Chemical Engineering Journal xxx (2012) xxxxxx

Contents lists available at SciVerse ScienceDirect

Chemical Engineering Journal

journal homepage: www.elsevier.com/locate/cej

Preferential CO oxidation over bimetallic PtCo catalysts prepared via double

complex salt decomposition
D.I. Potemkin a,b, E.Yu. Filatov b,c, A.V. Zadesenets b,c, P.V. Snytnikov a,b,, Yu.V. Shubin b,c, V.A. Sobyanin a,b
a

Boreskov Institute of Catalysis, Pr. Lavrentieva 5, Novosibirsk 630090, Russia

Novosibirsk State University, Pirogova St. 2, Novosibirsk 630090, Russia
c
Nikolaev Institute of Inorganic Chemistry, Pr. Lavrentieva 3, Novosibirsk 630090, Russia
b

" Catalyst preparation via

"
"
"
"

[Co(H2O)6][Pt(NO2)4]2H2O double
complex salt decomposition.
Close contact between Pt and Co
atoms.
Bimetallic alumina and ceria
supported PtCo catalysts.
PtCo/Al2O3 catalyst exhibited high
activity and selectivity.
Platinum-rich PtCo alloy
nanoparticles supported over the
alumina surface.

a r t i c l e

i n f o

Article history:
Available online xxxx
Keywords:
CO removal
Preferential CO oxidation
Hydrogen-rich gas
PtCo catalysts
Bimetallic catalysts
Microchannel reactor

g r a p h i c a l a b s t r a c t
100

80

Pt 0.5Co 0.5

XCO, %

h i g h l i g h t s

60
40
20

PtCo-Ce
PtCo-Al
Cu-Ce

0
50

100

150

200

250

T, C

a b s t r a c t
Bimetallic alumina and ceria supported PtCo catalysts were prepared via the decomposition of a
[Co(H2O)6][Pt(NO2)4]2H2O double complex salt. Catalysts were tested in CO preferential oxidation
(PROX). PtCo/Al2O3 catalyst exhibited high activity and selectivity. It provided the CO conversion higher
than 80% and selectivity above 60% in the temperature interval 90165 C at WHSV of
260,000 cm3 g1 h1 and O2/CO ratio of 0.6. XRD and TEM analysis indicated the formation of a platinum-rich PtCo alloy nanoparticles supported over alumina surface.
2012 Elsevier B.V. All rights reserved.

1. Introduction
The low-temperature proton-exchanged membrane fuel cell
(PEM FC) is an attractive power source for transport and portable
applications. One of the promising methods of hydrogen production for application in a PEM FC is the on-board generation from
hydrocarbon fuels, such as gasoline, natural gas, alcohols, and
ethers through its reforming, followed by the CO water gas shift
(WGS) reaction. Typically, the obtained hydrogen-rich gas contains

Corresponding author at: Boreskov Institute of Catalysis, Pr. Akademika

Lavrentieva 5, Novosibirsk 630090, Russia. Fax: +7 383 326 97 48.
E-mail address: pvsnyt@catalysis.ru (P.V. Snytnikov).

0.52.0 vol.% CO, which poisons the FC anode catalyst and must be
removed to a level below 10 ppm. CO preferential oxidation
(PROX) is an efcient method for CO removal from a hydrogen-rich
gas mixture.
Supported monometallic noble (Pt or Ru), gold and copperceria catalysts are reported to be highly active in CO PROX [110].
Among supported bimetallic systems proposed for CO PROX, Pt
Co catalysts are one of the most active and could oxidize CO in
H2-rich gas in a wide temperature interval [1116]. As noted in
the most published research articles, these systems demonstrate
higher activity compared to respective monometallic catalysts
with similar platinum or cobalt loadings.
PROX performance of PtCo catalysts in the packed-bed reactors and wall-coated microreactors were studied in several works

