Lectura 0. Past, Present and Future of Heterogeneous Catalysis

Catalysis Today 189 (2012) 227
Contents lists available at SciVerse ScienceDirect
Catalysis Today
journal homepage: www.elsevier.com/locate/cattod
The past, present and future of heterogeneous catalysis

Ioana Fechete a , Ye Wang b , Jacques C. Vdrine c,
a
Laboratoire des Matriaux, Surfaces et Procds pour la Catalyse, CNRS UMR 7515, Universit de Strasbourg, 25 rue Becquerel, F-67087 Strasbourg, France
State Key Laboratory of Physical Chemistry of Solid Surfaces and National Engineering Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters, College of Chemistry
and Chemical Engineering, Xiamen University, Xiamen 361005, PR China
c
Laboratoire de Ractivit de Surface, CNRS UMR 7197, Universit Pierre et Marie Curie, 4 Place Jussieu, F- 75252 Paris, France
b
a r t i c l e
i n f o
Article history:
Received 18 January 2012
Received in revised form 4 April 2012
Accepted 5 April 2012
Available online 10 May 2012
Keywords:
Heterogeneous catalysis
History
Industrial realisations
Future
Challenges
New materials
Chemicals
Energy
Environment
a b s t r a c t
This review highlights key catalytic discoveries and the main industrial catalytic processes over the last
300 years that involved commodities, ne chemicals, petrochemicals, petroleum transformation for fuels
and energy supply, emission control, and so forth. In the past, discoveries have often followed events such
as wars or embargos, whereas the current driving forces of studies, researches and then discoveries aim
at a better understanding of catalytic processes, at reducing the costs of raw materials and processes, at
developing new catalytic materials and at addressing environmental issues. This review focuses on the
history of many catalytic industrial processes, environmental issues, catalytic materials, especially their
expected catalytic properties, on catalyst characterisation by physical methods and development of in situ
conditions, i.e., characterisation under actual working conditions with reactants and products analyzed
on-line. Emphasis is also placed on high selectivity in catalytic reactions and the major challenges for the
future, such as environmental issues, energy supply, pollution control for vehicles and industrial plants,
air/VOCs/water purication, hydrogen sources and carbon dioxide storage/up grading, transformation of
biomass as a promising source of raw materials, and catalytic water splitting perspectives.
This review is a survey of heterogeneous catalysis and is not comprehensive but leads to the conclusion
that, although many catalysts and catalytic processes have already been discovered and developed over
the past century, many opportunities nevertheless exist for new developments, new processes and new
catalytic materials. It follows that substantial challenges exist for the younger generation of researchers
and engineers, as emphasized at the end of the manuscript.
2012 Elsevier B.V. All rights reserved.
1. Introduction
Catalysis is an important eld in chemistry, with some 90% of
chemical processes involving catalysts in at least one of their steps
[1]. At present, because of environmental issues, catalysis appears
to be even more important than before and to constitute one of
the major sources of improvements in our society [2,3]. A survey
of U.S. industries revealed that the annual revenue from chemical
and fuel production topped all other industrial sectors. The survey
also showed that more than 60% of the 63 major products and 90%
of the 34 process innovations from 1930 to 1980 have involved
catalysis, which illustrates the critical role of this eld in the fuel
and chemical industries.
This review is intended to present some historical background
of catalysis and the major challenges that this eld has faced in the
last half century and that it still must face in the future. This review
is focused only on heterogeneous catalysis.
Corresponding author. Tel.: +33 144275514.

E-mail address: jacques.vedrine@upmc.fr (J.C. Vdrine).
0920-5861/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2012.04.003
Our aim in this manuscript is to highlight the major catalysisrelated discoveries and processes that have been developed over
the past three centuries. The history of catalysis and its contribution to chemical industries has already been widely described in
the literature, e.g. [46]. We intended to review some historically
signicant steps in the development of catalysis and catalytic processes. Without discussing ancient beer or wine fermentation, it is
interesting to recall some old processes, as summarized in Table 1
[713].
Some of these processes have been developed in response to
driving forces designated as pullers like the expected Chilean
embargo on saltpeter as a nitrate source, which motivated Haber
and Bosch to develop a process for the xation of atmospheric
nitrogen in ammonia synthesis (1909). Similarly, the need for a
more energetic gasoline inspired racing driver and French mechanical engineer Eugne Houdry to develop the oil (hydrocarbon) acid
cracking process (1930), and catalytic reformation and alkylation
(1940), which have allowed the Allied forces to access a powerful
fuel for air planes during World War II.
More recently, driving forces (pullers) have changed and now
correspond more to a market-driven strategy, in which simpler
I. Fechete et al. / Catalysis Today 189 (2012) 227
Table 1
Historical aspects in heterogeneous catalysis [713].
Catalytic process
Catalyst
Main author
Year
Sulfuric acid
Dehydration of alcohols
Esterication of organic acids
Dehydrogenation of alcohols (ethanol)
Oxidation of alcohol
Decomposition of H2 O2 and NH3
Hydrolysis of starch to glucose
Combustion
Decomposition NH3
Oxidation
Oxidation SO2 to SO3 (contact process)
Denition of catalysis
Oxidation of NH3 to nitric acid
HCl + O2 Cl2
Esterication of acid
Hydrolysis of esters
Sulfuric acid
Friedel-Crafts reactions
Nitric acid synthesis
NH3 synthesis from N2 and H2 under high pressure
Hydrogenation
Active site concept
Theory of adsorption
Industrial process of NH3 synthesis under pressure
CO + H2 CH3 OH
CO + H2 hydrocarbons
Contact catalysis theory
Hydrogenation vegetable oils
Catalytic cracking of petroleum
Synthesis gas
Alkylation reaction for gasoline fuel
Synthetic zeolites
Exhaust gas treatment
Lead chamber
Acid
Acid
Metal
Pt black
Metals
Acid
Pt
Fe > Cu > Ag > Au > Pt
Pt
Pt
Roebuck
Priestley
Scheele
Van Marum
Priestley & Dbereiner
Thnard
Kirchoff
Davy
Dulong
Fusinieri
Phillips
Berzelius
Kuhlmann
Deacon
Bertholet
Bertholet
1746
1778
1782
1796
1810
1813
1814
1817
1823
1824
1831
1836
1838
1875
1879
1879
1875
1877
1904
1909
1912
1913
1915
1918
1923
1923
1925
1926
1930
1931
1940
1946
1976
Pt
Cu
Acid
Acid
V2 O5
Lewis acids (AlCl3 )
Pt gauzes
Fe
Ni
Fe
ZnO-chromia
Fe, Co
Ni
Acid
Acid
and less-capital-incentive processes and the use of cheaper feed

stocks are preferred. Since the end of the twentieth century, societal concerns have also become an important modern motivation,
with intensive research being devoted to convert by-products to
useful products and to treat all kinds of wastes for the preservation and protection of the environment. More stringent legislation
has been established which has led to research on new catalytic
materials and more efcient processes. More specically, with
respect to environmental issues, hydrodesulfurization started in
the 1960s as an important method for the removal of sulfur from
fuels. Hydrodesulfurization has resulted in a considerable reduction in global emissions of sulfur oxides, while creating increased
demand for the selective methane reaction (SMR) for H2 production; auto emission control catalysts developed in 1974 (oxidation),
1978 (three-way), and in the 1990s (Pd three-way); the selective catalytic reduction of NOx by NH3 or N2 H4 (SCR) for power
plants in 1980 using V, W, and Ti oxides extruded into monolith forms [14]; ozone emission control catalysts developed by
Engelhard (now BASF); the replacement of CFCs by HCFCs for the
reduction of topospheric ozone concentration (ozone holes), the
catalytic destruction of volatile organic compounds from the consumer products industry; the production of foods and chemicals;
the development of diesel oxidation exhaust catalysts in 1990 using
cerium salt as additive; a variety of solutions that use metal oxides
for catalytic decomposition of N2 O (which resulted in an 81% reduction of all N2 O emissions from the world adipic acid plants); the
development of PtRh-alkali NOx storage catalysts; the development of the Toyota Motor in 1994; the development of diesel
particulate elimination catalysts in 2003; the development of urea
SCR for NOx emissions control in vehicles in 2004; the development
of NOx removal in FCC regenerator units in 2007, and so forth.
New studies have also appeared in the past two or three decades
under driving forces considered as pushers for the development
Friedel & Crafts

Haber
Sabatier
Michaelis
Langmuir
Haber
BASF
Fischer & Tropsch
Taylor
Raney
Houdry
Bergius & Bosch
Ipatieff & Pines
Barrer & Breck
General Motors & Ford
of a molecular-level understanding of catalyst function, surface sensitive spectroscopies, in situ/operando characterisation

