pt catalysts was carried
Dihydroxyacetone
O
OH HO
OH
OH HO
Glycerol
Mesoxalic (or -ketomalonic) acid
O
O O
OH OH
Hydroxypiruvic acid
O
O HO
OH
Glyceraldehyde
OH
O HO
H
Glyceric acid
OH
O HO
OH
Tartronic acid
OH
O O
OH OH
Scheme 5 Reaction pathway of the aerobic oxidation of glycerol.
Catalysis, 2010, 22, 279317 | 285
out (Fig. 1).
32
The presence of alkali and the use of carbon as the supporting
material allowed the successful performance of the reaction. Monometallic
gold catalysts led to humble TOFs, favouring the oxidation of the primary
alcoholic function to monocarboxylates and leading to gluconate and
gulonate with very low amounts of dicarboxylate (glucarate).
An improvement of activity was achieved by employing bimetallic
Au Pd and Au Pt catalysts, resulting in full conversion. The bimetallic
system was superior to monometallic gold also for the selectivity to
monocarboxylates at a given conversion, resulting in superior values almost
independently from the nature of the second metal.
2.5 Oxidation of allyl alcohol to 3-hydroxypropionic acid
The importance of 3-hydroxypropionic acid as a new building block has been
highlighted in a ocial classication.
33
Presently, 3-hydroxypropionic acid is a
rare and expensive chemical which is commercialized as an aqueous solution
HO
OH
OH
OH
OH
OH
HO
O
OH
OH
OH
OH
O
-
HO
O
OH
OH
OH
OH
O
-
Sorbitol
Gluconate
Gulonate
O
O
OH
OH
OH
OH
O
O
-
-
Glucarate
Scheme 6 Aerobic oxidation of sorbitol
0
30
60
90
120
150
180
1%Au/C 1%Pd/C 1%Pt/C
Conversion %
Selectivity %
(Gluconate+Gulonate)
Selectivity % (Glucarate)
TOF (h
-1
)
Fig. 1 Activity and selectivity of carbon dispersed metals in sorbitol oxidation.
286 | Catalysis, 2010, 22, 279317
by a few suppliers. Beside the traditional stoichiometric reactions, also catalytic
methods are reported for its synthesis and many patents have recently
raised.
3440
In spite of all the eorts, however, none of the proposed new processes is
eectively operating to our knowledge.
Recently, a new, unexplored route to 3-hydroxypropionic acid based on
the aerobic oxidation of allyl alcohol has been reported.
41
Its economical
advantage lies on the fact that allyl alcohol (2-propene-1-ol) is a large scale
chemical (over 50 000 tonne per year production) derived from the petro-
chemical industry via propene and propene oxide as intermediates.
42
As in many fortuitous discoveries, gold catalysis, very selective in the
aerobic oxidation of many hydroxylated molecules under mild conditions,
was tested in order to transform allyl alcohol to acrylic acid.
Surprisingly, reacting allyl alcohol in aqueous alkali solutions, a slow
oxidation takes place which produces 3-hydroxypropionate beside minor
amounts of acrylate and glycerate. Indeed, the oxidation can be controlled
by tuning the alkali amount and temperature, as reported in Table 5.
According to the reported data, a high selectivity at full conversion to the
high value 3-hydroxypropionic acid can be achieved with an excess of
NaOH at mild temperature, 323 K.
Further experiments were carried out for comparing the home-made
0.3% Au/C catalyst with the reference catalyst 1.5% Au/TiO
2
provided by
World Gold Council,
43
under the same conditions (Table 6).
Table 5 Allyl alcohol oxidation in the presence of 0.3%Au/C catalyst. ALA=allyl alcohol,
ACA=acrylic acid, GLA=glyceric acid, GLY=glycerol. Reaction conditions: [allyl
alcohol]=1M, pO
2
=3 bar, allyl alcohol/metal=4000 (molar ratio), t=24 h. Yields by HPLC
analysis on the crude reaction product.
Yield%
Test
NaOH/ALA
(molar ratio) T (K) Conv % 3-HPA ACA GLA GLY
1 1 298 98 19 15 38.5 traces
2 3 298 100 16 30.5 5 0
3 1 323 98 42 13 33 traces
4 3 323 100 79 9.5 11 0
5 3 353 100 74 18 6 0
Table 6 Allyl alcohol oxidation in the presence of 1.5%Au/TiO
2
catalyst. Experimental
conditions as in Table 5.
Yield %
Test
NaOH/ALA
(molar ratio) T (1C) Conv % 3-HPA ACA GLA GLY
6 1 298 37 8 23.5 0 0
7 3 298 25 7 18 0 0
8 1 323 94 50 37 8 0
9 3 323 97 53 32 12 0
10 3 353 97 11 21.5 6 0
Catalysis, 2010, 22, 279317 | 287
It can be outlined that Au/C catalyst presents the best results, in terms
of yields of 3-hydroxypropionic acid (79% for Au/C against 53% for
Au/TiO
2
)
.
The reaction mechanism of allyl alcohol aerobic oxidation leading to the
unexpected product is of hard interpretation. The progressive sampling
during the 24 h, in fact, does not help to nd the rst transformation of the
reagent, because no transient species could be detected beside acrylic acid
and glyceric acid, while glycerol was detected only in trace amounts (o1%).
Further tests showed that glycerol could be transformed into glyceric acid
under the above reported conditions but neither acrylic acid, nor glyceric
acid and 3-hydroxypropeneoxide (glycidol) could produce 3-hydro-
xypropionic acid in detectable amounts. Dierent pathways for the various
products during allyl alcohol oxidation should be guessed. Moreover, using
acrolein as a one pot reagent no 3-hydroxypropionic acid was recorded
beside the yellow solid material, probably a condensation product. The slow
addition of acrolein (1.1 ml), in progressive small portions (ten microliters
every 0, 5 h), to the reacting mixture resulted in the formation of 3-hydro-
xypropionate (10% yield after 24 h reaction). This test suggests acrolein as
a probable non detectable intermediate, undergoing a base catalyzed
Michael-addition of water to give 3-hydroxypropanal, whose rapid oxi-
dation would give the observed 3-hydroxypropionate (Scheme 7).
A specic catalyst, 0.3% Au/C, was prepared as in Section 2.2, using
glucose as a protecting agent, decreasing the pH of the gold colloid to 4 by
means of HCl and calcining at 673 K under H
2
for 2 hours.
41
2.6 Other alcohols
The conversion of aliphatic and aromatic alcohols to aldehydes under
neutral conditions can be successfully performed by gold catalysis. The
facile achievement of the corresponding carboxylates is reached in the
presence of alkali. Hutchings et al. have reported exciting results using
Au-Pd bimetallic catalysts, owing to a synergistic eect between the
metals,
44
while Corma et al. have demonstrated the synergistic eect be-
tween Au nanoparticles and the supporting nanometric CeO
2
material
under solvent-free conditions.
45
For many practical applications in organic
synthesis, gold catalysis applied to alcohols oxidation is relatively slow
(TOF values around dozens or hundreds h
1
). To overcome the intrinsic
low activity of gold, Hutchings and co-workers studied the contribute of a
second metal, in particular palladium. Thus, Au-Pd on TiO
2
was reported
to show an extraordinary enhancement compared to monometallic gold.
Benzylic alcohol, under solventless conditions, could be oxidized to alde-
hyde ve times faster in the presence of Au-Pd/TiO
2
than Au/TiO
2
at 373 K
and 2 atm of O
2
with selectivity to aldehyde over 90% at 75% conversion.
Under similar conditions, an exceptional value of TOF=26 9000 h
1
was
reported for 1-phenylethanol oxidation, using Au-Pd/TiO
2
. Other supports,
as Al
2
O
3
or Fe
2
O
3
, were not producing catalysts as active and selective as
Au-Pd/TiO
2
. A variety of alcohols were selectively oxidized in the absence
of solvent; however, when toluene or water were used as solvents, a general
dropping in activity of the catalyst could be observed.
288 | Catalysis, 2010, 22, 279317
Corma et al. developed a peculiar catalyst by supporting Au on nanosized
CeO
2.
This catalyst appeared to be not only highly selective toward the
oxidation of alcohols to carbonylic derivatives, but also very active oper-
ating, without any solvent, at 353 K and atmospheric pressure. Benzylic and
cinnamyl alcohols were smoothly oxidized to aldehydes, whereas secondary
alcohols were transformed to ketones. Primary alcohols, such as 3-phenyl-1-
propanol, however produced 3-phenylpropyl-3-phenylpropanoate in 83%
selectivity at 73% conversion.
The detailed description of this wide and important research area has
been recently reported.
3
2.7 Aminoalcohols
The doping eect of the amino-group on traditional metal catalysts may be