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.07.037

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

[1116]. Authors of [13] investigated samples with different cobalt

content. The catalyst containing 5 wt.% Pt and 4.5 wt.% Co, that corresponds to Pt:Co atomic ratio of 1:3, was found to be the most
active and selective. XRD analysis showed the presence of Co3O4,
CoO and spinel CoAl2O4 phases, no peaks referred to metallic Pt
or bimetallic PtCo phases were detected, probably due to high
Pt dispersion. According to XPS and TPR data, the authors attributed high CO PROX activity and selectivity to the formation of
PtCo solid solution. The same conclusion was made in recent
work [14] on the basis of SAED analysis of catalysts TEM images,
which showed the formation of PtCo interphase, probably Pt3Co
intermetallic compound. Kwak and co-workers [12] demonstrated
that sodium additive to the PtCo/Al2O3 catalysts inhibited the
interaction between cobalt and alumina, resulting in the suppression of the formation of the surface cobalt spinel species. As a result, sodium promoted the formation of the PtCo bimetallic
interphase on the platinumcobalt catalysts and increased the
low temperature CO PROX activity. Komatsu and Tamura [15]
investigated the CO PROX performance of silica supported Pt3Co
intermetallic compound, and noted that synergetic effect of Co
additive to Pt in CO oxidation reaction could be attributed not only
to higher Pt dispersion but also to intrinsic activity increase. They
proposed two main reasons for this synergetic effect:
 realization of bifunctional mechanism, when CO adsorption and
activation occur over Pt, oxygen activation occurs over Co and
reaction proceeds over PtCo interface;
 extension of the PtPt atomic distance (geographic effect) and
electron transfer from Pt to Co (electronic effect) result in a
weaker CO adsorption and accelerated CO oxidation.
Thus, since unmodied Pt/Al2O3 catalysts show insufcient CO
PROX selectivity [2], it is critically important to provide close contact of Pt and Co atoms for reaching high activity and selectivity of
bimetallic PtCo/Al2O3 catalysts.
Microreactors provide much more efcient approach for realization of on-board or portable hydrogen purication by CO PROX
process [4,1720]. Microchannel reactors are characterized by high
heat and mass transfer rates, high surface to volume ratio and
small scales. A high rate of heat removal from the thin catalytic
lm deposited onto the microchannel walls allows near-isothermal
operation and thus prevents the side reactions (viz., hydrogen oxidation or reverse WGS), rising selectivity and extending the operational window [17,21,22]. The performance of PtCo/Al2O3
catalytic coatings in microreactors was investigated in several
works [11,13,14]. Kim and co-authors [11] compared performance
of CuO/CeO2 and PtCo/Al2O3 coated microchannel reactors. The
PtCo system showed higher activity, but was less selective than
the copper-ceria one. A microreactor proposed in work of Yu and
co-workers [14] demonstrated selectivity less than 35% at high
conversion values. Low selectivity of PtCo catalysts could be associated with unselective formation of bimetallic particles over support surface, since without contact with cobalt, monometallic
platinum behaves in CO PROX in the same way as Pt/Al2O3 catalyst,
thereby decreasing the process selectivity. The catalysts were typically prepared by alumina coating sequential incipient wetness
impregnation with chloroplatinic acid and cobalt nitrate. The samples were dried and calcined after each impregnation and nally
reduced by hydrogen [11,13]. Another method consisted in coimpregnation of alumina with chloroplatinic acid and cobalt nitrate acidic solution [14]. Thus, in both cases there was no specic
interaction between Pt and Co atoms providing selective formation
of bimetallic particles. Moreover, since alumina surface in acidic
medium can adsorb anions on amphoteric hydroxyl groups, formation of highly dispersed monometallic platinum particles could be
predominant.

Our aim was to develop the preparation procedure for PtCo

catalysts providing close contact of Pt and Co atoms over the support surface and appropriate for catalyst washcoat preparation.
The proposed approach is based on the decomposition of double
complex salts directly on the support surface that provides an
effective and simple way to obtain supported alloy nanoparticles.
Double complex salts (DCSs) of transition metals coordination
compounds composed of a complex cation of one metal and complex anion of another metal have a number of advantages as precursors for nanoalloy catalysts:
 complexing metals in a double complex salt are mixed on a
molecular level that allows one-step formation of alloys and
intermetallides (including the meta-stable ones) upon salt
decomposition;
 stoichiometry of a precursor complex determines the composition of the polymetallic products;
 possibility to preset exact phase composition and morphology
of the alloy nanoparticles by varying the DCS decomposition
conditions temperature and atmosphere (oxidizing, reducing
or inert one).
In our previous work [16], we studied Pt0.5Co0.5/C, Pt0.5Co0.5/
Al2O3 supported catalysts and Pt0.5Co0.5 powder prepared via the
decomposition of a double complex salt [Co(NH3)5NO2]
[Pt(NO2)4]1.5H2O in hydrogen. The platinumcobalt powder consisted of the Pt0.5Co0.5 unordered solid solution phase with additives of a PtCo intermetallic compound and Pt0.9Co0.1 alloy
phases. Unfortunately, only indirect proofs allowed conclusion on
the formation of similar bimetallic particles on support surface;
attempts to detect these particles by physicochemical methods
appeared unsuccessful.
In present work we report our results on catalyst preparation
via the [Co(H2O)6][Pt(NO2)4]2H2O double complex salt decomposition, catalyst characterization and testing in CO PROX; the comparison with Cu/CeO2x catalyst is given as well.

2. Experimental
2.1. [Co(H2O)6][Pt(NO2)4]2H2O preparation
K2[Pt(NO2)4] (1.00 g) was dissolved in 10 ml of water, then
equimolar amount (0.80 g) of Co(ClO4)26H2O was added. The solution was cooled to 0 C and kept for 1 h. The obtained deposit of
KClO4 was separated on a glass porous lter and washed out with
ice water, acetone and ether. After boiling out in air, large crimson
crystals were obtained. Since the product readily lost water upon
staying in open air, it was left in the mother liquor and stored in
a cup under Paralm cover.

2.2. Catalyst preparation

The ceria support with a BET surface area of 100 m2 g1 was
prepared by calcination of Ce(NO3)36H2O at 400 C for 2 h in air.
Bimetallic PtCo catalysts were prepared by incipient wetness
impregnation of support materials (c-Al2O3 (commercial) with
SBET = 200 m2 g1, and CeO2) with the required quantities of
[Co(H2O)6][Pt(NO2)4]2H2O aqueous solutions. Then the samples
were dried overnight at room temperature. Afterwards the
catalysts were reduced in hydrogen stream at 400 C for 4 h.
The Cu/CeO2 catalysts was prepared by incipient wetness
impregnation of ceria with the required quantity of an aqueous
solution of Cu(NO3)2, then dried at 110 C in air, and calcined at
400 C in air for 2 h.