techniques, scientic computing, quantum chemistry, molecular
modelling, thermodynamics and kinetics, reaction and reactor
modelling, high-throughput catalyst screening and testing, and
so forth. Signicant improvements have been made in all of these
domains, and further developments should continue in the future.
2. The catalysts
Since ancient times, the development and use of materials have
been one of the basic objectives of our world. Eras, the Stone Age,
the Bronze Age, and the Iron Age, have been named after the fundamental material used by mankind to construct their tools. Materials
science is the modern activity that provides the raw material for this
endless need, demanded by the progress in all elds of industry and
technology, for new materials for the development of society.
The International Union of Pure and Applied Chemistry (IUPAC)
has dened a catalyst as a substance that increases the rate of
a reaction without modifying the overall standard Gibbs energy
change in the reaction [15]. The chemical process of increasing
the reaction rate is called catalysis, and the catalyst is both a reactant and a product of the reaction, i.e., the catalyst is restored after
each catalytic act. Furthermore, the catalyst does not inuence the
thermodynamical equilibrium composition after the cessation of
the reaction.
More efcient catalytic processes require improvements in the
catalytic activity and selectivity. Both aspects can be improved
by the tailored design of catalytic materials with the desired
structures and the desired dispersion of active sites. Materials
such as zeolites, AlPO, SAPO, mesoporous materials, PILC, MOFs,
etc. offer such possibilities in this regard, with controlled large and
accessible surface areas of the catalysts but without standalone
ne particles. Moreover, one of the most important applications of these novel porous solid catalysts is the replacement
of environmentally hazardous, corrosive, difcult-to-separateand-dispose-of homogeneous catalysts (viz. mineral and Lewis
acids, organic and inorganic bases and toxic metallic compounds)
employed in the liquid-phase synthesis of bulk and ne chemicals
(vide infra) [16]. There are many families of solids catalysts like
metals, oxides, suldes, carbons, etc. as bulk materials or supported
on a more or less catalytically active support like silica, alumina,
zirconia, titania, ceria, carbons, etc. These materials may possess
specic chemical properties, such as acid-base or redox or dehydrogenating or hydrogenating or oxidizing, and physical properties
like porosity, high surface area, attrition resistance, thermal and/or
electrical conductivity, etc. The largest family corresponds to
oxides whatever zeolites, clays, mesoporous materials, mixed
oxides as catalysts or as supports. Among them porous materials
present some fascinating properties, which are described below.
2.1. Zeolites
In the petrochemistry and organic synthesis elds, zeolites have
played a major role in the twentieth century. Zeolites are inorganic
crystalline aluminosilicates which structures consist of a threedimensional arrangement of TO4 tetrahedra (where T is usually
Si4+ and Al3+ tetrahedrally coordinated atoms) assembled together
through the sharing of oxygen atoms to form subunits, which repeat
to form an innite lattice [17], consisting of three-dimensional,
fourfold interconnected TO4 tetrahedra linked via TOT bridges.
The TOT angles are ideally 140150 and rarely over 180 . The
existence of Al in a tetrahedrally coordinated Si structure leaves a
negative framework charge, which requires the existence of compensating cations, located in the porous system.
Consequently, an interesting feature of zeolites is the versatility
of their structures that arises from a large number of modication procedures which also tailor their catalytic properties. The
catalytic activity is associated with the presence of active centres
in the framework. Such centres may be acid, their strength and
number (Brnsted, Lewis) being adjusted in a controlled manner
either during synthesis by isomorphous replacement of the central
Si atom in tetrahedral sites in the zeolite lattice, by for example
trivalent elements like Al, B, Fe, Cr, Sb, As, or Ga, and tetravalent
elements like Ge, Ti, Zr, or Hf; and/or post-synthesis including the
steam procedure, chemical vapor deposition, ion exchange of interstitial cations, reduction of exchanged metal ions to a lower valence
state.
A distinction has been made between small-, medium- and
large-pore zeolites. In the case of small-pore zeolites, such as zeolite A, eight SiO4 tetrahedra form a ten member ring (10MR) with
a diameter a 0.41 nm and in the case of large-pore zeolites, such
as Y-zeolite (Fig. 1), a cavity with a diameter of 0.74 nm is formed
Fig. 1. Framework of Faujasite (FAU) zeolite (Y or X-Type Si/Al = 2.5 or 1).
by twelve SiO4 tetrahedra. The medium-pore zeolites, such as pentasil zeolites, contain a ten member ring with an ellipsoidal tubular
diameter of 0.55 0.56 nm. The system of channels and cavities in
these molecular sieves produces solids with very high surface areas
and pore volumes, which are capable of adsorbing large amounts
of hydrocarbons.
Zeolites can be used as sorbents and as catalysts in some catalytic processes. The major breakthrough in zeolite catalysts arose
from the uid catalytic cracking (FCC) process for oil transformation to fuels and chemicals. The addition of zeolites (FAU and MFI)
to acid clays and silicaalumina cracking catalysts in the mid-1960s
resulted in a drastic increase in conversion and gasoline yields as
well as in lower quantities of coke and dry gas [18]. The new catalysts gave gasolines with lower octane numbers, primarily because
of their lower olenicity [1921]. The rst octane-enhancing FCC
catalysts were introduced by catalyst manufacturers in USA in the
mid-1970s. Octane FCC catalysts consist of two major components,
and the zeolites can be used to boost gasoline octane. Chester et al.
[22] have reported that, in addition to MFI (ZSM-5), different members of the MFI family of zeolites (MEL, ZSM-12, ZSM-23, ZSM-35,
ZSM-38) have octane-boosting abilities. Zeolites beta (BEA) [23]
and offretite (OFF) [24] have been reported to produce higher gasoline octane numbers than conventional Y (FAU) zeolites and can be
used as octane-boosting additives.
Major milestones in this domain are summarized below:
R. Milton (Union Carbide in 1950s), D. Breck, R. Barrer and E. Flanigen developed commercially viable routes to various zeolites and
MeAPOs.
J. Rabo, working at Union Carbide, applied the use of zeolites to
petroleum rening (isomerization, 1959), whereas C. Plank and E.
Rosinski of Mobil Oil applied zeolites to catalytic cracking (1962)
of heavy oil fractions.
P. Weisz and V. Frilette of Mobil Oil developed the concept (1960)
of shape-selective catalysts, and W. Haag applied shape selectivity to the production of aromatics.
G. Kerr of Mobil Oil discovered high silica zeolites in 1967 (ZSM-5,
subsequently designated as MFI) and the rst large scale commercial cracking trial was run in 1983.
W. R. Grace discovered the steaming of Y zeolite to produce ultrastable Y (USY) zeolite in 1969.
Mobil Oil developed the siliceous mesoporous-type materials
designated as MCM, HMS, and so forth in the late 1990s.
M. Taramasso, G. Perego, and B. Notari discovered TS-1 (titanium
silicalite-1 with the MFI structure), a selective oxidation catalyst
for the epoxidation of olens, at ENI-SNAM Progetti in 1983.
UOP/HYDRO (1995) developed SAPO-34, a silicoaluminophosphate molecular sieve applied for methanol to olens (MTO
process).
Another fascinating property of zeolites arises from their molecular size porous network, which allows certain reactants to enter
and products to easily leave the pores or cavities, or to remain
trapped, or to leave the pores with difculty if they are too bulky.
This concept, of shape selectivity, pioneered by Mobil scientists
[25], has been developed to explain reactions that do not obey
the classical laws of thermodynamics and that are strongly inuenced by the size of the pores or cavities relative to the size of
the reactant or product molecules. Matching the size and conguration of reacting molecules, intermediates and products with
the geometry and tortuosity of the zeolite channel/cavity system
provides the basis for controlled shape selectivity. Diffusion and
shape-selectivity catalysis in zeolites have been reviewed in several publications [2628]. However, the shape selectivity in zeolites
can manifest itself through: reactant selectivity, product selectivity, transition-state selectivity, molecular trafc control, etc.
Fig. 2. Illustration of a molecule in a pore and shape selectivity in dealuminated mordenite zeolite.
The reactant selectivity, results in the exclusion of molecules too

large to diffuse into the zeolite pores; a simple example is the dehydration of alcohols. Over the narrow-pore zeolite (CaA), n-butanol
is dehydrated, and isobutanol is not. Conversely, as expected, isobutanol is more readily dehydrated than n-butanol over NaX (which
has wider pores). The former result is readily explained because
both forms can enter NaX, but the bulkier isobutanol is excluded
from CaA product selectivity. In addition to size exclusion, entrance
to zeolite crystals may hinder when the unfavorable orientation of
a reactant is caused by electrostatic effects. In this case, the alignment of a zeolitic electrostatic eld (perpendicular to the plane of
the window) and a molecule dipole may restrict entry by electrostatic repulsion, which allows only small molecules formed during
the reaction to diffuse out of the zeolite pores. For example, in the
alkylation of toluene by methanol over H-MFI, yields of p-xylene are
enhanced because the diffusivity of p-xylene is much greater than
that of o- and m-xylenes (vide infra). Even if the primary product of
alkylation is not rich in p-xylene, its more rapid exit from the zeolite allows further isomerization of o- and m-xylenes and results in
increased yields of the p-isomer. Restricted transition-state selectivity occurs when certain reactions are prevented because the
corresponding transition state would require more space than is

available in the pores. Molecular trafc control [29] occurs in zeolites with two types of channel systems. The relationship between
the length of the molecules and the size of the zeolite cage as well
as variations in molecular oscillations [30] also affect zeolite shape
selectivity. In addition to geometric factors, shape selectivity can
be due to electrostatic effects [31] which result from the interaction
between the electric eld at the pore mouth and the dipole moment
of the reactant molecule. Such an interaction can favour or inhibit
the diffusion of the reactant molecule into the zeolite.
The shape selectivity of zeolites can be modied by ion
exchange, dealumination, changes in the framework Si/Al ratio, or
by any modication that affects the pore size or geometry [3245].
The shape selectivity of a zeolite is often characterized by its constraint index, which is the ratio of the cracking rate constants for
n-hexane and 3-methylpentane [46]. Large-pore zeolites have constraint indices less than 1; medium-pore zeolites have constraint
indices between 1 and 12; small-pore zeolites have constraint
indices higher than 12.
The shape selectivity phenomenon is illustrated in
Fig. 2 for the synthesis of 4,4 -di-isopropyl-biphenyl and 2,
Fig. 3. Principe of connement A and anti-connement C, dimensionality [4749].
Fig. 5. Adipic acid processes using the old process (left) and the new process (right).
Fig. 4. Variations of van der Waals energy W and the force between a spherical molecule (radius d) and a spherical micropore (radius a) vs. curvature (s = d/a)
[4749].
6-di-isopropyl-naphthalene compounds that are intermediates

for polyesters or liquid crystals, by alkylation of naphthalene by
propylene on dealuminated mordenite. The narrow size of the
mordenite (10-membered ring) zeolite favours the formation
of the less-bulky para isomer of the di-isopropyl naphthalene,
followed by the ortho isomer relative to the meta isomer, as is
expected from the thermodynamic equilibrium of approximately
25:25:50, respectively.
Another aspect of zeolite properties is the connement effect, as
developed by E. Derouane [4749], which simply considers van der
Waals forces, i.e., neglecting Pauli repulsive forces, as illustrated in
Fig. 3.
Derouane et al. have proposed the following equation of the
van der Waals energy (W) of a spherical molecule of van der
Waals radius (d) conned in a spherical micropore of a radius (a):
W(s) = (C/4d3 ) (1 s/2)3 with C = h
/2, where = e2 /m2 is the
polarizability of an atom seen as a punctual dipolar momentum,
uctuating at a frequency , and s is the surface curvature. This
latter parameter, s = d/a, can vary between 0 and 1, depending on
the relative sizes of the conned molecule and the micropore. The
van der Waals force is F = (3C/4d4 )[(1 s)/(1 s/2)4 . The extreme
cases correspond to a at surface (s = 0) and to a molecule with the
same size as the pore (s = 1); this latter case has been referred to by
Derouane et al. as a oating molecule which should diffuse very
rapidly because its motion is not hindered by its interaction with
the wall, as compensated by the van der Waals force. It also follows
from the van der Waals equation that Ws=1 = 8Ws=0 , which means
that, according to this model, the adsorption energy due to the van
der Waals connement factor within the zeolite pore can be up to
8 times greater than that corresponding to a at surface. The type
of variation of W versus s can be found in Fig. 4.
As a consequence, molecules within the pores may interact more
or less strongly with their environment depending on their size
relative to that of the pores, e.g., 90 kJ mol1 for p-xylene in SAPO11. They can also contract themselves to enter the pores, whereas
the zeolitic lattice may also slightly contract upon adsorption, as
shown by XRD [50].
At present, more than 300 different types of zeolite frameworks
are known, with only a few (BEA, FAU, MFI, MOR, SAPO-34) having
important industrial catalytic applications; however, many more
have applications for the manufacture of ne chemicals. Some studies are described below to exemplify some of their properties.
The synthesis of adipic acid is an interesting example. The classical process (annual production of 0.7 Mt, off-gas concentration of
2540%) uses nitric acid as an oxidizing agent with the formation of
N2 O, which has to be re-oxidized further to nitric acid and which is
an important greenhouse gas. A catalytic process was subsequently
developed for N2 O decomposition. However, a process that uses a
Fe-MFI catalyst, which is able to oxidize benzene directly to phenol
[5158] has been discovered at the Boreskov Institute of Catalysis
in Novosibirsk, RU, and a process was developed with Monsanto
Co in a spin-off company called Solutia, but does not appear to be
commercialised, according to our knowledge. This process is much
more environmentally friendly because N2 O is used instead of oxygen to oxidize benzene to phenol. The scheme for this process is
presented in Fig. 5.
Another interesting example is FriedelCrafts reactions on
acidic zeolites. The rst mention of acylation related to the later
Al2 Cl6 method of Friedel and Crafts appeared in 1873 in a preliminary communication by Grucarevic and Merz [59], as reported by
Olah in a historical review about FriedelCrafts chemistry [60,61]
on the metal-catalyzed acylation of aromatic compounds. The
FriedelCrafts acylation reaction consists primarily of the production of an aromatic ketone by reaction of an aromatic substrate
with an acyl component in the presence of a catalyst. Many papers
and books have been published and numerous patents have been
granted on this topic, as summarized in a recent review [62]. Interests in electrophilic acylation studies and in the optimization of
preparative processes were spurred by the considerable practical
value of the aromatic ketone products, which constitute important
intermediates in the pharmaceutical, fragrance, avour, dye and
agrochemical industries. The electrophilic acylations are catalyzed
by Lewis acids (such as ZnCl2 , AlCl3 , FeCl3 , SnCl4 , and TiCl4 ) or protic acids (such as HF or H2 SO4 ). However, the use of metal halides
causes problems associated with the hydrolysis of the complex,
which results in the loss of catalyst and the generation of large volumes of corrosive waste streams. Great efforts have thus been made
to achieve the goal of making the Lewis acid using heterogeneous
solid catalysts, in particular acid zeolites. A detailed description of
FriedelCrafts reactions for arenes (e.g., benzene, toluene, xylenes),
aromatic ethers (e.g., anisole) with acetic anhydride or other acylating agents on zeolites and on clays, metal oxides, and so forth is
given in Ref. [60]. The roles of shape selectivity and deactivation by
the products and hydrophobicity versus hydrophilicity for zeolites
have been emphasized. For example, acylation of anisole or toluene
with acetic anhydride was performed on BEA zeolite at 90 C, to
replace the classical AlCl3 catalyst which led to many salts in the
efuents, corrosion problems, low selectivity and a short lifetime
Fig. 6. Scheme of the effect of the adsorption rate of reactants on the reactivity,
depending on the polarity of the reactants versus that of the zeolite [63,64].
of the catalyst, as already discussed. At variance, the use of H-BEA