the cause of the lack of literature regarding the aerobic oxidation of ami-
noalcohols. Gold has been shown to be a pleasant exception for oxidizing
this important class of aminoacids.
26,4649
In fact, we rstly discovered that
nanometric gold represents a much better catalytic system if compared to
palladium and platinum under similar conditions (Table 7). Alkali increases
OH
Allyl alcohol
OH HO
OH
Glycerol
OH
O
HO
O
OH
Acrylic Acid
O
H
Acrolein
OH
O
HO
OH
Glyceric acid
(traces)
3-hydroxypropionic acid
Scheme 7 Pathways during the oxidation of allyl alcohol.
Catalysis, 2010, 22, 279317 | 289
the oxidation rate, despite the amino group already ensures the presence of
a basic solution.
26
The material employed as the gold support is relevant for aecting the
catalytic performance, as it has been outlined also in other cases: alumina is
a better supporting material for gold nanoparticles than carbon (Table 8).
An interesting problem of chemo-selectivity is present in the catalytic
oxidation of aminoalcohols of formula R
1
R
2
N(CH
2
)
n
CH
2
OH. As high-
lighted in former experiments on primary aminoalcohols
26
and in more
recent results on tertiary amines,
49
this oxidation can result into the cor-
responding aminoacid as well as the N-oxide. The resulting product is de-
termined by the nature of the nitrogen substituents, experimental conditions
and catalytic system.
Table 7 Catalytic oxidation of aminoalcohols with carbon dispersed metals in the: a)
absence of alkali [Substrate]=0.4M, substrate/metal=1000, pO
2
=3 bar, T=343 K, t=2h. b)
presence of alkali, [Substrate]=0.4M, substrate/metal=1000, substrate/NaOH =1, pO
2
=3
bar, T=343 K, t=2h.
HO
NH
2
1% Au/C 5% Pd/C 5% Pt/C
Conversion (%) a) 3 0 0
Conversion (%) b) 20 0 0
H
3
C
OH
NH
2
1% Au/C 5% Pd/C 5% Pt/C
Conversion (%) a) 22 0 0
Conversion (%) b) 65 0 0
HO
NH
2
1% Au/C 5% Pd/C 5% Pt/C
Conversion (%) a) 3 0 0
Conversion (%) b) 20 0 0
H
3
C
OH
NH
2
1% Au/C 5% Pd/C 5% Pt/C
Conversion (%) a) 22 0 0
Conversion (%) b) 65 0 0
290 | Catalysis, 2010, 22, 279317
In the case of N-substituted aminoalcohols, the oxidation takes place
exclusively at the nitrogen atom. Thus, the reaction of 3-dimethylamino-1-
propanol with O
2
in the presence of gold-containing catalysts produces the
corresponding N-oxide with 100% regioselectivity.
49
Table 9 and Fig. 2
show that the oxidation of the amino group is possible both in the absence
and in the presence of alkali. In the absence of alkali, 100% selectivity has
been also observed with dierent metal catalysts, but only gold containing
catalysts allowed 100% conversion, while Pt/C resulted inert and Rh/C led
to only 20% conversion towards unidentied compounds.
These data underpin the observation that aliphatic amines cause the
catalytic deactivation of the traditional noble metals.
The same test carried out in the presence of NaOH at pH 10.8 resulted in
worse performances with all the catalysts, except for Rh/C which arose its
activity up to 33% (Fig. 2).
A general evaluation on the role of alkali in promoting or depressing the
catalyst activity is risky to be done, because of the limited number of tested
substrates.
26,49
The nature of substrates, however, has been outlined to be
essential for aecting gold catalytic performance.
Table 9 Aerobic oxidation of 3-dimethylamino-1-propanol. Reaction con-
ditions: substrate 0.4 M, substrate/M=1000, pO
2
=2 atm, T=363 K, t=24 h.
Selectivity of N-oxide as a sum of the free N-oxide and its hydrated form.
Catalyst Conversion %
Selectivity to
N-oxide %
Selectivity to
Aminoacid %
1%Au/C 100 100 0
1%Au/Al
2
O
3
100 100 0
1%Au/TiO
2
95 100 0
1%Rh/C 20 0 0
1%Pt/C 0 0 0
0.5%Au-0.5%Rh/C 33 100 0
0.5%Au-0.5%Pt/C 40 100 0
Table 8 Catalytic oxidation of aminoalcohols with 1% Au/Al
2
O
3
in
the presence of alkali. [Substrate]=0.4M; substrate/metal=1000;
substrate/NaOH=1; pO
2
=3 bar; T=343 K; t=2 h.
Substrate Conversion %
H
2
N
OH
23
OH
NH
2
100
H
2
N OH
27
H
2
N OH
OH
32
Catalysis, 2010, 22, 279317 | 291
3. Selective oxidation of carbohydrates
The worldwide availability of carbohydrates is attracting the interest in their
oxidative transformation. As a general trend, in the oxidation of aliphatic
oxygenated compounds with supported gold particles the following order of
reactivity has been observed: aldehydesWprimary alcoholsWsecondary al-
cohols; tertiary alcohols and carboxylic acids are almost inert under mod-
erate conditions (up to 363 K and 3 bar). In particular, the aerobic oxidation
of aldehydes can be performed using water, organic solvents and solvent
free conditions, also in the absence of alkali. We discovered that Au is able
to easily oxidize aldehydes in water solution and, dierently from Pt, no
deactivation was observed on recycling. According to the expected trend,
catalytic aldose oxidation occurs at the aldehydic group leading to carb-
oxylic acid or carboxylates.
3.1 Glucose to sodium gluconate
Gluconic acid and gluconates are industrial intermediates widely employed
in food chemistry, surfactants and cleansing agents. That is why the oxi-
dation of glucose, a cheap renewable starting material, appears as a
charming topic. Moreover, the present industrial production is only via
fermentation by enzyme (Aspergillus niger mould), but the low productivity
of this process has prompted the interest in nding eco-friendly technologies
based on the use of oxygen in aqueous solution, under mild conditions by
heterogeneous catalysis. Many eorts have been so far carried out: Pt-based
catalysts, for example, allowed high conversion and good selectivity, but
quickly deactivated because of leaching, self-poisoning and over-oxidation.
These limits could be partly overcome by using bi- and tri-metallic catalysts
and the promoting eect of Bi.
50,51
0
20
40
60
80
100
Au/C Au/Al
2
O
3
Au/TiO
2
Rh/C Pt/C Au-Rh/C Au-Pt/C
Conversion Selectivity (N-oxide) Selectivity (Aminoacid)
%
Fig. 2 Oxidation of 3-dimethylamino-1-propanol. Reaction conditions: substrate 0.4M,
substrate/M=1000, pO
2
=1, T=343 K, t=2h, pH=10.8.
292 | Catalysis, 2010, 22, 279317
The rst application of gold catalysis for transforming glucose into glu-
conates was soon excellent in terms of activity, selectivity and durability. A
comparison among dierent Pd, Pt and Au catalysts, performed at 323 K
and atmospheric pressure, demonstrate the great peculiarity of gold: while
palladium and platinum catalysts led to selectivityo95%, Au resulted in a
selectivity close to 100% at total conversion.
52
Although superior to Pt and
Pd catalysts, in the rst experiments gold was shown to be less ecient with
respect to enzymatic catalysis.
Encouraged by the promising achievements, eorts were addressed to the
deep improvement of the catalytic system, in order to nd an alternative process
to the biochemical route. A fundamental contribute was also played by the
mechanism studies (Section 3.1.1) which were carried out side by side. Starting
from TOF of a few hundred h
1
units, we reached the exceptional value close
to sixty thousand units,
17
which is similar to the behaviour of enzymatic cata-
lysis. Following a detailed study on the kinetics of enzymatic oxidation,
53
we
compared Hyderase (from Amano Enzyme Co., U.K.), a biological preparation
containing glucose oxidase and catalase as active components and avine-ad-
enine dinucleotide (FAD) as the rate controlling factor (1.310
6
mol g
1
),
with the most ecient gold catalyst, 0.5% Au/C prepared as in Section 2.2,
containing metal particles of 3.6nm mainly at the surface.
Kinetic data of glucose oxidation to gluconate were recorded using a glass
reactor interfaced to an automatic titration device equipped with NaOH as
a reagent. Magnetic stirring and high speed turbine were alternatively used
during the tests. A careful control of various parameters such as pH, tem-
perature, glucose concentration and stirring speed led to the comparative
results reported in Scheme 8.
53
Hyderase Au/C
[Glucose]
1 M 3 M
Catalyst/Glucose 5 6
pH
9.5 5-7
T
303 K 323 K
Stirring
900 rpm 39000 rpm
Spec. Activity
218 h
-1
145 h
-1