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

Thus, 3.85 wt.% Pt1.15 wt.% Co/CeO2, 3.85 wt.% Pt1.15 wt.%
Co/Al2O3 and 5.0 wt.% Cu/CeO2 catalysts, further denoted as
PtCoCe, PtCoAl and CuCe, respectively, were prepared.
2.3. Thermal analysis
Thermal properties of the prepared samples were studied on a
NETZSCH STA 409 PC Luxx thermoanalyzer with Al2O3 powder as
a standard. The experiments were run in an open alumina crucible
in a helium stream at a heating rate of 515 C min1. Analysis of
thermal data was carried out with the NETZSCH Proteus Thermal
Analysis v.4.8.1 software.
2.4. Catalysts characterization
The single crystal X-ray diffraction study was carried out on a
BRUKER X8 APEX CCD diffractometer at room temperature and at
196 C using graphite-monochromated Mo Ka irradiation (h/2h
scanning in the range of 1.530). The structures were solved by
the standard heavy atom method and rened in anisotropic
approximation. All calculations were performed with the SHELX97
program package.
The XRD analysis of the sample powders was performed on a
DRON-SEIFERT-RM4 diffractometer
(Cu Ka irradiation, graphite
0
monochromator d001 = 3.345
A, room temperature). The scanning
range was 560 (2h) for double complex salts and 20120 (2h)
for catalysts with a step of 0.03. The experimental diffraction data
were processed using the PowderCell v.2.4 and WINFIT 1.2.1 programs, which allowed a calculation of the quantitative phase composition, the lattice parameters, and the crystallite size. Data from
the PDF database [23] were used as the reference. Bimetallic phase
compositions were determined from the lattice parameters using
experimental calibration curve built on literature and experimental data according to [24]. The error in the composition determination did not exceed 0.03 at.%.
The composition of the catalysts was determined by atomic
absorption spectrometry (AAS) on a Hitachi Z-8000.
The BET specic surface area (SBET) and pore volume of the catalysts were determined from the complete nitrogen adsorption
isotherms at 196 C (ASAP 2400 instrument).
The AAS and textural data of the samples are presented in the
Table 1.
HR TEM measurements were performed using a JEM-2010 electron microscope (lattice plane resolution 0.14 nm at accelerating
voltage of 200 kV). Images of periodic structures were analyzed
by Fourier method. Local energy-dispersive X-ray analysis (EDXA)
was carried out using an EDX spectrometer (EDAX Co.) tted with
a Si (Li) detector with a resolution of 130 eV. The error of the metal
particle composition determination typically was not less than
0.05 at.%. The samples for the HRTEM study were prepared on perforated carbon lm mounted on a copper grid.
X-ray photoelectron spectroscopy (XPS) studies of PtCoAl before and after the reaction were carried out using an ES300 electron spectrometer by Kratos Analytical with Al Ka irradiation
0
(hm = 1486.6 eV). Analysis maximum depth did not exceed 100
A.
The spectra were calibrated using the Al2p line with energy of
74.5 eV. The qualitative analysis of catalysts chemical composition
was done using samples integral spectra, the integral intensities of

the lines or their components (energy range 01000 eV, step 1 eV

and HV = 50). The quantitative chemical composition of catalyst
surface was calculated using the intensities of the most intensive
lines of each component, subject to the atomic sensitivity factors
reported in [25].
2.5. Activity test for preferential oxidation of CO
The CO PROX reaction was performed in a xed-bed U-shape
quartz ow reactor (i.d.: 3 mm, catalyst bed length: 30 mm) at
1.3 bar pressure. A portion of 0.05 g of the catalyst (particle diameter 0.10.2 mm) mixed with 0.15 g of quartz (the same fraction as
that of the catalyst) to facilitate dissipation of the reaction heat,
was placed in the reactor. The temperature was measured by a
K-type thermocouple in the middle of the catalyst bed.
The experiments were performed with the following model gas
feed compositions, vol.%: 1 CO, 0.6 O2, 10 H2O, 20 CO2, 60 H2 with
He as balance. Total feed ow rate was 230 cm3 min1 (STP) which
corresponded to WHSV of 276 000 cm3 g1 h1. Prior each experiment, the catalyst was treated for 1 h in the reaction mixture at
200 C in the case of PtCo samples and at 250 C in the case of
Cu/CeO2. Afterwards, several cycles of temperature decreasing/
increasing were performed.
The inlet and outlet concentrations were determined using a
Chromos GC-1000 chromatograph equipped with molecular sieve
5A and Porapak Q columns and with thermal-conductivity (TCD)
and ame-ionization (FID) detectors. The combination of a methanator (containing a reduced NKM-4 nickel catalyst) and the FID allowed highly sensitive analysis of CO, CO2, and the gaseous
hydrocarbons in the gas mixture. The detection limit of the CO,
CH4, and CO2 concentrations was 1 ppm, that of O2 10 ppm.
The conversions of CO (XCO) and O2 (XO2), and the selectivity towards oxygen consumption (SCO) were calculated from the following equations:

XCO

COinlet  COoutlet
 100%
COoutlet

X O2

O2 inlet  O2 outlet
 100%
O2 inlet

SCO

1 COinlet  COoutlet

 100%;
2 O2 inlet  O2 outlet

where [CO]inlet and [O2]inlet are the inlet concentrations of CO and

O2, respectively; [CO]outlet and [O2]outlet are the outlet concentrations of CO and O2, respectively.
3. Results
3.1. [Co(H2O)6][Pt(NO2)4]2H2O decomposition
The structure of
double
complex salt
[Co(H2O)6]
[Pt(NO2)4]2H2O (CCDC 424506) was conrmed by single crystal
X-ray diffraction technique. Thermal properties of the compound
were studied in inert and reducing atmospheres. The double complex salt readily lost coordination water even at room temperature.
In hydrogen ow, thermal explosion occurred at 140C due to

Table 1
The AAS and textural data.
Sample

Pt measured (set) (wt.%)

Co measured (set) (wt.%)

Pt/Co atomic ratio

SBET (m2 g1)

Pore volume (cm3 g1)

PtCoCe
PtCoAl
CuCe

3.9 (3.85)
3.2 (3.85)

1.1 (1.15)
1.0 (1.15)

1.07
0.97

88
190
80

0.21
0.48
0.21

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

500
400
300

90
85

200

80

100

PtCo-Ce

T, C

140C

95

m, %

TG

100

CeO 2

T
75
0

10

15

20

25

30

35

30

0
40

35

t, min
[Co(H2O)6][Pt(NO2)4]2H2O

100
90

45

50

PtCo-Al

Co[Pt(NO2)4]2H2O

80

m, %

40

2,o

Co[Pt(NO2)4]

-Al2O3

70

difference curve

60

Co2O3 + Pt
CoO + Pt

50

20

40

60

2,

40
100 200 300 400 500 600 700 800 900

80

100

T, C

Fig. 2. XRD patterns of PtCoCe (a), PtCoAl (b) and support materials.

Fig. 1. TG curves for DCS [Co(H2O)6][Pt(NO2)4]2H2O in hydrogen (a) and helium (b)
atmospheres.

cles on their surface. The EDX analysis of these areas proves the
presence of both platinum and cobalt, with atomic ratio Pt/Co
being close to 1, in good agreement with the catalyst preparation
protocol. However, the microphotograph resolution appeared
insufcient for determining interplanar distances and identication of nanoparticle composition. The problem of the particle
metallic or oxide nature remains unclear so far.
The micrograph of PtCoAl as-synthesized catalyst (Fig. 3b) also
shows the presence of nanoparticles of predominant size 25 nm
on the alumina surface. Besides, some amount of large (10
20 nm) particles is observed as well (Fig. 3b). The EDX analysis of
large area (Fig. 3b, area 2) proves atomic ratio Pt/Co to be close
to 1 that complies with the synthesis protocol. However, analysis
of areas 1, 3, 4 (Fig. 3b) with high concentration of metal particles
shows that predominant composition of the particles is close to
Pt0.9Co0.1. Due to high metal particle composition determination
error and low number of the analyzed particles, this result does
not contradict with the XRD data.
Catalyst PtCoAl showed no signicant morphological changes
during the reaction (Fig. 3c and d). The active component consisted
mainly of bimetallic alloy nanoparticles of composition Pt0.9Co0.1.
At the same time, some amount of monometallic Pt and Co particles (Fig. 3c) and bimetallic particles of composition Pt0.5Co0.5
(Fig. 3d) were observed as well.

rapid reaction of complete metals reduction (Fig. 1a). Single-phase

unordered solid solution Co0.5Pt0.5 was the end product of thermolysis. At 400C (nal TGA temperature), the average crystallite size
was 8 nm (according to XRD data).
In helium atmosphere (Fig. 1b), no cobalt reduction occurred.
Complete removal of water from the salt structure yielding
Co[Pt(NO2)4] was reached at ca. 170 C. Afterwards, coordination
surrounding of platinum decomposes releasing metallic platinum.
Upon further heating, cobalt oxide phases appeared with a
stepwise-decreasing content of oxygen. Chemical formulas of the
compounds presented in Fig. 1b were calculated using mass loss
values; composition of nal products of thermolysis (mixture of
Pt and CoO) was proved by powder diffraction data.
3.2. XRD
The XRD pattern of catalyst PtCoCe (Fig. 2a) contains only ceria
peaks; no peaks of metals and platinum or cobalt oxides are observed. The XRD pattern of PtCoAl demonstrates the peaks of support (c-Al2O3) and phase with FCC lattice (Fig. 2b). The processing of
the difference curve of the supported catalyst and support allowed
determination of the FCC phase lattice parameter a = 3.909 , that
corresponds to solid solution Co0.05Pt0.95. This composition mismatches the precursor stoichiometry and therefore residual cobalt
most likely presents in a form of highly dispersed cobalt oxide particles, or surface species of spinel CoAl2O4. The average size of
Co0.05Pt0.95 particles estimated from XRD data was 3 nm.
3.3. TEM
The TEM image of PtCoCe catalyst (Fig. 3a) clearly shows the
ceria crystallites with small (predominantly 25 nm) metal parti-

3.4. XPS
The Pt4f and Co2p regions of the as-synthesized and used PtCo
Al are shown in Fig. 4. The Pt4f line overlapped with strong Al2p
line. Spectra deconvolution showed that Pt existed in metallic state
and no changes in binding energies were observable after the reaction. Cobalt in the catalysts was found in the oxide form with bond
energies corresponding to Co2+ and Co3+ [26]. The authors of [26]
also note that the amount of cobalt oxides over the surface of the
studied 40 wt.% PtCo(1:1)/C catalyst is substantially higher in

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

Fig. 3. TEM images of as-synthesized PtCoCe (a) and PtCoAl (b) and used PtCoAl (c and d) catalysts.