zeolite resulted in 6 times fewer steps, 10 times less solid and 100
times less aqueous discharge, primarily because the hydrophilicity
versus the hydrophobicity of the zeolite, for more or less polar reactants, which allowed the reactant molecules to enter more or less
easily within the pores while the solvent molecules were prevented
from entering. The relative adsorption rates of reactant molecules
within the pores regulate the stoichiometry of the reaction inside
the pores, i.e., depending on the relative adsorption rates of the
reactants, and one has thus to choose a stoichiometry in the liquid medium surrounding the zeolite particles that is different from
that expected from the reaction. For example, a 20:1 stoichiometry might be chosen for a 1:1 reaction for toluene (non polar
reactant) acylation by acetic anhydride (polar reactant). This helds
true particularly for gas phase reactions with solid zeolites, but also
for liquid phase reactions on solid zeolites, which is an important
aspect of ne chemical reactions in zeolites, as schematized in Fig. 6.
Another interesting example relates to the production of
para-xylene (p-xylene). Xylenes, especially the para isomers, are
compounds in high demand in the organic chemical industry
for the production of polyethyleneterephtalate (PET) bres, plastics, resins, lms, and so forth because p-xylene is a chemical
intermediate in these processes. The main source of xylenes is
the C8 cut produced by catalytic reformation and steam cracking
[6568]. However, a convenient way to increase p-xylene production is to transform less-valuable C7 and C9 methylaromatics by
catalytic alkylation of toluene with methanol followed by disproportionation and transalkylation with trimethylbenzene. Catalysts
for these reactions range from common Brnsted acids (H2 SO4 ,
H3 PO4 , HF) to Lewis acids (metal halides) and further to solid

acids (Al2 O3 , SiO2 Al2 O3 , zeolites). It must be noted, that as a consequence of environmental concerns, the zeolite-based catalysts
currently play a signicant role in the production of alkyl aromatics. Studies reported in the literature describe a wide variety of
zeolitic catalysts that are active in the alkylation of toluene with
methanol [36,38,39,6978], toluene disproportionation [7984],
transalkylation of toluenetrimethylbenzene [8589], and xylene
isomerization [9092]. In general, the catalytic properties (especially the selectivity) and the surface deactivation of zeolites
during these reactions strongly depend on the nature, number
and strength of the acid centres in the catalyst. For example, the
catalysts with strongly acidic sites have been reported to be less
selective and easily deactivated by coke [93]. Modication of the
acidity and structure of zeolites (with large and medium pores)
can be considered a way to reduce by-reactions and improve
the selectivity to p-xylene. High activity and predominant shape
selectivity was observed on ZSM-5 [9497], and the reaction is
effective above 450 C. The high p-selectivity of modied ZSM5
has been attributed to the restricted diffusion inside the channels, i.e., the p-xylene, which rapidly diffuses out of the narrow
channels, is preferentially produced. Large-pore zeolites with 12member channel systems, particularly mordenite [98,99], have also
emerged as shape-selective catalysts. Although the size of pores is
important for the para selectivity, this phenomenon was observed
on large-pore zeolites when the acidity was modied by isomorphous substitution or ionic exchange with rare-earth metals. The
formation of p-xylene was also investigated on the zeolite MCM22 [100102], discovered by Mobil, which has a unique crystal
structure [103]. It is composed of two channel systems, both of
which are accessed through a 10-membered ring (10-MR) window.
One system consists of two-dimensional, sinusoidal channels with
10-MR opening, whereas the other contains large supercages that
consist of 10-MR and 12-MR openings with an inner free space
of 0.71 0.71 1.82 nm. These channel systems are independent
of each other, and molecules cannot pass from one to the other
within the same crystallite. The catalytic properties, such as the
shape selectivity of MCM-22, have been shown to be intermediate between 10-MR and 12-MR zeolites in various reactions. The
results for MCM-22 highlight the inuence of cages and windows
on the shape selectivity. In such cases, the experimentally observed
shape selectivity was attributed to variations in the Si/Al ratio and
the nature of the extra framework cations. Toluene disproportionation over dealuminated MCM-22 was found to occur mainly in
the supercages of MCM-22 but not in the 10-MR channels of MCM22 at the investigated temperatures. The fraction of p-xylene was
higher than its equilibrium value and increased further by the
Fig. 7. Historical view of functions of coordination polymers reported from 1990 to 2005. Structures of 3-D porous coordination polymers, [Cu(SiF6 )(4,4 -bpy)2 ]n (1, left),
[Zn4 O(BDC)3 ]n (2, right), and the 1-D oxygen array are listed [124].
Fig. 8. Self-assembly of polymetallic cluster nodes (left; top: m4-oxo {M4 O(-CO2 )6 }; bottom: {M2 (-CO2 )4 } paddlewheel) and organic linkers (right) yielding metalorganic
frameworks (center) [125,126].
dealumination. p-Xylene formed within the supercages as a primary product would be isomerized to o- and m-xylene by the acid
sites not only on the external surface but also within the 10-MR
channels. The improvement in the para selectivity by dealumination resulted from the suppression of isomerization activity; the
dealumination treatment probably eliminated framework Al atoms
predominantly on the external surface and inside the 10-MR channels compared with those inside the supercages [102].
Many other ne-chemical reactions have been developed by
Corma, Garcia and their teams [2] at ITQ, Universidad de Valencia,
Spain. These reactions pertain largely to the eld of applications of
zeolites in catalysis, which has previously been limited to petrochemical reactions.
2.2. AlPO4 -n SAPO4 -n, Me-AlPO4 -n, Me-APSO4 -n
In the early 1980s, the discovery of a new family of molecular sieves was reported by researchers at Union Carbide. Wilson
et al. [104,105] described the microporous aluminophosphates prepared hydrothermally from alumina, phosphoric acid and an amine
or quaternary ammonium salt as organic templates. The product
composition for these materials is xRAl2 O3 1.0 0.2 P2 O5 yH2 O,
where R is an organic template located in the intracrystalline
pore system. The crystallized materials consist of alternating AlO2

and PO2 tetrahedra joined together into electrovalently neutral,
three-dimensional frameworks whose structure depends upon the
preparation conditions. These frameworks contain no Al O Al
or P O P bonds. The AlPO4 -5 structure consists of 4- and 6membered rings joined together to form the unidimensional
cylindrical channels of 12-membered rings with a free diameter of approximately 0.8 nm [106,107,50,108,109]. The porosity
of the structures described by Union Carbide researchers varies
from very small pores (0.3 nm) to relatively large pores (0.8 nm).
Because AlPO4 frameworks are neutral, they have no ion-exchange
capacity. They exhibit good thermal and hydrothermal stability
and have weakly acidic catalytic properties. The absence of strong
acidity limits the application of these materials in cracking catalysis. By isomorphic substitution of a series of elements into the
AlPO4 framework, a new generation of crystalline molecular sieves
was prepared [110]. The elements include framework cationic
species that range from monovalent to pentavalent, such as Li,
Be, B, Mg, Si, Ga, Ge, As, Ti, Mn, Fe, Co, and Zn. The addition of
silicon to the aluminum and phosphorous framework elements
results in silicoaluminophosphate (SAPO) molecular sieves [111].
The SAPO structures are mildly hydrophilic and have low-tomoderate acidity, depending upon the silicon concentration and
Fig. 9. MOFs structures: Left: MIL-53, metal terephtalate (with Al, Cr, Fe ou V), which captures hydrogen into the framework formed of tunnels. Centre and right: MIL-100,
whose octahedra, constituted by chromates (CrO6 ), organise in tetrahedra and form cavities of diameter 23 nm as observed by electron microscopy from [127].
the structure type. According to Martens [112], even the highly

siliceous SAPOs have a lower catalytic activity as compared with
zeolites, such USY. SAPO-37 is very active cracking catalyst [113].
Several patents describe the use of SAPO-5, SAPO-11, SAPO-37 and
SAPO-40 in octane FCC catalysts [114]. The isomorphic substitution
of metal ions into AlPO4 frameworks results in metal aluminophosphates (MeAPO), whereas the isomorphic substitution of metal
ions into SAPOs results in metal silicoaluminophosphate frameworks (MeAPSOs). Their properties are similar to those of the
parent molecular sieves. The thermal and hydrothermal stability
of MeAPSO is somewhat lower than that of AlPO4 and SAPO molecular sieves. MeAPSOs exhibit weak to strong acidity, depending on
the metal type and the framework structure.
2.3. Pillared interlayer clays (PILCs)
Pillared interlayered clays (PILCs) have been studied since
the late 1970s as microporous materials with larger pore size
(0.42.0 nm, but less uniform) and more tunable compositions
than those of zeolites [115117]. PILCs were identied as good
candidates for heterogeneous catalysis because their pore size
distribution is quite broad and is still largely in the microporous range [2]. The parent clay materials are composed of
charge-balancing cations sandwiched between negatively charged
aluminosilicate sheets. PILCs are prepared by swelling the clay
sheets, ion exchanging the cations with [AlO4 Al12 (OH)24 (H2 O)]7+
aluminum polyoxocations, and calcining the material to create aluminum oxide pillars within the clay sheets. The result is a highly
porous structure with a large intracrystalline surface area suitable for molecular sieving, adsorption and catalysis [118]. PILC-like
materials, termed PCHs (porous clay heterostructures) have been
prepared using surfactant templating within the clay sheets [119].
The PCHs have controllable, uniform pore sizes of 1.42.2 nm and
retain the sheet-like characteristics of the original clay material.
Fig. 10. MOF: MIL-101 metal terphthalate with cages of 3.2 nm [128].
Descriptions of the structures and porosities of several MOFs are

illustrated in Figs. 911 for better comprehensiveness of their specic properties. According to Fig. 11, some MOFs may expand upon
adsorption (breathing motion) or be distorted, which may result
in different catalytic and adsorptive properties [130135]. Desorption may be slow without pumping; this property was suggested
by Ferey et al. to be used for the slow delivery of a drug into the
blood stream when inoculated to a sick person, e.g., for diabetes
[127].
For a catalytic point of view one can distinguish three aspects of
MOFs properties related to: (1) framework atoms or ions activity,
(2) encapsulation of active species and (3) post synthesis modication/functionalisation. Fig. 12 shows the relative sizes of different
zeolites and MOFs compared to organic molecules. It is clear that big
2.4. Layered double hydroxides (LDHs)

Layered double hydroxides (LDHs), also known as hydrotalcitelike compounds, are ionic lamellar compounds that consist of
positively charged hydroxide sheets with their interlayers lled
with anions and water molecules. Their structure is linked to
that of the natural mineral brucite, Mg(OH)2 [120,121]. The most
common group of LDHs can be represented by the general formula [M2+ 1x M3+ x (OH)2 ] [An x/n mH2 O], where M2+ and M3+ are
di- and tri-valent metal cations that occupy octahedral positions
within the host layers of hydroxide sheets, and An is an interlayer
anion that compensates for the charge on the layers. Positive charge
on the host layers arises from isomorphous replacement of a fraction of the divalent cations with trivalent cations. The combination
of Mg and Al has been studied most frequently, with a variety of
Mg:Al ratios and interlayer anions.
2.5. Metal organic frameworks (MOFs)
The metalorganic frameworks, designated MOFs, are new
materials that were discovered approximately 40 years ago by polymer scientists. The rapid proliferation of papers in the literature
started only approximately 20 years ago [122,123]. Their synthesis
corresponds to the reaction of organic and inorganic groups, such
as arsenates, silicates, sulfates, phosphates, phosphonates, etc. This
reaction builds up three-dimensional frameworks formed of inorganic and organic moieties linked by strong bonds. The organic
part is variable in nature, length and amount of space occupied
because it includes more- or less-branched carboxylic acids, amino
complexes, etc. The history of MOFs is schematized in Figs. 7 and 8.
Fig. 11. Schematic behavior observed upon adsorption, desorption of guest

molecules (a) induced pores (b) breathing pore; (c) pores exchanging guest with
deformation, (d) annealing pores [129].
10
Table 2
Comparison of MOFs with zeolites for some properties relevant to catalysis [131].
Properties
Zeolites
MOFs
Lewis acidity
Brnsted acidity
Surface area
Pore volume
Thermal stability
Chemical stabilility
Diffusion
Basicity
Metal site density
Framework defects
Active site environment
Poisoning of active sites
Chirality
High
Bridging Si(OH)Al hydroxyl groups
200500 m2 g1
0.10.5 cm3 g1
>450 C
High
High for small molecules in gas phase, slow in liquid phase
Arises from framework oxygens
Low
Important role in many reactions
Mostly hydrophilic, but may also be hydrophobic
Reactivation by thermal treatment
Not possible or difcult
Low to medium
Introduced by post synthesis
Up to 5000 m2 g1
Over 1 cm3 g1
300 C
Limited, depends on solvents
High but strongly inuenced by linkers
Introduced post synthesis or through linkers
High
Expected to play a minor role
Considerably hydrophobic
Thermal treatment not valid
Homochiral solid from chiral linkers or post synthesis modications
molecules can access the large pores, which should be important for
catalytic purposes, if the MOF structure has been functionalised or
has active sites and presents accessible framework atoms or metal
cationic sites (Table 2).
Garcia et al. have described [131] the use of metalorganic
frameworks (MOFs) as heterogeneous catalysts for oxidation reaction using hydroperoxides or molecular oxygen. The authors have
limited themselves to the oxidation of cycloalkanes, oxidation of
benzylic positions, oxidation of cycloalkenes and aerobic oxidation
of alcohols, but many more oxidation reactions may be imagined
and studied. The use of MOFs as catalysts for enantioselective oxidations has also been considered with the peculiarity of the required
oxidants and the advantages of having homo chiral MOFs.
Main applications of MOFs concern: adsorption, gas storage
(H2 , CO2 , etc.), gas separation, acid (Lewis; Brnsted), basic, redox
and enantioselective (chirality) catalyses, biomass transformation,
biomimetism, enzymes, drug delivery, magnetism, non linear optic,
lasers, sensors, luminescence, etc. In catalysis, the thermal stability
and leaching have been a big problem for many years and restrained
researches, but now some new systems have been claimed to be stable up to 500 C. The MOFs may not replace zeolites in petrorening
but well for ne chemistry under more gentle reaction conditions.