Productivity
122 kg m
-3
h
-1

514 kg m
-3
h
-1

Scheme 8 Comparison between biological and inorganic catalysis in glucose oxidation.
Catalysis, 2010, 22, 279317 | 293
Considering the molecular eciency of the active FAD sites, a turnover
frequency of 600 000 h
1
was obtained, being this value undoubtedly better
than the eciency of active external gold atoms in the inorganic catalyst,
calculated as 90 000 h
1
. However, taking into account the lower FAD
concentration in the enzymatic extract and the potentiality of gold, which
allows a threefold higher glucose concentration, the nal productivity is
superior with gold by using a similar amount of total catalyst.
3.1.1 Kinetics and models. Kinetic investigations were performed on the
selective liquid phase oxidation of glucose, using carbon supported gold
particles
54
or unsupported colloidal gold particles
55
as the catalysts. The
rst study was carried out by Claus and co-workers: they proposed a
Langmuir-Hinshelwood model, considering the surface oxidation reaction
as the limiting factor of the whole reaction rate, while adsorption of sub-
strate and desorption of the product were regarded as fast steps. The
Authors nally suggested a dehydrogenation mechanism converting glucose
to sodium gluconate, supposing water as the reduction product of dioxygen
and detecting a scarce eect of glucose concentration on the reaction
rate. In the second paper, the application of naked gold particles as a
catalyst led to detect hydrogen peroxide-instead of water-as the reduction
product of O
2
.
Kinetic tests at low glucose concentrations (o0.1 M) recorded a rst
reaction order, leading to an asymptote at higher concentrations (0.5 M).
A rst order dependence was also found for the O
2
concentration. An Eley
Rideal mechanism, characterised by the adsorption of glucose in its hy-
drated form on gold, was then suggested because of the optimum tting
with the experimental evidence. As a consequence, a rate equation which ts
both the rst-order with respect to oxygen and the decreasing order with
respect to glucose was found.
55
In order to compare the enzymatic catalysis with the gold catalytic sys-
tem, a kinetic investigation of glucose catalysed by the above cited Hyderase
was performed under similar conditions applied for the gold catalysis.
According to measurements of initial rate as a function of initial glucose
concentration were recorded. A Michaelis-Menten mechanism resulted to
be coherent with the experimental data.
56
It is worth noting that both gold
catalysis and enzymatic catalysis are able to promote the oxidation of
glucose with the same stoichiometry where the 2 electrons reduction of
molecular oxygen produces hydrogen peroxide as the transient by-product.
Nevertheless, enzymatic and inorganic catalysis apply dierent strategic
mechanisms. Regarding the enzymatic system, the rate determining step is
the oxidation of the substrate by the enzyme, which is transformed into the
reduced form according to a faster step and showing a zero order with re-
spect to dioxygen. The oxidation of glucose by dioxygen dissolved in water
represents the rate determining step of the gold catalytic process, with a rst
order dependence of the reaction rate on pO
2
.
The corresponding rate determining steps interestingly recorded similar
activation energies (47.0 kJ/mol for gold and 49.6 kJ/mol for enzymatic
catalysis).
55,56
294 | Catalysis, 2010, 22, 279317
Scheme 9 visualizes the proposed molecular mechanism of glucose oxi-
dation on a gold nanoparticle.
57
This mechanism suggests that the presence of alkali is fundamental for
activating gold particles.
52
Kinetic experiments conrmed that there is no
dierence in the activity of unsupported and supported gold nanoparticles,
except for a better stability of the supported gold catalyst in the time, thus
excluding any role of the support in promoting the oxidation.
57
The key role of the particle size in aecting gold catalytic activity is a
leit motiv also characterizing glucose oxidation. The sudden loss of activity
of particles larger than 10 nm was recorded using unsupported colloidal
particles (10
4
M Au, 0.38 M glucose, 303 K under oxygen at atmospheric
pressure), due to a quasi-linear correlation between the initial specic molar
activity (moles of reacted glucose/ mole total gold h) and the inverse of the
mean diameter in the range 27 nm.
17
A correlation between surface structure and catalytic behaviour in solid
materials is of strategic importance for producing quick and clean industrial
reactions. This has prompted to derive a geometrical model for describing
the morphological properties of two catalysts made of carbon supported
gold particles, prepared as in Section 2.2, having a known size distribution
centred at 3.30 nm and 7.89 nm respectively.
58
For this purpose, the pro-
gressive poisoning eect of dierent molecules on these catalysts, performed
during the aerobic oxidation of glucose, has been used as a diagnostic tool.
The observed deactivation trend follows the order thiocyanateWcyanide
EcysteineWthiourea and each of them obeys an exponential law. The
kinetics of catalyst deactivation has been interpreted by considering the
R
O
H
HO

R
OH
H
R
OH
H
O
Au
-
O
2 slow
R
H
OH
O
O
R
O
O

H
2
O
2
R
OH
H
O

Au Au
degradation
R
O
H
+
O

+
Au
R
OH
H
O
Au

H
Au
+
Au Au +
Scheme 9 Molecular mechanism of aerobic glucose oxidation with gold nanoparticles.
Catalysis, 2010, 22, 279317 | 295
contribute of electronic factors which overlap the space shielding of active
sites, due to long range poison-catalyst interaction inuencing the entire
metal particle.
The consequent insight in the aerobic oxidation of glucose suggested a
molecular model for electronic interactions in gold nanoparticles: correl-
ating the nature of the molecules, which caused a consistent poisoning ef-
fect, and considering the promoting eect of OH