74.5

3+

Al

70.8 Pt

Pt4f

After reaction

Before reaction

70

75

80

Binding energy, eV

781.8

2+

Co2p

Co

787.5

Atomic percentage

Al

Pt

Co

PtCoAl before reaction

PtCoAl after reaction

9.4
13.8

74.1
69.4

15.6
15.9

0.13
0.13

0.78
0.83

etc.) 3d-transition metal [12,2628]. To observe true cobalt

state under the reaction conditions, in situ XPS experiments are
needed. This suggestion explains also the absence of metal cobalt
signal in XPS spectra of the samples. The cobalt state remained
unchanged after the reaction. The surface atomic compositions of
the PtCoAl sample before and after the reaction are presented in
Table 2. The Pt content on the catalyst surface did not change
during the reaction, while Co content slightly increased that could
be associated with partial reduction of cobalt oxides during the
reaction (or with full reduction of small CoOx particles in the
reaction atmosphere and their partial oxidation in the ambient air).

3+

Co

3.5. PROX
After reaction

781.5

Before reaction

780

Table 2
Atomic surface composition of PtCoAl samples before and after the reaction.

795

810

Binding energy, eV
Fig. 4. Pt4f (a) and Co2p (b) spectra of PtCoAl before and after the reaction.

relation to their Co-metal content. This observation can be explained by the oxidation of the surface cobalt atoms by ambient
oxygen which is typical for systems noble metal (Au, Pt, Rh,

The CO PROX performance of the catalysts was studied in the

oxygen decient mixture to make clearly observable the difference
in samples activity and selectivity and to minimize the non-isothermicity of the catalyst bed.
The obtained results are presented in Fig. 5. All catalysts demonstrated typical volcano-type CO conversion curves. The decrease in CO conversion at elevated temperatures occurs due to
oxygen scarcity caused by acceleration of undesirable concurrent
hydrogen oxidation reaction. Reverse watergas shift reaction does
not occur under these conditions. No CO formation was detected in
model experiments with the CO-free mixture at temperatures below 200 C in the case of PtCoAl and 300 C in the case of Cu
Ce. No methane formation was observed in all experiments.
In case of PtCoAl and CuCe catalysts, the observed temperature dependences of XCO, SCO and XO2 were fully reproduced in subsequent cycles of temperature increasing/decreasing. On the
contrary, the PtCoCe catalyst showed transient behavior at low

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

100

ture region of high CO conversions with CuCe was much narrower

than that with PtCoAl.

80

4. Discussion

XCO, %

60
40
PtCo-Ce
PtCo-Al
Cu-Ce

20
0
50

100

150

200

250

200

250

T, C
100

SCO, %

80
60
40
PtCo-Ce
PtCo-Al
Cu-Ce

20
0
50

100

150
o

T, C
100

60

XO , %

80

40
PtCo-Ce
PtCo-Al
Cu-Ce

20
0
50

100

150

200

250

T, C
Fig. 5. The temperature dependences of CO conversion (a), selectivity (b) and
oxygen conversion (c) for PtCoCe, PtCoAl and CuCe catalyst. Inlet gas composition (vol.%): 1.0 CO, 0.6 O2, 10 H2O, 20 CO2, 60 H2 and He-balance. WHSV:
260,000 cm3 g1 h1. Points with lines are experimental data. The crosshatched
regions are the experimental points with the random variations of PtCoCe
catalysts activity and selectivity at temperature below 155 C.

temperatures. The XCO, XO2 and SCO values of the PtCoCe catalyst
were within the crosshatched regions at temperatures below
155 C (Fig. 5). All experimental points were between upper and
lower temperature curves with the random variations of catalysts
activity and selectivity both for increasing and decreasing cycles of
the catalyst temperature during the experiments.
The PtCoAl catalyst showed the highest CO conversion of 93.4%
at 109 C and selectivity of 72%. At this temperature, the oxygen
conversion over PtCoAl reached 100%. PtCoAl demonstrated high
CO conversion and selectivity in a wide temperature range,
XCO > 80% and SCO > 60% in the temperature range 90165 C. The
maximum CO conversion demonstrated by the PtCoCe catalyst
was 66.3% at 109 C. The CuCe catalyst showed high CO PROX performance at high temperatures 150250 C with maximum CO
conversion of 84.2% at 196 C and selectivity of 77%. The tempera-