Already many papers have appeared for some reactions such as
oxidation, Lewis-type reaction of cyanosilylation of acetaldehyde
[137], etc.
It is clear that catalytic studies with MOFs are in their infancy.
It is certainly possible to go into more sophisticated materials with
organic ligands between the metals could be formed by transition
metal complexes with one or two metals at controlled distance.
Such types of materials will allow synthesis of heterogeneous catalysts based not only on transition metal complexes but also by the
combination of mono- or multimetallic sites. Such design may lead
to materials having a catalytic behaviour similar to that observed
with enzymes.
The possibility to synthesise MOFs with a large variety of transition metals could be largely exploited for Lewis acid-type catalysis,
provided that the metal is accessible (free valency available) and
able to accept electrons from the reactant. In addition, the organic
component of the MOF should support acid, base, or acid-base
pairs and should allow one to perform successive reactions. There
may be interest in the chemical industry in exploiting MOFs as
heterogeneous catalysts. Examples include epoxide ring aperture
with alcohols by zinc carboxylates, ne chemical reactions as Fries
rearrangements, acylations, alkylaromatic oxidation using cobalt
salts in acetic acid, etc. MOFs offer also some promises as enantioselective catalysts, a topic that has not been possible to develop
using zeolites. Asymmetric syntheses are routinely practiced in the
synthesis of drugs, and these reactions are almost completely performed using expensive homogeneous catalysts. By using chiral
ligands, a vast number of new MOFs could be available and tested
in this eld. Considering the simplicity of the synthesis of MOFs and
their affordability, it will be important to know if MOFs can outperform in large-scale or asymmetric reactions to replace expensive
homogeneous processes.
Finally, there is a need for theoretical studies in this new eld,
assisting the design of MOFs and providing insight into the interaction of the substrates and MOFs. Clarifying the reaction mechanism,
the geometry of the transition states, and the controlling step in the
reaction mechanisms may help to develop MOFs in which each of
the components plays the expected role, as catalytic sites of natural
enzymes.
2.6. Hierarchical zeolites
Fig. 12. Comparison of sizes of cavities and organic molecules diameters [132].
Hierarchical and mesoporous zeolites and mesoporous oxides

(alumina, titania, etc.) have received increasing attention because
of their improved performance in catalyzed reactions with respect
to conventional (purely microporous) zeolites or common metal
oxides [59,138,139]. The principle involves the creation of mesoporosity within the zeolite or within any metal oxide particles.
Combined micro- and mesoporous materials have been claimed to
11
Fig. 13. World energy consumption in 2005 (13 TW or 87 Gbarrels oil) [245].
have advantages compared with the exclusively micro- or mesoporous materials. The reactant molecules are thus expected to
diffuse more easily [140] within these pores to reach the active
zeolite sites. These materials provide better hydrothermal stability
[141], better multifunctionality to process a large variety of feedstocks, more controlled leaching rates for a constant and gradual
release of active components, and are more capable of encapsulating wastes in the micropores [142144]. Different porous
materials that combine micro- and meso-pores, such as SBA-15,
plugged hexagonal templated silica (PHTS), mesoporous aluminum
silicates (MAS), mesoporous titanium silicates (MTS), UL-ZSM-5,
and zeolites, have been developed within the last few years. Of
these materials, the latter four are mesoporous materials built up
from zeolite precursors. Such porosity in the mesoporous materials with zeolite character can be created after synthesis by
chemical treatments, including hydrothermal, acidic, basic, desilication/dealumination [2] or recrystallization treatments [145,146],
or templating [147149] or carbon-based [150153] approaches.
Desilication in alkaline media has become a widely applied preparation method to tailor these modied zeolites because of the
methods optimal combination of efciency and simplicity. Alkaline treatment is also a key step in strategic combinations with
other post-synthesis modications.
2.7. Carbon materials
Carbon nanotubes (CNTs) constitute another class of porous
materials. They have been widely studied since their discovery
in 1991 [154]. CNTs have highly unique electronic, mechanical,
catalytic, adsorption, and transport properties, which make them
interesting for a variety of applications. Carbon multiwall nanotubes (MWNTs) and single-wall nanotubes (SWNTs) should be
distinguished. They are easily fabricated and may be employed
either as catalyst supports, by entrapping active moieties within the
pores, or to improve photoconversion and electrical energy storage
(vide infra) [136,155160]. Other forms of nanographitic carbon
may also prove to be promising in the development of renewable
energy devices. For example, graphene, which consists of a single sheet of graphite, is considered a promising form of carbon for
device engineering applications and catalysis [161165]. A signicant volume of literature devoted to graphene and other forms of
carbon, including graphitic nanobers, has suggested that CNTs are
not the only promising nanostructures for either photoconversion
or electrical energy storage applications. The highly unique physical
properties of carbon nanotubes have been demonstrated for a variety of photovoltaic devices as well as for improved Li-ion batteries
and electrochemical capacitors.
2.8. Mesoporous materials

Many mesoporous silica-type materials have been synthesized
in the years after the pioneering works by Mobil researchers
on the M41S family (MCM-41, MCM-48, MCM-50) [166168].
MCM-n mesoporous materials are synthesized using surfactants
as structure-directing agents and can be characterized by welldened pores of tunable sizes in the range between 2 nm and 10 nm
and by specic surface areas between 600 m2 g1 and 1300 m2 g1 .
The most representative M41S materials are MCM-41 and MCM48. MCM-41 consists of regular pseudo-one-dimensional pores
in a honeycomb arrangement, whereas MCM-48 exhibits cubic
symmetry that consists of two interwoven but unconnected threedimensional pore systems of cylindrical pores. MCM-48 is more
difcult to synthesize and high-quality materials can typically be
obtained in the pore-size range between 2 and 5 nm [169]. MCM-50
comprises a lamellar phase. Independently, a family of mesoporous
silica materials with properties similar to those of MCM-41 was
discovered [170,171]; an important member of this family is FSM16 [171]. At the microscopic scale, these materials are essentially
amorphous. Whereas the pore diameter range of MCM-41 materials is restricted to 10 nm, ordered mesoporous silica with pore
diameters up to approximately 30 nm (SBA-15) can be obtained
using an amphiphilic block copolymer as a template [172,173].
SBA-15 (similar to MCM-41) consists of a hexagonal packing of
cylindrical channels; however, depending on the details of the
synthesis procedure, this material can possess irregular intrawall
micropores that connect adjacent channels [174,175]. Moreover,
a great variety of mesoporous materials have been synthesized,
such as SBA-1, SBA-2, SBA-12, SBA-16, HMS [176], MSU [177],
KSW-2 [178180], TUD-1 [181], periodic mesoporous organosilicas
(PMOs) [182184], nanoporous carbon with ordered mesostructures [CMK-1, CMK-3) [185,186]. Pure-silica mesoporous materials
are known to exhibit low catalytic activity because of the absence of
active sites, which typically require heteroatoms. Therefore, one of
the emerging trends in the area of mesoporous materials synthesis is the incorporation of heteroatoms that serve as catalytically
active sites. Considerable research interest currently exists in the
preparation and use of heteroatoms that contain mesoporous silicas as heterogeneous catalysts. Several elegant procedures have
been reported for the incorporation of heteroatoms that also permit the design of the catalysts with active sites located on highly
accessible internal surfaces of the pore channels. These procedures include impregnation [187190], grafting by liquidsolid
reaction [191196], grafting by gassolid reaction [197], grafting by solidsolid reaction [198,199], isomorphous substitution
[200210], molecular designed dispersion approach [211213] and
12
template ion exchange method [214,215]. The objective was to synthesize porous materials able to accommodate bulky molecules and
thus treat heavier petroleum feedstocks. For example, the introduction of Al into such silica frameworks led to medium-strength
acidity compared with the acidity of normal zeolites because of
larger Si O Al bond angles. The applications of such materials in
petrochemistry were subsequently limited. At present, research is
focused on the introduction of catalytically active functions within
the mesopores (i.e., functionalization of the walls) or of nanoparticles of metals or oxides. Interesting results were obtained;
however, to our knowledge, no study has yet produced a breakthrough in catalytic processes. H-Al-MCM41 materials have been
used as catalysts for the conversion of a large variety of substrates
in reactions as diverse as hydrocarbon cracking, hydrocracking and
hydroisomerization, olen polymerization, oligomerization and
isomerization, FriedelCrafts aromatic and phenol alkylations and
acylations, acetylazations, Beckmann rearrangements, glycosidation, aldol condensations, and Prins condensations. Several reviews
on the subject have been published [2,216,217].
Interesting results for the metal-mesoporous materials were
reported with respect to the FischerTropsch reaction [218,219],
hydrodesulfurization [220222], the conversion of methylcyclopentane [199,201], the acylation of phenol [223], the naphthalene hydrogenation [224], the hydrogenation of arenes [225],
cyclohexane hydrogenation [226], NO reduction with CO [227],
the acylation of aromatic compounds [228], the benzoylation of
benzene [229], the metathesis of oct-1-ene [230], and the photocatalytic decomposition of NO [231], the oxidation reactions [232,233]
and soforth.
2.9. Versatile heterogeneous catalytic systems
Combining connement and synergy effects has appeared
recently as a promising way to synthesise efcient and versatile
heterogeneous catalytic systems. For instance, many studies have
been performed in the past half century to immobilize homogeneous catalysts on solid supports to synthesize heterogeneous
catalysts [234], known to result in easy separation of the catalyst
from the reactants and products. Originally, the active centres were
designed to be away from a support surface in order to minimize the
support destructive inuence on the catalytic sites and to maintain
the homogeneous metal complexes environment of ligands with
a long spacer and thus catalytic properties [235]. Later on, it was
observed that a support can even have some benecial effects on
the anchored homogeneous catalysts [236] such as connement
[237] and synergy effects [238240]. Heterogeneous bifunctional
and even trifunctional catalysts could then be prepared and studied because a synergy between multifunctional groups could be
developed within conned spaces. An important further objective
was to try to synthesise heterogeneous catalysts with enantioselectivity enhanced after chiral catalysts are introduced into conned
spaces. For example, Raja and Thomas [241] have shown that,
compared with the racemic products obtained in homogeneous
catalysis, improved enantioselectivity (ee% 5394%) in asymmetric
hydrogenation reactions was obtained after chiral RhI complexes
were introduced into the channels of mesoporous silica. He et al.
[242] have also shown that after a bifuntional catalyst, 9-thiourea
epi-quinine, was incorporated in the channels of mesoporous silica
SBA-15, the heterogeneous catalyst exhibited improved selectivity and enantioselectivity (92.5% selectivity and 99.2% ee versus
83.8% selectivity and 93.2% ee) in asymmetric FriedelCrafts reaction between indoles and imines.
Layered compounds, with two-dimensional exible interlayer
regions, are also promising supports for the immobilization
of homogeneous catalysts. For instance, the immobilization of
copper complexes in laponite clay was found [243] to increase the
ee from virtually zero to values ca. 40% in the reaction of methyl