, we found that the

dioxygen reduction step is dierently inuenced by soft and hard-nucleo-
philes. In conclusion, it has been underlined how the competition of the
poisoning molecule with the reagents can be discussed considering two
extreme cases: for a hard nucleophile, no back-donation from metal to the
Lewis base is expected, leaving in the reacting solution the original or a
higher catalytic eect, as in the case of OH

. Regarding a nucleophile, N,
showing p back-bonding ability, the removal of the electron density from
the metal inhibits dioxygen reduction thus decreasing the catalytic property
of the entire gold particle (Schemes 9, 10).
3.2 Free gluconic acid
Many eorts have been devoted to nd a one-pot synthesis of free gluconic
acid, because the present method-from calcium gluconate and sulfuric acid-
leads to large amounts of CaSO
4
as a by-product. Despite all the attempts,
following either enzymatic or inorganic routes, no interesting results were so
far recorded due to the inhibition of the catalytic systems at low pH values.
Focusing on this challenging topic, multi-component catalysts resulted
more active than monometallic gold particles. In particular, an important
synergistic eect between gold and platinum was observed (Fig. 3).
The most promising Au Pt combination was further optimized, leading
to a quite active catalyst for alkali-free oxidation of glucose containing gold
and platinum in the ratio 2:1 (w/w). The synergistic eect was detected in a
series of experiments which compare colloidal catalysts and supported
catalysts.
59
A direct synthesis of gluconic acid by aerobic oxidation of
glucose seems to be possible with gold-based catalysts, starting from the
encouraging TOF values around 1000 h
1
.
4. Selective oxidation of hydrocarbons
In order to highlight the versatility of heterogeneous gold catalysis, some
applications of unsubstituted hydrocarbon oxidation are considered.
H
R
O
OH
O
O
Au
N