The CO PROX promising catalysts must meet the requirements

of operability in the temperature interval from 80 (working temperature of Naon-based fuel cell) to 250 C (low temperature
watergas shift reaction) and ability to decrease the CO concentration from 12 vol.% to 10 ppm consuming the minimum amount of
oxygen (i.e., minimizing the side reaction of hydrogen oxidation).
Pure noble metal-based catalysts, such as Al2O3-supported Pt or
Pd are excellent catalysts for hydrogen oxidation through the classical LangmuirHinshelwood mechanism [12]. In the presence of
CO, hydrogen oxidation is inhibited due to strong CO adsorption
and high CO coverage that blocks the sites for H2 and O2 adsorption
and dissociation [29]. With a rise in temperature, the CO coverage
decreases and the CO and H2 oxidation reactions start competing
for oxygen. Therefore, the selectivity of unmodied Pt and Pd catalysts is not very high.
Addition of 3-d transition metals, such as Co [1116], Fe [30,31]
or Cu [28,32,33], to platinum catalysts to produce bimetallic species opens an additional low-temperature CO oxidation reaction
pathway through oxygen activation over additional atoms and
CO oxidation at the interface between two metals.
In the present work, we succeeded to obtain highly active and
selective CO PROX catalyst PtCo/c-Al2O3. The catalyst active component consists mainly of the Pt-rich alloy species of composition
Pt0.95Co0.05, while the major part of cobalt seems to be distributed
over support surface in a form of dispersed cobalt oxide species.
This conclusion is suggested by the results of the catalysts analysis
by various physicochemical methods, which agree well with each
other. Nonselective formation of solid solution species on the alumina surface may be attributed to competitive adsorption of cobalt
aqua-complex [Co(H2O)6]2+ on the surface hydroxyl groups.
Compared to literature data [1114], our catalyst differs by considerably lower cobalt loading. The authors of [13] noted that the
catalysts which showed the best CO PROX performance contained
5 wt.% Pt and 4.5 wt.% Co, that corresponds to Pt: Co atomic ratio
ca. 1:3. Evidently, during preparation of PtCoAl catalyst, a part
of cobalt cations form a double complex salt, that provides a most
tight contact of Pt and Co atoms at subsequent thermal treatment.
As a result, the catalyst demonstrates improved activity and selectivity together with lower Co loading as compared to [13].
In contrast to catalyst PtCoAl, the PtCoCe sample demonstrated unusual catalytic performance in low-temperature region
that may be explained by unsteady-state kinetics of the reaction
in this region and incomplete isothermality of the catalyst bed.
In contrast to alumina, ceria contains active lattice oxygen which
can participate in the reaction. Simultaneous existence of several
active oxygen species on the catalyst surface (which induces nonlinearity of respective kinetic equations describing the catalyst
behavior) enables unsteady behavior and alteration of catalyst surface state with time [34], as it was demonstrated in the simplest
model of the self-oscillation in CO oxidation rate over Pd, proposed
by Sales et al. [35,36]. Detailed investigation of the observed phenomenon stays beyond the frames of the present work; it is
planned to be studied later. Lower selectivity of PtCoCe samples
could be also associated with the ceria oxygen mobility and with
strong interaction of metals particles with the support.
As mentioned above, to rich the most efcient CO removal and
wide temperature window, it is worth to perform the CO PROX
process in microchannel reactors containing thin catalyst lms
(coatings) on the walls. The catalyst can be prepared through
two main steps. First, the coating is formed from the support by