phenyldiazoacetate with tetrahydrofuran.
The idea is to graft, anchor or thether catalytic active entities
to mesoporous silica. These species may be identical or different
which may lead to bifunctional, trifunctional entities within the
pores. Their proximity may result in synergistic effect for some
reactant within a conned space and opens an important eld of
discovery of new catalysts, by taking advantage of continuum range
of distance between anchored functional groups and intrinsic active
sites on the support surface. Synergistic effects within anchored
bifunctional catalysts, between two anchored functional groups,
and between the anchored groups and hydroxyl groups on solid
surface have been used to synthesise multifunctional catalysts. Lets
also remind that synergistic effects are widely utilized in nature
such as for enzymes which with limited functional groups can catalyze many reactions smoothly with high activity and selectivity at
near room temperature. [244]
3. Energy resources
Currently, petroleum and natural gas represent more than 60%
of the primary energy supplied to 7 billions inhabitants on earth.
Coal also remains an important source of energy, primarily in Asia.
Whether used for energy production, transport, heating or as a
source of chemical raw materials, the consumption of oil, natural gas and coal is expected to rise in the near future, while the
development of alternative sources is expected to rise rapidly after
a slow development in the past 20 years. The signicant increase
in energy demand over the past twenty years has primarily been
satised by increasing the production of fossil sources. Because of
this situation, several governments are approving new laws aiming
to reduce CO2 emissions by promoting the utilization of renewable
energy sources and biofuels. The total world consumption in 2005
was of 13 TW (87 Gbarrels of oil), of which 81% came from fossil
resources, as shown in Fig. 13.
Ten percent of the world energy use is derived from biomass,
and 7% is derived from nuclear power. Nuclear power is desirable
as long as the isotope uranium-235 (235 U) is employed. However,
a less than twenty-year supply of U235 , which may be recovered
at a reasonable cost, is available. When the supply of 235 U will be
exhausted, it will then be necessary to employ breeder reactors.
Unfortunately, the by-product of this reaction is the very hazardous
element, plutonium-239, 239 Pu (238 U 239 Pu). Moreover since the
disaster following the tsunami in Japan in 2011 and the collapse of
the nuclear plant in Fukushima, the construction of nuclear plants
have been hardly questioned in many countries, although nuclear
power is non CO2 producer and non fossil resource consumer.
3.1. The case of oil
It is difcult to evaluate the exact oil reserves because it corresponds to rough estimations called current reserves, which are
contingent resources (conventional and extra-heavy + bitumen)
concentrated in a limited number of countries (Saudi Arabia, with
20%, Iran, Iraq, and Venezuela; these four countries possess 50%
of the world reserves), with 75% in concentrated in 11 countries.
The current reserves correspond to approximately 1000 Gbarrels
therefore, approximately 35 years of production at actual consumption level, but less than the oil already extracted) and one may
add 200 Gbarrels for conventional resources and 200300 Gbarrels
more for extra-heavy oil and bitumen. Oil is extracted either by
simple pumping (20% of world production), by the injection of
water (2/3 of oil produced), or by the injection of water + chemicals
or gas (air, CO2 or gas produced (15%)). Efforts to discover new
resources are clearly important, and the substitution of oil by
13
3.3. Biomass as a source of raw materials and future energy
Fig. 14. Some perspectives of oil demand in a near future from WEO 2006. Note that
billions tonnes should read giga tonnes.
renewable energies is vital. Some prospects are presented in

Fig. 14.
3.2. Perspectives with natural gas (NG)

Natural gas constitutes the largest reserves of fossil resources.
Eleven countries possess 75% of world gas resources, with 45% for
Russia, 28% for Iran, and 25% for Qatar. The current reserves are
estimated to reach 175200 Tm3 (T = tera = 1012 ); however, large
resources exist in the form of methane hydrates, which are located
primarily in Polar Regions or in deep-water acreage. Natural gas
can be used as an energy source (in power plants or as a heating
source, for instance), but it can also be transformed into many
basic materials for chemicals. Nevertheless, currently, only its
conversion to syngas via steam reforming, partial oxidation or
autothermal oxidation appears to be industrially viable [246]. All
direct transformations to, for instance, methanol, dimethyl ether,
formaldehyde, aromatics, or olens are still not economically
viable. This lack of viability constitutes a real challenge for the
future, although many approaches have been attempted over the
past 50 years, starting with the dimerization reaction in the 1970s,
without commercialization success. The main possible reactions
are summarized below:
Steam reforming
1. CH4 + H2 O CO + H2
2. Cn Hm + nH2 O nCO + (n + m/2) H2
3. CO + H2 O CO2 + H2 (WGS)
H0 298 (kJ mol1 )

206
1175 (for nC7 H16 )
+41
CO2 (dry) reforming

4. CH4 + CO2 2CO + 2H2
247
Autothermal reforming (ATR)

5. CH4 + 1 O2 CO + 2H2 O
6. CH4 + H2 O CO + 3H2
7. CO + H2 O CO2 + H2
+520
206
+41
Catalytic partial oxidation (CPO)

8. CH4 + 1/2O2 CO + 2H2
+38
Total oxidation
9. CH4 + 2O2 CO2 + 2H2 O
+802
Boudouard reaction
10. 2CO C + CO2
+172
The main chemical products from natural gas are summarized

in Table 3.
Biomass, i.e., all products from plants (crops, algaes, wood, agricultural wastes, etc.), has emerged as an important future source
of energy and raw chemicals to replace, at least in part, coal, oil
and natural gas. The origin of biomass from CO2 and water under
solar photons and chlorophyll to produce sugar blocks at the origin of cellulose, hemicellulose, lignin, and so forth is well known.
Lignin constitutes one of the three major components of lignocellulosic biomass; the other two components consist of cellulose
and hemicellulose. Lignin is a three-dimensional amorphous polymer that consists of methoxylated phenylpropane structures. In
plant cell walls, lignin lls the spaces between cellulose and hemicellulose and acts as a glue that holds the lignocellulose matrix
together. Cross-linking with the carbohydrate polymers then confers strength and rigidity to the system [245,247].
In 2005, more than 3% of the total energy consumption in the
United States was supplied by biomass, and it recently surpassed
hydroelectric energy as the largest domestic source of renewable
energy. Similarly, the European Union receives approximately 66%
of its renewable energy from biomass, which surpassed the total
combined contribution from hydropower, wind power, geothermal energy, and solar power. In addition to energy, the production
of chemicals from biomass is also essential because it is the only
renewable source of liquid transportation fuel.
Over the last 30 years, three generations of biomass products
have emerged [248,249], which are distinguished by their nature.
Whereas oil was the principal source of energy in the twentieth century, the 21st century is expected to bring new sources of energy,
particularly renewable energies such as bioenergies [248].
Three strategies for biomass valorization can be followed [249].
In the rst strategy, biomass is gasied to syngas or degraded by
pyrolysis to a mixture of small molecules, which can be used to
produce chemicals using technologies developed for petroleum
feedstocks. In the second strategy, extensive removal of the functional groups present on the lignin monomers yields simple
aromatic compounds, such as phenol, benzene, toluene and xylene.
These platform chemicals are then reacted in a second step using
existing catalytic technology developed for petroleum reneries
to produce bulk and ne chemicals. In the third strategy, biomass
is converted directly to valuable chemicals in a one-pot process,
which requires highly selective catalysts that eliminate functionalities and linkages. This strategy is best suited for the production of
ne chemicals with a high degree of functionality, such as vanillin,
that already resemble the lignin structure; however, more complicated target molecules may also be produced with additional
improvements in catalytic technology. Indeed, this approach could
yield a plethora of complex aromatics that are not otherwise readily available via conventional petrochemical routes. Because none
of these strategies is expected to yield a single product in high
yield, product separation is an important component of each process. In each case, after the catalytic processing of the lignin stream,
the chemicals or fuels produced must be puried, which obviously
must be taken into account in evaluations of the environmental
impact of the whole process. Components from the cellulose and
hemicelluloses streams are integrated within the lignin framework,
but the process arrows are not fully depicted for clarity [245]
Fig. 15.
The transformation of cellulose, which is the main constituent
of the most abundant renewable lignocellulosic feedstock and is
non-edible, into chemicals and fuels has attracted signicant attention in recent years. Compared with other conversion routes, such
as high-temperature gasication and pyrolysis and enzymatic fermentation, a low-temperature and selective catalytic route for the
transformation of cellulose in, e.g., a water medium, into a platform molecule, which may be facilely transformed into valued
14
Table 3
Main chemical products from natural gas.
Products
Production (Mtons/y)
Energy consumption (GJ/t)
CO2 (t/t)
Main technology
Ammonia
Ethylene
Propylene
Methanol
Hydrogen
Synfuel
120
100
55
30
20
15
29
15
28
12.6
67
1.6
0 .65
0.28
9.0
1
Syngas/synthesis
Steam cracking of C2 H6
Steam cracking
Syngas/synthesis
Steam reforming
Syngas/synthesis
Source: IFP Energies Nouvelles.
chemicals and fuels in the subsequent step, is more desirable. Glucose, polyols, organic acids, and 5-hydroxymethylfurfural (5-HMF)
are all promising platform molecules. Some bifunctional catalysts
and catalytic systems that contain both acidity for the hydrolysis
of -1,4-glycosidic bonds in cellulose and metal nanoparticles for
the hydrogenation or oxidation of monosaccharide to polyols or
organic acids have been developed [250256].
Some analogies can be drawn between the twentieth century
petroleum renery and the twenty-rst century biorenery. In the
beginning, the petroleum renery made few products and incorporated little chemical and energy components. The development
of the petroleum renery required considerable effort-spanning
decades-to become the highly efcient, integrated system that
exists today. Many of the breakthroughs that allowed this remarkable transformation involved advances in catalysis. Similarly,
current bioreneries, which are still in their infancy, produce relatively few chemicals (primarily ethanol or bio-oils) with little
chemical and energy integration. Analogous to the history of the
petroleum renery, with the development of catalytic technology,
the biorenery may become an efcient, highly integrated system
to meet the chemical and fuel requirements of the twenty-rst century. To realize this system, in addition to the catalytic conversions
of cellulose and hemicellulose, the lignin fraction of biomass should
be transformed from a low-quality, low-price waste product into a
high-quality, high-value feedstock for bulk and specialty chemicals
by the development of the appropriate catalytic technology. The
direct transformation of lignin into valued chemicals appears to be
more difcult than the transformation of cellulose. However, this
transformation is critical because lignin represents the only viable
renewable source for the production of the aromatic compounds
on which society currently depends.
It can be concluded that biomass is currently the leading renewable energy source in the world. Moreover, the introduction of
biomass into energy systems presents certain advantages, such
as a reduction in greenhouse gas emissions, because its synthesis uses CO2 and water. However, its mobilization still presents
many challenges relative to the competition between uses and
the management of local natural resources (e.g., water, soil, biodiversity, farmer land and forest private properties). Therefore, the
technologies involved should be structured so that this resource
is developed to be truly sustainable. Two technologies exist for
the production of diesel replacement fuels: vegetable-oil methyl
esters (VOME) and hydrotreated vegetable oils (HVO). The latter
oils, blended with kerosene, have begun to be used as aviation
fuel.
Crop yields depend on the nature of the biosource, as detailed
in Table 4. Wood is an important source for lignin. The production
and transformation of wood into biofuel is presented in Table 5.
Algae as oil seed appears to be particularly efcient (yield of
70 t ha1 and fuel efciency of 14 toe ha1 ), whereas sugar cane
and sugar beets have high yields (ca. 70 t ha1 ) but lower fuel efciency (ca. 3 toe ha1 ). For comparison, the majority of the other
biomass resources have yields of 1020 t ha1 and efciencies of
24 toe ha1 . The cultivation of microalgae to produce oil biomass,
cellulose or hydrogen is free of many terrestrial constraints. Such
microalgae are cultured in photobioreactors and need only be in
proximity to water, light, heat and CO2 . Microalgae constitute the
prevailing trend in current research.
In the future, solar, geothermal, wind and presumably nuclear
power plants will presumably be used for electricity; biomass,
natural gas, coal and oil will be used for syngas and chemicals, hydrogen will be used for GTL and hydroprocessing, and
Fig. 15. Lignocellulosic biorenery scheme with particular emphasis on the lignin stream [245].