Scheme 10
296 | Catalysis, 2010, 22, 279317
In particular, oxidation of propene to propene oxide (PO), ethene to
vinylacetate monomer (VAM) and cyclohexane to cyclohexanol-cyclohex-
anone mixture (KA oil) were investigated in a more systematic manner.
Here we present an overview of the partial oxidation of hydrocarbons by
gold catalysis.
4.1 Propene epoxidation
All the eorts to produce propene epoxide (PO) commercially by direct
oxidation of propene, similarly to the silver promoted synthesis of ethene
oxide, have been so far vain and the largest amount of PO is still manu-
factured by chlorohydrine process (49%) and the indirect hydroperoxide
processes.
42
The progressive request for eco-friendly processes, which can
exclude chlorine dependence and huge amounts of undesired by-products,
has prompted basic research to nd alternative catalytic routes. In this
context, gold has been shown to be a very promising catalyst. In fact, the
pioneering Harutas work has reported that supported gold catalyst is able
to promote the gas phase epoxidation of propene by O
2
in the presence of
H
2
.
60
The behaviour of gold is unique, as shown by comparing dierent
metals dispersed on titania (M=Au, Pt and Pd) under moderate conditions
(298353 K) when equimolecular amounts of H
2
and O
2
are reacted with
C
3
H
6
. Only Au produces propene oxide (PO), while Pd and Pt promote
mainly the hydrogenation of C
3
H
6
to C
3
H
8
and the formation of small
amounts of acetone and carbon dioxide. All the experiments leading to the
total selectivity to PO, underlined the strategic role of TiO
2
as the support.
However, the low conversion needed to reach high selectivity represents a
weak point. As a consequence, most of the subsequent investigations were
devoted to improve PO yields meanwhile maintaining a high selectivity.
Au
Pt
Pd
Rh
Au-Pt
Au-Pd
Au-Rh
0
50
100
150
200
250
300
Conversion %
TOF (h
-1
)
Fig. 3 Aerobic oxidation of glucose with monometallic and bimetallic catalysts. Glucose/
Au=3000; T=343 K; pO
2
=3 bar; t=6.5h.
Catalysis, 2010, 22, 279317 | 297
Insights on gold catalysts supported on non-porous and mesoporous tita-
nia-silica allowed further progress in PO productivity, also indicating the
eect of preparation conditions and pre-treatments on their activity and
stability. A series of Au/TS-1 catalysts with dierent gold and titanium
contents was examined at 413473 K at a space velocity of 7000 mL
(h g
cat
)
1
. A catalyst prepared with a Si/Ti=36 (atomic ratio) and a gold
loading of 0.05 wt% produced 116 g
PO
(h kg
cat
)
1
at 473 K, which was the
highest rate at that time reported for a TS-1-based catalyst with no de-
activation during 40 h. Catalysts prepared with lower titanium and gold
contents resulted in very active catalysts, up to 350 g
PO
(h g
Au
)
1
at 473 K
for 0.01 wt% Au/TS-1 (Si/Ti=500), indicative of a more ecient use of gold
and titanium for the epoxidation reaction. The low gold loading coupled
with non-detectable gold particles in TEM micrographs suggested that, in
these materials, signicant activity is due to gold entities smaller than 2 nm.
61
An ecient Au capture on TS-1 support by a NH
4
NO
3
treatment led to a
fourfold increase in Au/TS-1 catalysts. The higher gold amount produced
catalysts allowing quite high conversions of propene (510%) with accept-
able selectivity (7585%), at 473 K and a space velocity of 7000 ml
(hg
cat
)
1
. The related productivity resulted in 134 g
PO
(hkg
cat
)
1
.
62
4.2 Oxidation of ethene to vinyl acetate (VA)
Beside ethene oxide synthesis, successfully performed by silver catalysts,
42
another important target in the selective oxidation of ethene is represented
by the acetoxylation to vinylacetate (VAM), the latter being the monomeric
unit for the production of polyvinylacetate (PVAc). Pd-Au bimetallic silica-
supported catalyst, promoted by potassium acetate, is the well-known
system commercially applied for the production of the monomer (VAM).
3
The relevant added value of vinyl acetate monomer has attracted the
interest of both academic and industrial research groups, thus leading to a
number of patents. Researchers at Celanese International Corporation were
particularly active in this area describing in details successful preparation
methods
63
: the general procedure, similar to the deposition-precipitation
technique, provides the active metals on the surface rstly as water-insol-
uble compounds which are reduced by a second step to the metallic form.
A shell-impregnated catalyst, Pd-Au on a silica support, was also de-
scribed for the synthesis of vinyl acetate which allowed a selectivity over
90%.
64
4.3 Oxidation of higher alkenes
Supported gold catalysts have been employed in the aerobic oxidation of
other alkenes without using a second reagent, H
2
, as a sacricial reductant
or CH
3
COOH as the acetilating reagent. Hutchings et al.
65,66
and other
research groups
6769
found that alkene oxidation fairly proceeds by adding
a catalytic amount of peroxides (either hydrogen peroxide or tert-butylhy-
droperoxide) as an oxygen chain initiator. These works fairly emphasize
how much selectivity and conversion are dependent on substrate, catalyst
and experimental conditions. The oxidation of cyclohexene, styrene, stil-
benes and cyclooctene was performed, the catalysts being home made gold
298 | Catalysis, 2010, 22, 279317
supported on carbon, alumina, titania which were compared with World
Gold Council reference catalysts.
43
Cyclohexene oxidation presented the highest selectivity to epoxide (50%)
and ketone (26%) at 30% conversion using Au/C as a catalyst in 1,2,3,5-
tetramethylbenzene solvent (TMB). Moreover, a promoting eect of bis-
muth on Au/C catalyst led to 98% selectivity of a valuable mixture of
products.
65
Styrene could be converted by aerobic oxidation into epoxide with a low
selectivity (29%), by using either a mixture of 1,2,4,5-tetramethylbenzene
(TMB)/1,4-dimethylbenzene (DMB) or hexauorobenzene as a solvent
and 1% Au/C as a catalyst. However, the major oxidation product was
benzaldehyde with a selectivity around 46% for both solvents, while acet-
ophenone was achieved with a selectivity of 15% with 1,2,4,5-TMB/
1,4-DMB and 11% with hexauorobenzene.
65
Tert-butylhydroperoxide (TBHP) as the oxidant was employed by Ying
et al.
68
in styrene oxidation in the presence of gold on mesoporous alumina,
obtaining 70% selectivity to epoxide along with a consistent production of
benzaldehyde.
Similarly, nanosized-gold deposited on TiO
2
by deposition-precipitation
method was shown to be an active and selective catalyst (around 50% se-
lectivity) for the epoxidation of styrene by TBHP. Furthermore, more exotic
oxides as supporting materials for the same reaction were investigated, such
as gallium, indium and thallium oxides, thus revealing a pretty good per-
formance of Au/Tl
2
O
3
(around 60% selectivity).
67
Cis-stilbene oxidation with dioxygen using a 1% Au/Graphite catalyst led
to the corresponding epoxide, with cis : trans ratio depending on the solvent
but always in favour of the trans conformation: 74% selectivity to trans-
stilbene epoxide at 48% conversion was found by means of i-propylbenzene
as a solvent.
65
The oxidation of cis-cyclooctene was investigated using 1% Au/C cata-
lysts both in the presence and absence of solvents by Hutchings et al.
65
The
best result was obtained with 1,2,3,5-TMB as a solvent, leading to 94%
selectivity to the epoxide at 28% conversion while in the absence of solvent
81% epoxide at 8% conversion was obtained.
4.4 Oxidation of alkanes
The activation of CH bond in the selective oxidation with dioxygen by gold
catalysis has appeared to be a promising reality. Research has particularly
focused on the synthesis of cyclohexanone and cyclohexanol, because it is a
matter of growing interest for chemical industry. These oxidation products,
in fact, are fundamental intermediates for making e-caprolactam and adipic
acid, thus leading to nylon-6 and nylon-6,6 manufacture beside less im-
portant applications as stabilizers, homogenizers for soaps and synthetic
detergent emulsions, and as solvents for lacquers and varnishes. Zhao and
co-workers
70
rst applied gold catalysis in the activation of cyclohexane:
Au/ZSM-5 and Au/MCM-41 favoured a selectivity around 90% and con-
versions of 10-15% at 423 K, even though a loss in both activity and
selectivity after their recycle is a drawback for industrial application.
Catalysis, 2010, 22, 279317 | 299
A number of eorts has been carried out in order to reach a satisfactory
one-pot oxidation of cyclohexane
65,7072
: Au/graphite without any solvent,
but using a halogenated benzene as an additive, led to 92% selectivity
(cyclohexanone cyclohexanol) at low conversion (1%).
65
Higher con-
versions (2030%) and selectivity (95%) were achieved by Zhu et al.
71
with
gold on mesoporous silica catalysts, a clearly better result compared to the
current industrial process leading to 7085% selectivity at 4% conversion
and based on the use of cobalt salt or metal-basic acid as catalysts.
Although of great interest for petrochemical and natural gas conversion,
the selective oxidation of other alkanes has been scarcely investigated.
3
5. Gold catalysis in material science
5.1 Conducting polymers: polyaniline and polypyrrole
Since the rst preparation of the highly conducting polyacetylene (PA) in
1977, much eort has been focused on the synthesis of other organic con-
ducting polymers such as polyaniline (PANI) (Fig. 4), polypyrrole (PPy)
(Fig. 5) and polythiophene (PTh) and their applications in devices com-
bining optical, electrochemical and conducting properties, owing to their
great versatility.
73,74
PANI, in particular, is unique because of its tuneable
conductivity being connected to the degree of acid-doping (pH) and oxi-
dation state of the material. Equal numbers of oxidized and reduced units
(emeraldine form), with one proton doping every two units, guarantee op-
timum conductivity of the polymer.
Recently, great attention has been put on the morphology of PANI
nanostructure, as nanobers and nanotubes. In general, PANI nano-
structures are achieved by a template synthesis route using zeolite
channels, track-etched polycarbonate and nanosized alumina membrane as
templates, which address the growth of the nanostructures.
75
Even though
this method allows the perfect control of the length and diameter of the
products, by template selection, in most applications the template must be
removed, requiring additional workup and causing disorder or modication
of the micro/nanostructures. It has been demonstrated that the morphology
and chemical properties of PANI are closely associated with the preparation
method and many synthetic procedures have been experimented.
76
Gener-
ally, aniline polymerization is performed through oxidative coupling of
aniline or its dimer, N-(4-aminophenyl)aniline, using oxidants such as am-
monium persulfate (APS), K
2
Cr
2
O
7
, KIO
3
. The most common oxidant used
for the preparation of conducting polymers is APS, but its inorganic by-
product (ammonium sulfate) represents a limit for further applications.
77
The use of other metals in a high oxidation state does not overcome this
drawback.
7579
A recent application of chloroauric acid (HAuCl
4
), as
an oxidant for the polymerization of aniline, resulted to be eective for
achieving nanobers, nanotubes,
80
and nanoballs.
73
The introduction
of metal species can deeply inuence the electronic and chemical properties
of the polymer. Chattopadhyay and co-workers reported a new route for
synthesizing AuPANI composites based on the use of H
2
O
2
as the
bifunctional reagent for the reduction of HAuCl
4
and the oxidation of
aniline, leading to the formation of interesting PANIgold composites.
78
300 | Catalysis, 2010, 22, 279317
N
H
H
N
H
N
H
N
H
N
H
N
H
N
H
N
2
L
e
u
c
o
e
m
e
r
a
l
d
i
n
e

N
H
N
N
N
H
N
H
N
H
N
H
N

E
m
e
r
a
l
d
i
n
e

C
o
n
d
u
c
t
i
n
g

E
m
e
r
a
l
d
i
n
e

N
H
N
H
N
H
N
H
N
+
N
+
N
+
N
H
H
H
H
C
l
-
C
l
-
C
l
-
P
e
r
n
i
g
r
a
n
i
l
i
n
e