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037

D.I. Potemkin et al. / Chemical Engineering Journal xxx (2012) xxxxxx

depositing it onto the channel walls [4,14,17,37], or the support/

catalyst layer is prepared directly from the wall material [38]. Second, the active component is deposited onto this support coating,
typically by impregnation. This approach imposes some limitations
on the catalyst preparation procedures. In the case of supported
bimetallic alloy nanoparticles, such techniques as decomposition
of cluster compounds or preparation of surfactant-stabilized colloids that provide selective formation of alloy nanoparticles, are
not feasible. Decomposition of double complex salts inside the
pores of support is an effective and simple way to deposit alloy
nanoparticles directly on the support-coated channel walls.
5. Conclusions
Thus, simple and convenient procedure to prepare bimetallic
PtCo catalysts, based on decomposition of double complex salt
[Co(H2O)6][Pt(NO2)4]2H2O, is proposed in the present work. The
procedure allows reaching close contact between Pt and Co atoms
that provides high activity and selectivity of the catalysts for CO
PROX reactions. The method can be adapted readily for supporting
thin catalytic lms over walls of microchannel reactors.
Acknowledgements
The authors are grateful to Dr. A.I. Stadnichenko and Mr. A.V.
Ishchenko for assistance in XPS and TEM analysis.
The work was partially supported by GC No. 11.519.11.3021 in
the framework of the Russian FFP 20072013, SB RAS Integration
Project No. 124 and RFBR Grant 11-03-00668.
References
[1] P.V. Snytnikov, V.A. Sobyanin, V.D. Belyaev, P.G. Tsyrulnikov, N.B. Shitova, D.A.
Shlyapin, Selective oxidation of carbon monoxide in excess hydrogen over Pt-,
Ru- and Pd-supported catalysts, Appl. Catal. A 239 (2003) 149.
[2] A. Manasilp, E. Gulari, Selective CO oxidation over Pt/alumina catalysts for fuel
cell applications, Appl. Catal. B 37 (2002) 1725.
[3] M.J. Kahlich, H.A. Gasteiger, R.J. Behm, Kinetics of the selective CO oxidation in
H2-rich gas on Pt/Al2O3, J. Catal. 171 (1997) 93105.
[4] G. Kolb, V. Hessel, V. Cominos, C. Hofmann, H. Lwe, G. Nikolaidis, R. Zapf, A.
Ziogas, E.R. Delsman, M.H.J.M. de Croon, J.C. Schouten, O. de la Iglesia, R.
Mallada, J. Santamaria, Selective oxidations in micro-structured catalytic
reactorsFor gas-phase reactions and specically for fuel processing for fuel
cells, Catal. Today 120 (2007) 220.
[5] D.L. Trimm, Minimisation of carbon monoxide in a hydrogen stream for fuel
cell application, Appl. Catal. A 296 (2005) 111.
[6] D.I. Potemkin, P.V. Snytnikov, V.P. Pakharukova, G.L. Semin, E.M. Moroz, V.A.
Sobyanin, Coppercerium oxide catalysts prepared by the Pechini method for
CO removal from hydrogen-containing mixtures, Kinet. Catal. 51 (2010) 119
125.
[7] P.V. Snytnikov, A.I. Stadnichenko, G.L. Semin, V.D. Belyaev, A.I. Boronin, V.A.
Sobyanin, Coppercerium oxide catalysts for preferential carbon monoxide
oxidation in hydrogen-rich mixtures: I. Catalytic activity, Kinet. Catal. 48 (3)
(2007) 439447.
[8] G. Avgouropoulos, T. Ioannides, H.K. Matralis, J. Batista, S. Hocevar, CuOCeO2
mixed oxide catalyst for the selective oxidation of carbon monoxide in excess
hydrogen, Catal. Lett. 73 (2001) 3340.
[9] Y. Denkwitz, B. Schumacher, G. Kucerova, R.J. Behm Activity, Stability, and
deactivation behavior of supported Au/TiO2 catalysts in the CO oxidation and
preferential CO oxidation reaction at elevated temperatures, J. Catal. 267
(2009) 7888.
[10] C. Galletti, S. Fiorot, S. Specchia, G. Saracco, V. Specchia, Catalytic performance
of AuTiO2 catalysts prepared by depositionprecipitation for CO preferential
oxidation in H2-rich gases, Chem. Eng. J. 134 (2007) 4550.
[11] K.-Y. Kim, J. Han, S.W. Nam, T.-H. Lim, H.-I. Lee, Preferntial oxidation of CO over
CuO/CeO2 and PtCo/Al2O3 catalysts in micro-channel reactors, Catal. Today
131 (2008) 431436.
[12] C. Kwak, T.-J. Park, D.J. Suh, Effects of sodium addition on the performance of
PtCo/Al2O3 catalysts for preferential oxidation of carbon monoxide from
hydrogen-rich fuels, Appl. Catal. A. 278 (2005) 181186.