Table 4
Crops mobilised for energy pruposes versus total production in 2007.
Total harvest (Mt) % for bioenergies
606
Corn
With USA
Rape sunower
0.3
120
77
With USA
Soybean
23
With USA
144
193
With Asia
Sugar beet
165
With EU
0.3
4
115
1591
With South America
8
15
641
606
Wheat
2
0.2
247
Sugar cane
51
1
221
Palm oil
1
17
With EU
37
0.3
120
From FAOSTA, FAPRI.
reneries will be used to produce heat, electricity, transports, and

bulk chemicals (CO2 sequestration).
4. Hydrogen as a future energy source
The future supply of energy is dependent on hydrogen as a
clean energy carrier. Hydrogen can be produced from fossil fuels,
water electrolysis and splitting or biomass. However, the current
debates concerning hydrogen economy are intimately linked to the
clean production of hydrogen from fossil fuels (e.g., natural gas,
coal propane, methane, gasoline, light diesel), from dry biomass
and biomass-derived liquid fuels (e.g., methanol and biodiesel),
and from water. Because of the low cost and wide availability of
coal, coal gasication to syngas and then to hydrogen through the
watergas shift (WGS) reaction is a promising route to cheap hydrogen. The success of such a hydrogen production route will only be
possible if carbon dioxide is sequestered safely and economically.
The key to the cost effective conversion of coal to hydrogen and carbon capture is the development of nanomaterials, such as catalysts
for the WGS reaction and inorganic membranes for hydrogen/CO2
separation. In the future, hydrogen will be the dominant fuel and
will be converted to electricity in fuel cells, leaving only water as a
product.
4.1. Watergas shift reaction (WGS)
Since the early 1940s, the WGS reaction has represented an
important step in the industrial production of hydrogen [257].
Interest in the study of WGS catalysts has recently been renewed
because of the importance of such catalysts in PEM fuel cell applications [258,259]. The WGS reaction is an old industrial process in
which water in the form of steam is mixed with carbon monoxide to
obtain hydrogen and carbon dioxide. The WGS reaction is reversible
and exothermic. Because of its moderate exothermicity, the WGS
reaction is thermodynamically unfavorable at elevated temperatures, as illustrated by the continuous decline and eventual sign
15
change in the Gibbs free energy as a function of temperature and the

corresponding decreasing equilibrium constant as the temperature
is increased. Low temperatures thermodynamically favour higher
CO conversion. For maximum efciency and economy of operation,
many plants operate both a high-temperature stage (350400 C)
and a low-temperature stage (180240 C). The commercial catalyst is composed of copper, zinc oxide, and alumina. The copper and
zinc oxide forms are stable under WGS reaction conditions. Copper,
the active species, remains active at temperatures as low as 200 C.
The zinc oxide provides some protection of the copper from sulfur
poisoning by reacting with adsorbed sulfur compounds while also
acting as a support for the copper. Because of the relatively low
melting point of copper, the commercial low-temperature stage
catalyst is more sensitive to deactivation caused by sintering. Different catalysts are employed in the WGS reaction, including Fe
[260,261], Ni [262,263], Cu [264,265], Ru [266,267], Au [268,269],
Pt [270].
The essential role of the industrial WGS reaction is to increase
the production of hydrogen for renery hydroprocesses, bulk storage and redistribution. This role includes the need for gases of
appropriate H2 /CO ratios in the production of organic bulk chemicals such as ammonia, methanol, and alternative hydrocarbon
fuels through FischerTropsch synthesis. These gas mixtures, when
applied in industry, are usually referred to as synthesis gas, or
syngas, and are produced in large-scale facilities by the hightemperature reaction of carbonaceous materials in the presence
of water or oxygen and supported-nickel catalysts.
4.2. Hydrogen production by steam reforming of ethanol
Ethanol is an excellent candidate for the production of hydrogen. The aim of the procedure for the steam reforming of ethanol
is to generate a large amount of hydrogen and carbon dioxide by breaking the ethanol molecule in the presence of steam
over an appropriate catalyst [271275]. However, numerous reaction pathways occur in the ethanol steam-reforming process that
depends on the nature of the catalysts used. These pathways
include the dehydration of ethanol to ethylene and water followed
by ethylene polymerization to form coke [276], the decomposition or cracking to methane followed by steam-reforming [277],
dehydrogenation to acetaldehyde [274] followed by decarboxylation or steam-reforming of C2 H4 O, decomposition into acetone,
CH3 COCH3 , followed by steam reforming [278], and steam reforming of ethanol to syngas [274]. These processes are accompanied by
the watergas shift reaction, coking reaction, and other reactions.
Tremendous progress is needed to obtain a highly selective catalyst
to develop a process for hydrogen generation by ethanol steaming, which is a sustainable solution for the problem of hydrogen
production.
4.3. Water splitting as a hydrogen source [279]
Pure hydrogen may be the nal destination in the evolution
of fuel usage from coal to petroleum to natural gas, which has
Table 5
Commercial uses of wood (in Mm3 ) and breakdown of conventional energy uses in 2007.
World
Europe
North America
South America
Asia
Africa
Wood harvest
Sawn wood
Wood for paper
Wood for board
Wood for fuel
Fuel wood %
3,591
729
640
366
1,027
672
1,007
330
386
82
150
25
354
102
149
36
55
6
266
84
56
15
105
3
1,886
153
54
184
787
603
53
21
8
53
77
90
Source: IFP Energies Nouvelles, D. Lorne, Panorama 2010 Source: FAOSTAT.
16
followed a trail of increasing hydrogen content. A major bottleneck

for the hydrogen vehicle is the issue of hydrogen storage. Hydrogen
has the highest energy per unit mass, but occupies a large volume.
Even in liquid form, the energy density of hydrogen is only 8.4 MJ/L,
compared with 31.6 MJ/L for gasoline. MIL-53 is a potentially useful
material for hydrogen storage, as are graphene [280] and bimetallic
Pd-based alloys.
Because of its high energy capacity and environmental friendliness, hydrogen has been identied as a potential energy carrier in
many low-greenhouse-gas (GHG) energy scenarios. In a proposed
hydrogen energy system, hydrogen-containing compounds, such as
fossil fuels (mainly methane), biomass, or even water, are potential
sources of hydrogen. When hydrogen is derived from hydrocarbons such as fossil fuels or biomass, the capture and sequestration
CO2 are required in a low-GHG scenario. Although hydrogen produced from water does not present the challenge of unwanted
emissions at the point of conversion, it does require that energy be
supplied from an external resource. If this energy can be obtained
from a renewable energy source, such as solar energy, hydrogen
can then be considered a green energy alternative, and it is becoming increasingly relevant in our world. However, the technology
to produce hydrogen in a cost-effective, low-GHG manner has
not yet been developed. Since the discovery of hydrogen evolution through the photoelectrochemical splitting of water on n-type
TiO2 electrodes, the technology of semiconductor-based photocatalytic water splitting to produce hydrogen using solar energy has
been considered one of the most important approaches to solving the world energy crisis. Consequently, the development of the
necessary semiconductor photocatalysts has been the subject of
considerable research. Over the past 40 years, many photocatalysts
have reportedly exhibited high photocatalytic activities for splitting water into a stoichiometric mixture of H2 and O2 (2:1 by molar
ratio) in the UV-light region. These photocatalysts include La-doped
NaTaO3 , Sr2 M2 O7 (M = Nb, Ta), La2 Ti2 O7 , K2 La2 Ti3 O10, NiO/NaTaO3
and -Ge3 N4 , among others, photocatalyst, which shows the highest activity, with a quantum yield of 56% at 270 nm. However, these
oxide photocatalysts are only active under UV irradiation. With
respect to the solar spectrum, only a small fraction (ca. 4%) of the
incoming solar energy lies in the ultraviolet region, whereas the visible light in the solar spectrum is far more abundant (ca. 46%). It is
essential, therefore, as an alternative to UV-active photocatalysts,
to develop visible-light-driven photocatalysts that are stable and
highly efcient for the practical, large-scale production of hydrogen using solar energy. In recent years, continuous breakthroughs
have been made in the development of novel visible-lightdriven photocatalysts, which has led to the enhancement of
photocatalytic activity for water splitting and has inspired great
enthusiasm. A large number of semiconductor materials have been
developed as photocatalysts for the splitting of water to hydrogen under visible-light irradiation. Signicant process has been
achieved [281] with respect to semiconductor-based photocatalytic hydrogen generation through water in the hydrogen energy
system.
Photocatalytic systems for water splitting are classied as
one of two main kinds: sacricial-reagent-containing watersplitting systems and overall water-splitting systems. Thus far, the
sacricial-reagent-containing water-splitting systems constructed
from the Pt/CdS, Pt-PdS/CdS, and Zn/Cr layered double-hydroxide
photocatalysts have demonstrated the best performance for hydrogen production and oxygen production, with highest quantum
yields of ca. 60%, 93%, and 60%, respectively, at 420 nm. However, the efciency of overall water-splitting systems based on
visible-light-driven photocatalysts is still quite low, with a maximum quantum efciency of ca. 5.9% over Rh2y Cry O3 /GaNZnO
in the range of 420440 nm. This result is still far from the
quantum efciency (ca. 30% at 600 nm) designated as the initial
starting point for practical applications or the critical conversion efciency of light energy to hydrogen from photocatalytic
water decomposition (15%). Therefore, more efcient visiblelight-driven photocatalysts need to be developed to allow the
construction of the necessary high-efciency and cost-effective
water-splitting systems. To develop more efcient visible-lightdriven photocatalysts, the band gaps need to be narrowed to
harvest visible light in longer-wavelength regions of the spectrum and to enhance the photogenerated charge separation during
photocatalysis. Band-gap engineering for the modication of the
band structure of semiconductor photocatalysts using ion doping, semiconductor sensitization, or solid solutions all present
signicant opportunities to render such materials active in the
visible-light region. Computational predictions based on rstprinciples calculations could provide an efcient way to identify
candidates.
The loading of co-catalysts on the surface of the host photocatalysts has been shown to be rather effective in inhibiting charge
recombination. Alternative, more economical co-catalysts, such as
the non-noble metals and other derived metal-based compounds,
also need to be tested as possible substitutes for the most frequently
used noble metals, such as Pt, which is very efcient but expensive. In addition, new insights are needed into the water-splitting
mechanism, particularly regarding the identication of any thermodynamic and kinetic bottlenecks. Such determinations would
facilitate the design of the most effective photocatalytic watersplitting systems.
Presently, the available efciency for overall water-splitting
systems for the simultaneous production of hydrogen and oxygen under visible-light irradiation is still low because of the
fast charge recombination and backward reactions. To achieve
enhanced and sustainable hydrogen production, the continuous
addition of electron donors is required to make up half of the
water-splitting reaction to reduce H2 O to H2 . These sacricial
electron donors can irreversibly consume photogenerated holes
and thus prohibit undesirable charge recombination. Taking into
account the decreasing cost of solar-to-H2 energy conversion, polluting byproducts from industries and the low-cost renewable
biomass from animals or plants are preferential sacricial electron
donors in water-splitting systems. At little or no cost, they could
be exploited to simultaneously accomplish the task of hydrogen
production and that of waste treatment and biomass reforming.
Nevertheless, such an admirable goal for the practical application of water-splitting systems is especially interesting considering
worldwide energy and environmental concerns, but is still in its
infancy.
The current lack of industrial applications of the semiconductorbased photocatalytic hydrogen generation is largely due to two
reasons: the low photocatalytic efciency and the lack of extensive studies for a successful scale-up of the laboratory setup to an
industrially relevant scale.
In addition to TiO2 , heterogeneous photocatalysts such as ZrO3 ,
NaTaO3 , BaTa2 O6 , SrTa2 O6 , K4 Nb6 O17 , and K3 TaSi2 O13 can decompose water to evolve O2 and H2 without loading any co-catalysts
under UV irradiation [282]. The activities of the majority of these
photocatalysts are augmented by the loading of a co-catalyst, such
as NiOx, as a proton-reduction site. In this regard, high-donordoped layered perovskites loaded with NiO have demonstrated
photocatalytic ability for water splitting under UV irradiation.
These layered structures with a basic composition Am Bm O3m+2 ,
where m 4 or 5, A Ca or Sr, and B Nb or Ti, showed elevated
quantum yields and a stoichiometric evolution of H2 and O2 . However, SrTiO3 , KTaO3 , Ta2 O5 , Rb4 Nb6 O17 , K2 La2 Ti3 O10 , Rb2 La2 Ti3 O10 ,
Cs2 La2 Ti3 O10 , CsLa2 Ti2 NbO10 , Na2 Ti6 O13 , and BaTi4 O9 can also
evolve O2 and H2 with the aid of co-catalysts, such as Pt, Rh, and
RuO2 [282].
5. Challenges for reneries