N
H
N
N
N
N
N
N
N
F
i
g
.
4
O
x
i
d
a
t
i
o
n
s
t
a
t
e
s
o
f
P
A
N
I
Catalysis, 2010, 22, 279317 | 301
Metal particles can be introduced in the polymeric framework also in two
separate steps.
81
Mallick et al.
82
have described further preparation methods
and applications of goldpolyaniline composites. Nanoparticles of pre-
formed metallic gold have not yet been used as a catalyst in the oxidative
polymerization of aniline, but Bicak and Karagoz performed the synthesis of
emeraldine base from aniline and gaseous oxygen with Cu(II) as the cata-
lyst.
83
The use for organic solvents and a soluble catalyst, however, makes
this route far to be a real eco-friendly method, even though the achieved
yields were interesting. Also the application of H
2
O
2
for aniline polymer-
ization appears to be attractive, mainly for large-scale applications, because
its reduction product, H
2
O, improves recycling of the reagent. A limit,
however, is the slow reaction rate which is prompting research to nd
suitable catalytic systems for improving the kinetics:
77
Sivakumar and
Gedanken have successful applied ultrasonic irradiation for achieving con-
ductive polyaniline
84
and Aupolyaniline composites have been produced in
the presence of chloroauric acid.
78,84
The exciting performance of gold
nanoparticles as the catalyst in the oxidative polymerization of pyrrole
85
(Section 5.4), has suggested the investigation on this catalytic method for
oxidising aniline. While gold was shown to be almost inert towards the
aerobic oxidation of aniline, polyaniline could be synthesized using hydro-
gen peroxide as the oxidant under mild conditions.
86
As pointed out before,
the request of a simple and clean preparation method is required for par-
ticular technological applications, such as changeable conducting ma-
terials,
87
electronic displays,
88
electrode materials,
89
molecular electronic
circuit elements,
90
restoration of data,
91
detectors
92
and biochemical analy-
sis.
93
In fact, the electrical conductivity of PPy, due to the electrons hopping
along and across the polymer chains with conjugating bonds,
94,95
is par-
ticularly sensitive to residues of reagents and organic solvents disturbing the
co-planarity between interchains.
96
Similar considerations must be taken in
consideration for supporting new catalytic procedures for the synthesis of
conducting polypyrrole, which presently can be prepared by chemical,
97
electrochemical,
98
plasma,
99,100
vapour phase
101,102
and enzymatic routes.
103
5.2 Oxidative polymerization procedure of aniline
Polyaniline can be easily prepared by aniline oxidation in aqueous medium.
Various supramolecular structures of the nal product are obtained, de-
pending on the conditions of the reaction, but the mechanism of their for-
mation has not yet been elucidated. When aniline is oxidized in an acidic
aqueous medium with ammonium peroxydisulfate, a PANI precipitate is
produced. The blue pernigraniline form, present during the polymerization,
converts into the green protonated emeraldine at the end of the
N
H
N
H
N
H
N
H n
Fig. 5 Polypyrrole
302 | Catalysis, 2010, 22, 279317
polymerization. The reaction is exothermic and leads, besides PANI for-
mation, to sulfuric acid as a by-product. The progress of polymerization can
be followed in situ by recording either the temperature or the pH. It has been
recently reported
104
that the mechanism of aniline oxidation with ammo-
nium peroxydisulfate in aqueous solution of strong (sulfuric) or weak
(acetic) acids is substantially dierent. In sulfuric acid solution a granular
PANI was produced; in acetic acid solution, on the contrary, PANI nano-
tubes were obtained. It has been demonstrated that aniline polymerization
proceeds well even in water, without any added acid, when ammonium
peroxydisulfate was used as an oxidant. The sulfuric acid produced by the
decomposition of peroxydisulfate, in fact, gradually provides the necessary
acidity and the nal PANI is protonated with this acid. Nevertheless, the
conductivity of PANI prepared with this simple method is rather low.
The use of other oxidants, such as oxygen and hydrogen peroxide, in the
presence of gold-based catalysts has led to new exciting results.
5.3 Polymerization of aniline with gold catalysts
Aniline, dissolved in aqueous HCl, is inert towards oxidation with H
2
O
2
; on
adding a gold catalyst (Aniline: Au=1001000) the insoluble green polymer
emeraldine is formed. Purication of the product can be achieved by
extraction with 1-methyl-2-pirrolidone and evaporation of the solvent
under vacuum.
Among many catalytic systems, as colloidal gold, gold supported on car-
bon and gold supported on TiO
2
, this latter produced the highest yield
86
The
aniline/emeraldine emichloridrate redox potential is quite high (ca. 1.46 V),
105
thus suggesting a thermodynamic barrier to the aerobic oxidation of aniline
(E1 O
2
/H
2
O=1.23 V). As H
2
O
2
presents a higher value of E1=1.78 V, one
could expect this oxidant to be eective in aording the conductive polymer.
Actually, while no aerobic oxidative polymerisation of aniline was observed
using dierent catalytic systems with O
2
at 3 bar and room temperature, a
modest catalytic eect (typically 45% yield) was detected when a small
amount of colloidal gold (Au:Aniline=0.001) was used as a catalyst in
combination with the H
2
O
2
reagent. No product was isolated without any
catalyst, and no benet was recorded from using H
2
O
2
in excess (Table 10).
However, the PANI yield could be increased by increasing the gold
amount in the range Au:Aniline=0.0010.004 (molar ratio) reaching the
asymptotic value of 27% in 24h-tests (Fig. 6).
The humble catalytic life of gold naked particles in oxidation reactions
could be the cause for the limited conversion of aniline to PANI. The
Table 10 Oxidative polymerization of aniline in the pres-
ence colloidal gold and dierent H
2
O
2
amounts
Test Au:Aniline H
2
O
2
:Aniline Yield%
1 0 1 0
2 0.001 1 4.8
3 0.001 2 4.8
4 0.001 4 4.0
Catalysis, 2010, 22, 279317 | 303
oxidative polymerisation of aniline was consequently experimented also in
the presence of supported gold catalyst (0.5% Au/C, 1% Au/TiO
2
), which
was proven to be more stable in former catalytic applications.
17
The
achievements, reported in Table 11, show improved performances.
In particular, the high activity of Au/TiO
2
can be ascribed to a strong
contribution of the TiO
2
support. Dierently from unloaded carbon, which
was inert in aniline polymerisation by H
2
O
2
, P25 titania catalyzed the
partial oxidation of aniline to soluble dark oligomers. However, no solid
material was formed. The products obtained in all of the preparations were
identied as ES (emeraldine salt) according to the FT-IR.
81
UVvis,
74
and
XRD spectra
75
and
84
reported in Figs. 79.
The morphology of the products, investigated by transmission electron
microscopy (TEM) and scanning electron microscopy (SEM), revealed
emeraldine in form of nanospheres of 44160 nm (Fig. 10A) alternating with
micrometric rods (Fig. 10B and Fig. 11).
Concerning the morphological properties, similar nanospheres were ob-
tained for the Au/C and TiO
2
catalysts. In the case of Au/TiO
2
, however, the
nanospheres were assembled in a cluster-like organization, which was absent
in the product derived using the carbon-supported catalyst. The conductivity
of the polymer obtained in the high-yield conversion of aniline with Au/TiO
2
catalyst (Table 11, test 2) reached the value of 1.5 10
1
S/cm and was
determined with a standard conductivity cell (CONH Material Mates).
In conclusion, it has been shown that conductive PANI, mainly in form
of nanospheres, can be easily fabricated from aniline by H
2
O
2
oxidation in
the presence of gold nanoparticles as a catalyst. The conductivity values,
correlated with the bulk resistance of this polymer, are similar to those
obtained through other polymerisation methods.
84,106
0
5
10
15
20
25
30
0 0.005 0.01 0.015 0.02
Au/Aniline
Y
i
e
l
d