[13] K.-Y. Kim, S.W. Nam, J. Han, S.P. Yoon, T.-H. Lim, H.-I. Lee, Development of a
multi-layered micro-reactor coated with PtCo/Al2O3 catalyst for preferential
oxidation of CO, J. Ind. Eng. Chem. 14 (2008) 853859.
[14] X. Yu, H. Li, S.-T. Tu, J. Yan, Z. Wang, PtCo catalyst-coated channel plate
reactor for preferential CO oxidation, Int. J. Hydrogen Energy 36 (2011) 3778
3788.
[15] T. Komatsu, A. Tamura, Pt3Co and PtCu intermetallic compounds: promising
catalysts for preferential oxidation of CO in excess hydrogen, J. Catal. 258
(2008) 306314.
[16] P.V. Snytnikov, K.V. Yusenko, S.V. Korenev, Yu.V. Shubin, V.A. Sobyanin, CoPt
bimetallic catalysts for the selective oxidation of carbon monoxide in
hydrogen-containing mixtures, Kinet. Catal. 48 (2) (2007) 276281.
[17] P.V. Snytnikov, M.M. Popova, Y. Men, E.V. Rebrov, G. Kolb, V. Hessel, J.C.
Schouten, V.A. Sobyanin, Preferential CO oxidation over a coppercerium oxide
catalyst in a microchannel reactor, Appl. Catal. A. 350 (2008) 5362.
[18] D.I. Potemkin, P.V. Snytnikov, V.D. Belyaev, V.A. Sobyanin, Preferential CO
oxidation over Cu/CeO2x catalyst: Internal mass transport limitation, Chem.
Eng. J. 176177 (2011) 165171.
[19] P.V. Snytnikov, D.I. Potemkin, E.V. Rebrov, V.A. Sobyanin, V. Hessel, J.C.
Schouten, Design, scale-out, and operation of a microchannel reactor with a
Cu/CeO2x catalytic coating for preferential CO oxidation, Chem. Eng. J. 160
(2010) 923929.
[20] E.R. Delsman, B.J.P.F. Laarhoven, M.H.J.M. De Croon, G.J. Kramer, J.C. Schouten,
Comparison between conventional xed-bed and microreactor technology for
a portable hydrogen production case, Chem. Eng. Res. Des. 83 (2005) 1063
1075.
[21] X. Ouyang, R.S. Besser, Effect of reactor heat transfer limitations on CO
preferential oxidation, J. Power Sources. 141 (2005) 3946.
[22] X. Ouyang, L. Bednarova, R.S. Besser, P. Ho, Preferential oxidation (PrOx) in a
thin-lm catalytic microreactor: advantages and limitations, AIChE J. 51
(2005) 17581772.
[23] PCPDFWin, Ver 1.30, JCPDS ICDD, Swarthmore, PA, USA, 1997.
[24] A. Zadesenets, E. Filatov, P. Plyusnin, I. Baidina, V. Dalezky, Y. Shubin, S.
Korenev,
A.
Bogomyakov,
Bimetallic
single-source
precursors
[M(NH3)4][Co(C2O4)2(H2O)2]2H2O (M = Pd, Pt) for the one run synthesis of
CoPd and CoPt magnetic nanoalloys, Polyhedron 30 (2011) 13051312.
[25] J.F. Moulder, W.F. Stickle, in: P.E. Sobol (Ed.), Handbook of X-ray Photoelectron
Spectroscopy, PerkinElmer Corporation, Physical Electronics Division, Eden/
Prairie/Minnesota, 1992.
[26] A.S. Arico, A.K. Shukla, H. Kim, S. Park, M. Min, V. Antonucci, An XPS study on
oxidation states of Pt and its alloys with Co and Cr and its relevance to
electroreduction of oxygen, Appl. Surf. Sci. 172 (2001) 3340.
[27] X. Liu, A. Wang, L. Li, T. Zhang, C.-Y. Mou, J.-F. Lee, Structural changes of AuCu
bimetallic catalysts in CO oxidation: in situ XRD, EPR, XANES, and FT-IR
characterizations, J. Catal. 278 (2011) 288296.
[28] J. Kugai, R. Kitagawa, S. Seino, T. Nakagawa, Y. Ohkubo, H. Nitani, H. Daimon,
T.A. Yamamoto, C-Fe2O3-supported PtCu nanoparticles synthesized by
radiolytic process for catalytic CO preferential oxidation, Appl. Catal. A. 406
(12) (2011) 4350.
[29] P.V. Snytnikov, V.A. Belyaev, V.A. Sobyanin, Kinetic model and mechanism of
the selective oxidation of CO in the presence of hydrogen on platinum
catalysts, Kinet. Catal. 48 (2) (2007) 93102.
[30] A. Siani, O.S. Alexeev, B. Captain, G. Lafaye, P. Marecot, R.D. Adams, M.D.
Amiridis, Synthesis of cluster-derived PtFe/SiO2 catalysts for the oxidation of
CO, J. Catal. 255 (2008) 162179.
[31] M. Kotobuki, A. Watanabe, H. Uchida, H. Yamashita, M. Watanabe, High
catalytic performance of PtFe alloy nanoparticles supported in mordenite
pores for preferential CO oxidation in H2-rich gas, Appl. Catal. A. 307 (2006)
275283.
[32] J. Kugai, T. Moriya, S. Seino, T. Nakagawa, Y. Ohkubo, H. Nitani, H. Daimon, T.A.
Yamamoto, CeO2-supported PtCu alloy nanoparticles synthesized by
radiolytic process for highly selective CO oxidation, Int. J. Hydrogen Energy
37 (6) (2012) 47874797.
[33] T.S. Mozer, F.B. Passos, Selective CO oxidation on Cu promoted Pt/Al2O3
and Pt/Nb2O5 catalysts, Int. J. Hydrogen Energy 36 (21) (2010)
1336913378.
[34] E.M. Slavinskaya, O.A. Stonkus, R.V. Gulyaev, A.S. Ivanova, V.I. Zaikovskii, P.A.
Kuznetsov, A.I. Boronin, Structural and chemical states of palladium in Pd/
Al2O3 catalysts under self-sustained oscillations in reaction of CO oxidation,
Appl. Catal. A. 401 (2011) 8397.
[35] B.C. Sales, J.E. Turner, M.B. Maple, Oscillatory oxidation of CO over Pt, Pd and Ir
catalysts: theory, Surf. Sci. 114 (23) (1982) 381394.
[36] V.P. Zhdanov, Oscillations in catalytic reactions on the nm scale, Catal. Lett. 69
(2000) 2125.
[37] R. Zapf, G. Kolb, H. Pennemann, V. Hessel, Basic study of adhesion of several
alumina-based washcoats deposited on stainless steel microchannels, Chem.
Eng. Technol. 29 (12) (2006) 15091512.
[38] E.V. Rebrov, S.A. Kuznetsov, M.H.J.M. de Croon, J.C. Schouten, Study of the
water-gas shift reaction on Mo2C/Mo catalytic coatings for application in
microstructured fuel processors, Catal. Today 125 (2007) 8896.

Please cite this article in press as: D.I. Potemkin et al., Preferential CO oxidation over bimetallic PtCo catalysts prepared via double complex salt decomposition, Chem. Eng. J. (2012), http://dx.doi.org/10.1016/j.cej.2012.07.037