In reneries, we expect the synthesis of clean fuels components (syngas to liquids, reformulated gasoline with solid acid
alkylation to obtain branched C8 alkanes of high octane number
values), the reduction of S to less than 10 ppm after 2010 by the
development of new catalysts and new reactor technologies and
by bio-desulfurization, the reduction of aromatics (hydrogenation,
gasication, cracking), and the reduction of heavy metals from
crude oil by bio-demetalization will predominate. High-octane
non-aromatic blend stock that is sulfur and olen free will be
needed to meet the new specications. The future production of
hydrogen without the formation of CO2 should come from photocatalytic splitting of water (vide infra) and the conversion of
methane and light alkanes (C1 C3 ) to higher/aromatic hydrocarbons and hydrogen.
5.1. FischerTropsch synthesis (FT)

In 1922, Franz Fischer and Hans Tropsch converted a CO/H2
mixture to a mixture of hydrocarbons (HCs) and oxygenated compounds using an iron-based catalyst. The cobalt catalysts for this
process were discovered a few years later. Although these processes are old technology, they are still relevant. FischerTropsch
(FT) synthesis is a heterogeneous catalytic process for the production of clean hydrocarbon fuels or chemicals from synthesis
gas, which can be derived from a variety of non-petroleum carbon resources, such as natural gas, coal, biomass, oil sands, or
oil shales [283]. During World War II, FT technology was used in
Germany to produce synthetic fuel (16 kbarrels per day) on Co catalysts [284] and later, in South Africa (SASOL), in synergy with
coal gasication to produce synthetic fuel because of an embargo.
Later, SASOL switched to natural gas (NG) for the production of
syngas for FT. The FT synthesis has received renewed interest in
recent years because of the global demand for a decreased dependence on petroleum for the production of fuels and chemicals.
The product distributions with conventional FT catalysts usually
follow the AndersonSchulzFlory (ASF) distribution and are typically unselective with respect to the formation of hydrocarbons
from methane to waxes. Selectivity control is one of the formidable
challenges in this area.
The most common catalysts used in FT synthesis are still based
on iron or cobalt compounds that work at high pressures (16 MPa)
and at temperatures between 200 and 300 C. Under these conditions, the fuel is of high quality because of the low aromaticity
and the absence of sulfur. The iron-based catalysts produce gasoline, hydrocarbons, and linear alpha-olens, as well as a generally
unwanted mixture of oxygenates, such as alcohols, aldehydes, and
ketones, and excessive amounts of carbon dioxide. With cobalt
catalysts, high yields of long-chain linear parafns, which can be
efciently transformed into valuable products (middle distillates)
by hydroprocessing, are possible. Moreover, the syngas step should
be adapted to the type of catalysts to be used to optimize the CO/H2
ratio in reference to the optimal ratio for the FT catalyst/reactor. To
promote FT over methanation, the FT reactor typically operates at
a low temperature (200240 C), a mild pressure (23 MPa), and
in the presence of a catalyst (Co- or Fe-based). However, various
catalysts have been tested in the FT reaction [285287]. To optimize the overall liquid production, it is necessary to produce high
molecular weight linear waxes for further hydroprocessing steps.
To explain the mechanism of the FT reaction, some authors have
derived the LangmuirHinshelwood or EleyRideal types of rate
expressions for the reactant consumption, where, in the majority of
cases, the rate-determining step was supposed to be the formation
of the building block or monomer, methylene.
17
Recent developments in coreshell-structured catalysts that

contain conventional FT catalysts, such as Co/Al2 O3 as the core
and zeolite (H-ZSM-5) membrane as the shell, have increased the
selectivity to C5 C11 isoparafns because of the hydrocracking and
isomerization ability of zeolite [288]. The use of mesoporous zeolite (meso-ZSM-5) as the support for Ru nanoparticles signicant
enhanced the selectivity to C5 C11 hydrocarbons to greater than
80%, which was signicantly higher than expected from the selectivity based on the ASF distribution (45%) [289]. The use of CNTs
can also increase the selectivity to a particular fraction of hydrocarbons. For example, Ru/CNT gave a C10 C20 selectivity of 60%
[290]. The connement of iron oxide particles inside the CNTs or
carbon spheres could increase the selectivity to C5 + because of the
facile transformation of iron precursors to iron carbides, which are
believed to be responsible for CC coupling [291,292].
5.2. Hydrodesulfurization (HDS) and uid catalytic cracking
(FCC)
Gasoline has the highest concentration of sulfur compounds in
the FCC (uid catalytic cracking) stage of the renery process. Environmental regulations are becoming increasingly stringent with
regard to the sulfur content in fuels. At the same time, olens
present in the FCC naphtha make a major contribution to the octane
number in gasoline [293295]. In this context, desulfurization must
be performed to hamper olen saturation in FCC gasoline [293].
Hydrodesulfurization (HDS) of petroleum feedstock is one of the
most important processes in petroleum rening for the production of clean, high quality fuels [296299]. Sulfur compounds in
petroleum fractions include suldes, disuldes, polysuldes, mercaptans, thiophene, benzothiophene and dibenzothiophene, but
thiophene, benzothiophene and dibenzothiophene are used in HDS
studies as model molecules. For example, hydrodesulfurization of
thiophene is one of the most important reactions that occur in the
second-stage hydrogenation of pyrolysis gasoline in olen plants
[300,301]. A two-stage hydrogenation process is usually used
in industry to eliminate these impurities: (1) hydrogenation for
selective hydrogenation of diolens and (2) thiophene hydrodesulfurization. Therefore, there is a strong incentive to develop catalytic
systems for the FCC/HDS processes. Sulded CoMo or NiMo(W)based catalysts have been extensively used in industry for HDS
reactions [302,303] and have attracted attention as catalytically
active sites where Co decorates the edge sites of highly dispersed
MoS2 crystallites [304308]. However, the precise structures of the
active sites and the HDS reaction mechanism still remain ambiguous. The active sites of the catalysts are considered to be extensively
promoted by their selective preparation. The use of a chelating
agent in the preparation of HDS catalysts [309312] has been found
to be highly effective in increasing the amount of Co(Ni)MoS by
increasing the coverage of Co(Ni) on the edges of MoS2 particles.
The preparation of HDS catalysts using citric acid as a chelating
agent signicantly improves their catalytic activity [313316].
The literature contains reports of various attempts to develop
selective catalysts for this purpose including oxides [317322],
zeolites [323326] and mesoporous materials [327329], clays
[330332] and noble metal catalysts [300,324,333349]. Excellent
studies were conducted on the mild oxidation of thiophenes and
thioethers using green oxidizing agents [350] on mesoporous
materials [351,352].
6. CO2 emissions as a prospective source for fuels and
chemicals [353358]
CO2 is a major contributor to the so-called greenhouse effect,
which supposedly leads to warming of the earth and thus to
18
changes in the climate. The energy sector, which is the largest

source of CO2 emissions, is responsible for approximately 25% of
global CO2 emissions. Great efforts have been conducted in the past
to use carbon dioxide as a chemical raw material with a very low
or even negative cost rather than as a waste, e.g. CO2 reductions
under photoirradiation, or under electrolytic conditions, or production of synthesis gas by reforming natural gas. However, many of
these reactions produce rather simple molecules such as carbon
monoxide and formic acid. CO2 has the advantages of being nontoxic, abundant, and economical, attractive as an environmentally
friendly chemical reagent, especially useful as a phosgene substitute. The largest obstacle for establishing industrial processes
based on CO2 as a raw material is its low energy level. In other
words, a large energy input is required to transform CO2 . There
are several methodologies to transform CO2 into useful chemicals,
such as the use of high-energy starting materials such as hydrogen, unsaturated compounds, small-membered ring compounds,
and organometallics; the choice of oxidized low-energy synthetic
targets such as organic carbonates or the supply of physical energy
such as light or electricity. Selecting appropriate reactions can lead
to a negative Gibbs free energy of the reaction [353358].
Possibilities for the chemical recycling of carbon dioxide to fuels
have been studied largely as a complementary technology to carbon sequestration (CSS) and storage. CSS requires the minimization
of hydrogen consumption to produce fuels [29,258], which can be
easily stored and transported, and to use renewable energy sources.
From this perspective, the preferable option is to produce alcohols
(preferably C2) by use of solar energy to produce the protons
and electrons necessary for CO2 reduction. The chemical transformation of CO2 includes a reverse watergas shift reaction and
hydrogenation to produce hydrocarbons, alcohols, dimethyl ether
and formic acid, a reaction with hydrocarbons to syngas (such
as dry reforming of methane), and photo- and electro-catalytic
and thermochemical conversions [257,258,359361]. CO2 can be
used as a building block in organic syntheses to obtain valuable
chemicals and materials has been discussed in many reports and
review articles. The main applications of CO2 as chemical raw
materials [353] are syntheses of polycarbonates and polyurethanes.
Organic carbonates are roughly categorized into cyclic and linear
carbonates, which both compounds have three oxygens in each
molecule, and are suitable from a thermodynamic point of view
as synthetic targets starting from CO2 . Four industrially important
organic carbonates are ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), and diphenyl carbonate
(DPC). EC, DMC and DPC are useful intermediates for manufacturing polycarbonates through a non-phosgene process [353]. In
addition, EC, PC and DMC are employed as electrolytes in lithium
ion batteries and are widely used as aprotic polar solvents. Furthermore, the excellent properties of DMC as a fuel additive have
attracted much attention. DMC can be synthesised from methanol
and CO2 , over homogeneous catalysts or heterogeneous such as
solid acid catalysts of zirconia modied by Ce and acid additives
such as phosphoric acid, or as a support for heteropolyacids, or
via cyclic carbonates (CO2 with epoxides), the cycloaddition of oxiranes and oxetanes and CO2 over e.g. CeO2 ZrO2 or homogeneous
metal complexes catalysts, or coplymerisation of CO2 and oxiranes
on metal complexes, the synthesis of urea (CO2 + NH3 ) and urethane derivatives, e.g. CO2 + secondary or primary amines giving
carbamic acid which reacts with organic halides or alcohols giving
carbamates (urethanes) or are dehydrated to isocyanate without
using phosgene, the synthesis of carboxylic acids, e.g. acrylic acid,
the synthesis of esters and lactones by combining CO2 with unsaturated compounds such as vinyl ethers, the hydrogenation and
hydroformylation of alkenes by CO2 and H2 , and so forth [353].
Currently, the utilization of CO2 as a chemical feedstock is limited to a few processes, such as the synthesis of urea (for nitrogen
fertilizers and plastics), salicylic acid (a pharmaceutical ingredient)

and polycarbonates (for plastics). It is worth noting that the actual
use of CO2 corresponds to a small percentage of the potential CO2
that is suitable to be converted into chemicals; thus, a chemical
transformation of CO2 may signicantly contribute to a reduction
of its emissions, in particular for the fuel pool, the worldwide consumption of which is two orders of magnitude greater than that
of chemicals. Note that CO2 transformation requires energy, which
may produce CO2 . Thus, the importance of the transformation of
CO2 into useful chemicals should be closely related to the importance of utilizing a renewable feedstock [353].
Different options exist in heterogeneous catalysis for the conversion of CO2 . The hydrogenation of CO2 to form oxygenates
and/or hydrocarbons are the most intensively investigated area of
CO2 conversion. Methanol synthesis from CO2 and H2 has been
investigated at the pilot-plant stage with promising results. An
alternative possibility is the production of DME, which is a potential
diesel substitute. Ethanol formation, either directly or via methanol
homologation, and the conversion of CO2 to formic acid are also
potentially interesting routes. Methanol, ethanol, and formic acid
may also be used as feedstocks in fuel cells, which provide a route
to store energy from CO2 and then produce electricity.
The hydrogenation of carbon dioxide to hydrocarbons consumes
much more hydrogen (per unit of product) than the formation
of oxygenates. Therefore, this route is, in principle, only valuable
when hydrogen is made primarily from renewable or non-fossil
resources; however, other thermodynamic aspects must also be
considered. The dry reforming of methane with CO2 is a known
technology that is available on a nearly industrial scale, although
the positive impact on CO2 emissions is questionable [362364].
Specically, it is important to ensure that CO2 emissions due to
energy consumption are not greater than the amount of CO2 consumed in the reaction. An improvement in the positive direction is
tri-reforming, which operates autothermically and does not require
a pure CO2 feed stream; however, large-scale demonstration units
are necessary [365,366].
The conversion of CO2 at room temperature and atmospheric
pressure using solar light represents a highly challenging approach
to close the CO2 cycle and develop approaches that mimic photosynthesis. An interesting solution could be a photoelectrochemical
(PEC) reactor that operates in the gas phase and uses nanoconned
electrodes that differ from those used in conventional PEC systems,
as described [247].
7. Activation and upgrading of light alkanes