%

Fig. 6 Dependence of aniline polymerization by the amount of colloidal gold.
Table 11 Polymerization of aniline by supported gold catalysts.
(Aniline:Au=1000)
Test Catalyst Aniline/H
2
O
2
Yield%
1 0.5% Au/C 1 11.4
2 1% Au/TiO
2
1 70.1
304 | Catalysis, 2010, 22, 279317
5.4 PANI-based composites
Conducting polymers have been proven to be suitable host matrices for
dispersing metallic particles. Conducting polymer composites with metal
nanoparticles allow a facile ow of electronic charges through the polymer
matrix during electrochemical processes. Through a suitable combination of
conducting polymer and metal nanoparticles, novel promising electrodes
400 600 800
0.0
0.5
A
Wavelength (nm)
Fig. 8 UV-vis spectrum of emeraldine salt in NMP as the solvent.
4000 3500 3000 2500 2000 1500 1000 500
10
15
20
25
30
35
40
45
%
T
Wavenumber (cm
-1
)
Fig. 7 FT-IR spectrum of emeraldine salt in KBr pellet.
Catalysis, 2010, 22, 279317 | 305
could be generated with higher surface areas and enhanced electrocatalytic
activities, particularly interesting in the fuel cell technology.
5.4.1 Synthesis of PANI/MCM-41. PANI is insoluble in common
solvents and impossible to be molten. These drawbacks can be overcome by
modifying the polymer with the incorporation of inorganic materials.
As PANI/inorganic nanocomposites combine the advantages of PANI
and inorganic nanoparticles, extensive research has been carried out in this
eld. Silica nanoparticles, in particular, have received great attention be-
cause of their unique properties and wide applications. Primarily, the main
objective is to keep the conducting polymer in a stable colloidal form.
Fig. 10 TEM images of PANI synthesized with (A) (Bar=200 nm), H
2
O
2
and (B) (Bar=1 mm),
naked gold nanoparticles.
20 40 60 80
100
200
300
400
500
600
700
L
i
n

(
C
o
u
n
t
s
)
2-Theta-Scale
a
b
Fig. 9 X-ray diraction pattern of emeraldine salt.
306 | Catalysis, 2010, 22, 279317
Armes et al.
107110
succeeded in incorporating silica nanoparticles into the
core of PANI. Aniline was polymerized by ammonium peroxydisulfate in the
presence of silica colloids at low concentration of monomer and oxidant.
This technique allows to slow down the rate and degree of polymerization
and promote the polymerization on the colloidal surface rather than into the
bulk. Eectively, the outer PANI layer of PANI/SiO
2
colloids becomes
soluble to some extent. Porous silica possesses high surface area and the size
of pores can be tuned from 2 to 10 nm in a narrow diameter distribution by
changing the experimental conditions. PANI synthesis inside porous silica
channels has attracted more attention. Wu and Bein
111
fabricated a con-
ductive lament of PANI in MCM-41, by using MCM-41 as the host which
was contacted with aniline gas (not benecial to the environment) at 313 K
for 24 h, thus obtaining signicant conductivity. PANI/MCM-41 composite
was synthesized by chemical oxidative polymerization of aniline on the
surface of MCM-41 in the presence of HCl. It was shown that PANI was
present not only on the surface of MCM-41 but also inside the pores.
Moreover, the higher HCl concentration, the higher conductivity of the
composite, because of a wider delocalization of the resulting emeraldine salts.
5.4.2 Preparation of PANI nanoparticles by Fe
3
O
4
. Colloidal particles
with magnetic dipole moments are able to self-assemble into exible
chains. In particular, they can form chains with threefold junctions resulting
from a delicate balance between the dipolar interactions. These chains
can be thought as a living polymer whose length and organization
are determined not by the reaction conditions, but by a thermodynamic
balance of forces. Water soluble Fe
3
O
4
nanoparticles, with a coating
of polyethylene glycol nonylphenyl ether (NP5) and cyclodextrin (CD),
were synthesized and used as templates for the preparation of PANI
Fig. 11 SEM images of PANI synthesized with H
2
O
2
and naked gold nanoparticles
(Bar=500 nm)
Catalysis, 2010, 22, 279317 | 307
nanostructures.
112
NP5 was used to stabilize the magnetic nanoparticles by
formation of a suitable surface coating and CD for improving their misci-
bility with water. Y-junction PANI nanorods and nanotubes have been
synthesized by the use of in situ self-assembled magnetic nanoparticles as
templates and pH control of the reaction system. It has been found that an
initial pH of the reaction system around 810 favours the formation of
nanorods, whereas a starting pH range of 56 leads to the formation of
nanotubes. The morphology of Y-junction PANI nanostructures depends
on the reaction conditions such as on aniline concentration and the presence
of an organic solvent.
5.4.3 Preparation of PANI nanoparticles by Pt. The incorporation of Pt
alone or Pt with secondary metals including Ru, Os, Sn and Mo into PANI
has been primarily focused on exploiting the catalytic activity of the
metals.
113
For example, polymer supported Pt has been used in the catalytic
oxidation of methanol, formic acid and hydrazine, in addition to the re-
duction of dioxygen. The reaction of methanol at Pt surfaces has been the
focus of numerous studies. Laborde et al.
114
have studied the oxidation of
methanol with a platinum modied polyaniline electrodes in acidic medium.
The results indicate that methanol oxidation involves the direct formation
of CO
2
through reactive intermediates.
The synthesis of polyaniline/platinum composites has been achieved
using controlled electrochemical reduction of PtCl
2
6
and PtCl
2
4
. The
electrochemical and chemical syntheses of PANI/Pt by reduction of PtCl
2
6
and PtCl
2
4
produce morphologically dierent composite materials.
5.4.4 Preparation of PANI nanoparticles by CuSO
4
. A simple, one pot
and in situ chemical synthesis route for the preparation of polyaniline uses
cupric sulfate as an oxidizing agent. The reaction has been conducted in
methanol and the cupric sulfate has been added drop by drop. The size of
the copper nanoparticles varied in the range 25 nm. The formation
mechanism of micro or nanostructured polymer is not yet clear. In the rst
step, we can assume that an oligomeric form of aniline can be formed due to
the presence of a suitable oxidizing agent. The oligomerized aniline thus
produced may act as a nucleation centre, which catalyses the oxidation of
the remaining monomers present in the solution. The oxidizing agent gets
reduced and forms copper nanoparticles that lead to the formation of a
metal-polymer composite material, which could represent an important
advantage for further applications. This method involving copper has been
extended to gold and palladium systems.
74
5.4.5 Preparation of PANI-gold composites. A simple route for poly-
aniline-gold composites synthesis uses tetrachloroauric acid (HAuCl
4
) as
the oxidizing agent, forming metallic gold nanoparticles (1050 nm) at the
end of oxidation. The reaction is conducted in toluene with a phase-transfer
catalyst. Other works report the same reaction conducted in 1M HCl
aqueous
73
or in a solution of D-camphor-10-sulfonic acid.
115
A new method of synthesis of an Au nanoparticle-conducting polyaniline
composite has been proposed using H
2
O
2
both for the reduction of HAuCl
4
and polymerization of aniline in the same aqueous medium.
78
308 | Catalysis, 2010, 22, 279317
5.5 Oxidative polymerization of pyrrole by gold
The polymerization of pyrrole can be fairly performed by aerobic oxidation
by using gold catalysis.
85
Stirring pyrrole (Py) in acidic (HCl) aqueous
solution in air at room temperature (292295 K) and in the presence of
colloidal gold a slow oxidation takes place producing a dark product. The
observed yields, up to 75%, are depending on the total gold amount in the
range Py:Au=100010000, as reported in Table 12.
An acceleration of the reaction can be obtained by carrying out the re-
action under pure oxygen as reported in Table 13 thus allowing a higher
yield (82%) of polypyrrole in less time (24 h).
A great improvement of pyrrole polymerisation has been observed by
using H
2
O
2
instead of O
2
as the oxidant.
In this case we must outline that pyrrole plus HCl, dissolved in water
under nitrogen atmosphere, undergoes a slow oxidative polymerisation
also in the absence of catalyst, producing polypyrrole in 57% yield in 24 h
(Table 14). The addition of gold improves the polymerisation which can be
implemented to 99% of the product.
Fig. 12 visualizes the catalytic eect of gold in polypyrrole formation with
various oxidative agents. Fig. 13 reports the kinetics of polymeric material
Table 12 Aerobic polymerization of pyrrole with air.
Reaction time 3 days
Test Py/Au (molar ratio) Yield%
1 No gold 0
2 10000 42
3 5000 50
4 1000 75
Table 13 Catalytic polymerization of pyrrole with O
2
at 0.3 MPa
and dierent reaction times
Test t (h) Py/Au (molar ratio) Yield%
5 8 No gold 0
6 8 10000 0
7 8 1000 1
8 16 No gold 5
9 16 10000 31
10 16 1000 34
11 24 No gold 10
12 24 10000 50
13 24 5000 60
14 24 1000 82
15 72 No gold 12
16 72 10000 61
17 72 5000 72
18 72 1000 99
Catalysis, 2010, 22, 279317 | 309
formation, during pyrrole polymerisation by dioxygen in the presence of
dierent quantities of gold.
Using pure oxygen gas, a slow auto-oxidation produced a modest yield of
insoluble polymer (12%) after 3 days. On adding colloidal gold, a strong
catalytic eect was detected, as the polymeric material was formed with
almost total yield (99%) after 3 days (Fig. 13).
Using hydrogen peroxide as the oxidant, a consistent polymerization of
pyrrole was observed also in the absence of catalyst. In fact, the reaction
occurred with 57% yield with respect to pyrrole in 24 h. However, also in
this case, a catalytic contribute of gold was demonstrated because the yield
increased up to 99% by adding a small quantity of colloidal metal (Fig. 12).
A concert of dierent analytical techniques allowed the characterization
of the obtained polypyrrole structure.
116119
Independently from the syn-
thetic method, all the prepared polymers show a similar IR spectrum which
is represented in Fig. 14.
Fig. 15 shows typical X-ray diraction patterns of PPy synthesized in the
presence and in the absence of gold nanoparticles.
120
The TEM images of the various polymeric materials are reported in
Figs. 16 AE. The comparison among the dierent products highlights how
much the morphology is aected by the nature of the oxidising reagent. By
using H
2
O
2
, the quick polymerization led to a partially reticulated structure
0
20
40
60
80
100
120
0 0.0002 0.0004 0.0006 0.0008 0.001 0.0012
Au/PY
O
2
, 24h
H
2
O
2
, 24h
O
2
, 3 days
Air, 3days
Y
i
e
l
d

%

Fig. 12 Gold eect in the polymerization of pyrrole by air, O
2
and H
2
O
2
.
Table 14 Catalytic polymerization of pyrrole using
H
2
O
2
as the oxidant. Reaction time 24 h
Test Py/Au (molar ratio) Yield%
19 No gold 57
20 10000 66
21 5000 90
22 1000 99
310 | Catalysis, 2010, 22, 279317
without gold (Fig. 16A) and to amorphous material using gold catalysis
(Fig. 16B).
More ordered structures were achieved by the non-catalyzed polymer-
ization with gaseous oxygen (Figs. 16C, D). Abundant peculiar thin squares
were observed in the high yield polymerization catalysed by gold (Fig. 16E).
This latter structure is unusual also in the context of conventional poly-
merizations of pyrrole and could be interesting for tailor-made composite
applications.
The conductivity of the synthesized polypyrrole materials is similar to
that obtained in conventional chemical polymerization using stoichiometric
0
20
40
60
80
100
0 8 16 24 32 40 48 56 64 72
Reaction time (h)
no gold
Py/Au=10000
Py/Au=1000
Y
i
e
l
d

%

Fig. 13 Kinetic data of pyrrole polymerization under O
2
.
3200 2400 1600 800
10
20
30
40
%
T
Wavenumber (cm
-1
)
Fig. 14 FT-IR spectrum of a PPy sample in KBr.
Catalysis, 2010, 22, 279317 | 311
reagents and it was determined with the standard conductivity cell (CONH
Material Mates) also used for polyaniline (Section 5.2).
121,122
The s values,
determined for various preparations and measured in samples of dierent
thickness under dierent voltages (Table 15), ranged from 2.7 10
4
to
20 40 60 80
100
200
300
400
500
600
700
L
i
n

(
C
o
u
n
t
s
)
2-Theta-Scale
a
b
Fig. 15 X-ray diraction patterns of PPy synthesized in the absence (a) and in the presence (b)
of gold nanoparticles
A) By H
2
O
2
, no Au
B) By H
2
O
2
, Py/Au=1000.
C) By air,no Au. D) By O
2
,no Au E) By O
2
,Py/Au=5000
200 nm 100 nm
200 nm
100 nm 200 nm
Fig. 16 TEM images of dierent polypyrrole samples.
312 | Catalysis, 2010, 22, 279317
5 10
3
S cm
1
. These conductivities are typical for polymers obtained
by using FeCl
3
, AgNO
3
, Cu(NO
3
)
2
AlCl
3
,
123
VO(acac)
2
AlCl
3
O
2
,
124
AlCl
3
CuClO
2
125
but much lower than the values generally found in
electrochemical polypyrrole lm deposition.
117
A synthetic comparison
of s values is reported in Table 16, showing how the wide range in the
conductivities (from 10
10
to 10
2
Scm
1
) of the dierently synthesized
polymers allows a wide choice of application of these materials, according
to the required conductivity.
6. Conclusions
The last twenty years represent a milestone in the catalytic selective oxi-
dation of organic compounds under eco-friendly conditions and this state of
ferment goes on. In this context, a key role has been played by gold, whose
catalytic properties are rapidly owing into applications rich in promising
results. Starting from liquid phase processes carried out under mild con-
ditions, gold catalysis is fast extending to gas phase processes at higher
temperature with comparable perspectives. The focus of the extraordinary
peculiarities of gold in catalysis is often represented by its highly dispersed
nanometric particles.
A novel scenario is now emerging: the application of gold in material
science, particularly promising in the facile polymerization of aniline and
pyrrole via environmentally friendly routes. Even though methods and
techniques have still to be rened, the progress in oxidation reactions by
gold and its successful versatility will contribute to the denitive decline of
the so-called stoichiometric oxidants, so far used in organic synthesis but
producing undesired wastes.
Catalysis appears to be the powerful tool for making environmentally
friendly processes a wide reality.
Table 15 Conductivity data of polypyrrole samples
Sample (thickness [mm]) 0V (S c
1
) 0.5V (S cm
1
) 1V (Scm
1
)
2 (0.69) 2.46 10
3
5.88 10
4
4.80 10
4
3 (1.10) 5.09 10
3
1.38 10
3
3.84 10
3
4 (0.63) 8.94 10
4
1.39 10
3
4.09 10
3
18 (0.64) 8.47 10
4
9.97 10
4
7.23 10
4
19 (0.60) 1.33 10
3
6.17 10
4
3.34 10
4
20 (0.67) 4.81 10
3
2.70 10
3
4.85 10
3
21 (0.64) 9.00 10
4
6.04 10
4
4.56 10
4
22 (0.68) 2.74 10
4
5.53 10
4
4.97 10
4
Table 16 Comparison among dierent conductivity data
Research groups Conductivity (S cm
1
)
Rossi et al.
85
2.7 10
4
5.1 10
3
Chao and March
116
5.0 10
3
2.8
Toshima and Tayanagis
125
10
2
Izumi and Toshima
124
10
10
2.1 10
2
Diaz and Fanazawa
117
10100
Catalysis, 2010, 22, 279317 | 313
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