Alkanes are currently two to three times cheaper than the corresponding olens and are thus quite valuable for upgrading. Olens
are mainly used for polymerization processes. There are several
possibilities to up-grade to light alkanes (C2 C6 ). An isomerization
reaction on an acid catalyst can yield branched alkanes of higher
octane number. An acid catalyzed alkylation reaction on isobutane
with butene can yield trimethyl pentanes of high octane number
or other isomers, such as dimethyl hexanes, of much lower octane
number [367369]. The main industrial catalysts are HF and H2 SO4
in solution [370], although signicant efforts have been made in
the past 30 years to nd a solid substitute without yielding any
reliable/promising process. No industrial processes could emerge
as deactivation due to fouling by butene polymerization residues
was too important and selectivity to TMP versus dimethyl hexanes (DMH) of low octane number was too low (5060). Another
approach is to proceed by dehydrogenation, e.g., on Pt-Sn/Al2 O3 ,
or by oxydehydrogenation of alkanes on V-based mixed oxides.
The former reaction is endothermic and highly sensitive to deactivation by coke deposits [371373]. The latter is exothermic with
low deactivation by coke fouling, but it may lead to total oxidation and CO2 formation and, thus, to a lower selectivity to alkenes.
A third way is oxidizing/ammoxidizing the alkanes to the corresponding oxygenates or oxynitriles such as aceto or acrylo-nitriles,
aldehydes, ketones or acids. Two processes have been developed
industrially, oxidation of butane to maleic anhydride on a vanadyl
pyrophosphate based VPO catalyst or ammoxidation of propane to
acrylonitrile on MoVTeNb mixed oxide catalysts. Maleic anhydride
is a raw monomer for resin and for THF an industrial solvent produced by Reppe process of maleic ahydride reduction pn Pd catalsyt
as well as a monomer for segmented polyurethanes (Lycra) and
copolyester elastomers (Hytrel). Vanadium-based catalysts [374]
and in particular, vanadium phosphates (VPOs) are very well known
as the only catalysts for industrial process of n-butane oxidation
to maleic anhydride [375378], which is a precursor of polyester
resins [379]. In general, VPO catalysts are inexpensive and attractive in selective oxidation processes since they are environmentally
friendly [380]. The reaction follows Mars van Krevelen mechanism
where the adsorbed organic molecule is oxidized by lattice oxygen
from the catalyst, which is subsequently restored by oxygen reaction feed. Acrylonitrile was produced in ammoxidation reaction of
propylene using FeBiMoO and FeSbO systems as catalysts
but this process would be replaced in a near future by ammoxidation of propane due to the lower cost and abundance of propane.
Acrylonitrile is the main raw material for production of synthetic
bers, plastics, elastomers and polymers as styreneacrylonitrile
and acrylonitrilebutadienestyrene. By polymerization of acrylonitrile with butadiene synthetic rubber is produced. This process
includes multifunctional molybdates and antimonates as catalysts.
However, propane conversion is about ten times lower than that
of propylene in the same conditions since the activation energy
of C H bond is higher. The more performing catalyst developed
recently by Japanese industrialists [381,382] is a mixed MoVNbTe
oxide active for the (amm)oxidation of propane to (acrylonitrile)
acrylic acid [381384]. A process, designated AlkyClean using a
solid acid catalyst (HY-zeolite based) and claimed to be competitive with other two processes, was proposed [355] by Akzo Nobel,
ABB Lummus Global and Fortum with a demonstration unit constructed at Fortum facilities in Porvoo, Finland. The reaction is
carried out in liquid phase at 5090 C with isobutane to olen ratio
(i/o) of 8 to 10 against 410 C and i/o = 810 for H2 SO4 and 3238 C
and i/o = 1215/1 for HF respectively. Regeneration was realized at
250 C under hydrogen. For this research part see special issue of
Appl Catal A, Ed. G.S. Patience, J.M. Lpez-Nieto [385].
8. Waste air, water and VOCs treatments

Wet air oxidation (WAO) is a liquid-phase reaction between
organic material in water and oxygen. The WAO process is used
around the world to treat industrial wastewaters and sludges
at moderate temperatures (180315 C) and at pressures from 2
to 15 MPa. Under these conditions, complex organic compounds
are primarily oxidized to carbon dioxide and water, along with
simpler forms that are biodegradable. Unlike other thermal processes, WAO produces no NOx , SO2 , HCl, dioxins, furans or y ash.
However, the efciency of aqueous-phase oxidation can be significantly improved by the use of catalysts, either heterogeneous or
homogeneous. Moreover, key points to be solved are the stability
of the heterogeneous catalysts and the recycling of the homogeneous catalysts. Commercial catalytic WAO (CWAO) processes
started as early as the mid-1950s in the USA. Several Japanese
companies developed CWAO technologies that relied on heterogeneous catalysts based on precious metals deposited on titania or
titaniazirconia. Compared with conventional WAO, CWAO offers
lower energy requirements and signicantly higher oxidation
19
efciencies. Further developments of this technology should

include highly durable and low-cost catalysts. CWAO provides an
environmentally attractive option to manage the growing problems
of the treatment of organic sludge and toxic wastewater [386,387].
The treatment of toxic nitrogen-containing compounds, which
are mainly produced in the chemical and pharmaceutical industries, is one of the major applications of the wet air oxidation
(WAO) process. Many studies have dealt with the oxidation of aniline, which is often chosen as a model molecule of a dye-industry
pollutant. Particular attention has been paid to selectivity toward
organic by-products (especially azo, nitroso and nitro compounds,
phenolic compounds and carboxylic acids) and inorganic forms of
nitrogen (NH4 + , N2 , NO2 , NO3 ). Usually, similar catalysts can be
used for the CWAO of oxygen-containing (phenol, carboxylic acids)
and nitrogen-containing organic compounds. Ammonia is one of
the most refractory by-products formed during catalytic WAO of
nitrogen-containing organic pollutants and is itself a pollutant.
Very high selectivities to dinitrogen have been obtained on certain
noble-metal catalysts. As a rule, catalysts that are active and selective for ammonia oxidation are different (nature of active phase,
support, etc.) from the solids proven to be the best catalysts for the
CWAO reactions of organic compounds. Multifunctional catalysts
are therefore required for the treatment of nitrogenous organic
compounds.
Volatile organic compounds (VOCs) are signicant atmospheric
pollutants due to their high toxicity and malodorous nature.
VOC emissions arise from mobile sources and industrial applications. In this context, the degradation of VOCs has become a
major area of research in environmental protection during recent
decades [388,389]. Common VOCs such as halogenated hydrocarbons, ketones, alcohols and aromatic compounds have been widely
used in many industries and are often found in the emissions ow
[390,391].
Traditional methods of removing VOCs from the polluted air
stream include adsorption onto activated carbon or zeolite and
thermal combustion. These methods have inherent limitations. The
adsorption process includes recovery treatments that require the
regeneration of the adsorbent and also requires durability, whereas
the high temperature of VOC degradation makes thermal degradation not economically feasible.
Many advanced technologies have been developed for the rapid
and economical removal of VOCs from indoor air. Among these,
catalytic oxidation is the most innovative and promising approach.
This oxidation process is promising for air purication because
the pollutants can be oxidized to H2 O and CO2 . The catalysts play
the most important role by converting polluting compounds into
relatively harmless compounds at low operating temperatures.
A series of catalysts were evaluated for VOC decomposition
[388,389,392402]. The most active catalysts are the noble metal
catalysts dispersed on high surface area supports. The dispersion
increases both the available metal surface area and the thermal
stability. Many researchers have suggested that the performance of
noble metal supported catalysts for the oxidation of VOCs is highly
dependent on the oxidation state of the metal. Some authors have
suggested that the oxide species are more active than the metallic
species for catalytic oxidation, while others argue the opposite.
In the case of catalysts with the same oxidation state, the particle
sizes may play a more important role in the catalytic activity [403].
Several studies have shown a correlation between the catalytic
activity and the oxidation state of the catalyst, the nature of the
support, the metal-support interaction, and the morphology of the
catalyst particles [389,403417]. However, the use of noble metals
leads to a high cost purication system and the natural reserve of
noble metals is limited. Therefore, the substitution of noble metals
with ubiquitous elements is required for environmental and
economic reasons. Metal oxides have been reported as relatively
20
high activity catalysts for the complete oxidation of VOC [392,393].

Research efforts in this eld are oriented towards the development
of new catalytic materials with low manufacturing costs that show
high activities at moderate temperatures.
9. Photocatalysis
In the 1930s, the term photocatalysis was introduced as new
branch of catalysis. Photocatalysis is dened as a change in the rate
of a chemical reaction under the action of light in the presence
of photocatalysts that absorb light quanta and are involved in the
chemical transformations of the reaction participants [418,419].
The photocatalyst is dened as a solid that functions by photoinduced electron transfer at moleculesemiconductor interfaces
[282,420423].
Among photocatalytic applications, photocatalytic oxidation
and the reduction of organic compounds in water have become
important and have received considerable attention during the last
few years [282,424427]. These applications involve the oxidation
or reduction of an organic compound to an intermediate that contains oxygen or to carbon dioxide, water, and a mineral acid if a
heteroatom such as nitrogen or chlorine is present. The mechanism of the photocatalytic decomposition of organic compounds is
supposed to follow these steps: under UV-light illumination, the
absorption of photons creates an electronhole pair if the photon
energy is greater than that of the band gap; thereafter, the pairs
migrate to the surface and are trapped by OH surface groups and
other surface sites, thereby forming hydroxyl (OH ), hydrosuperoxide (H2 O) and superoxide (O2 ) radicals; these free radicals
nally cause the oxidation of the organic compounds [425428].
This process can be used in various areas such as the elimination of odor from drinking water, the degradation of oil spills in
surface-water systems, and the degradation of harmful organic
contaminants, such as herbicides, pesticides, and refractive dyes.
One of the most widely studied metal oxides is semiconducting
TiO2 [423]. Three common TiO2 polymorphs exist in nature, which,
in the order of abundance, are rutile, anatase, and brookite. An
additional synthetic phase, called TiO2 (B), and some high-pressure
polymorphs are also known [428]. The rutile and anatase polymorphs are primarily used in photocatalysis. Both the rutile and
anatase crystal structures comprise distorted octahedra. In rutile,
a slight distortion from orthorhombic geometry occurs, where the
unit cell is stretched beyond a cubic shape. In anatase, the distortion
of the cubic lattice is more signicant, and thus, the resulting symmetry is less orthorhombic [429]. Titania, in anatase form, exhibits
a strong photocatalytic effect, which generates electronhole pairs.
As a result, the material can harvest photons in the near-UV region
(<410 nm) to provide its surface strong oxidizing power to decompose organic molecules. Photocatalysis is a rapidly growing eld of
study that has attracted intense attention of chemical and materials
researchers in recent years.
Even though TiO2 exhibits excellent photocatalytic activities
in the decomposition of VOCs and other organic compounds, the
study new photocatalysts with different structures that exhibit
higher activity is desirable. In this regard, the novel photocatalysts made of highly donor-doped (110) layered perovskites, have
recently been developed and were found to be much more efcient than bulk-type TiO2 . This higher activity results from the
highly donor-doped electronic structure, which leads to a narrower depletion region and a more facile separation of the charge
carriers.
Selective photocatalysis can be achieved using proper molecular sieves, such as the titanosilicate ETS-10, which provides
an alternative approach. The photocatalytic activity of ETS-10 is
due to the presence of photoexcitable TiOTi chains and the
three-dimensional interconnected pore system of large 12membered ring channels in its structure, which endow the material
with excellent diffusion properties [430]. This regular channel system has a direct effect in determining the shape selectivity of the
degradation process [431]. Another approach is the introduction
of some transition metals, such as Cr, V, Fe, Cu, Mn, Co, Ni, Mo,
or La, into the synthesis mixture of the MCM-41 and MMS [432].
The authors then demonstrated that the presence of the transitionmetal salts in the gel during the hydrothermal synthesis process
hinders the action of the template, which results in MCM-41 pores
that are not well formed. These materials were then loaded with
TiO2 via the solgel method, and the activity of the TiO2 /TM-MCM41 catalysts toward the degradation of 4-chlorophenol was tested
in the presence of UV and/or visible light. The results showed that,
although some metals were deleterious, others improved the performance of the photocatalysts and even enabled them to utilize
visible light. A wide range of other semiconductors and materials
have been tested for photocatalytic activity. In general, they have
been found to be less active than titanium dioxide; signicant work
has been conducted with V2 O5 , Fe2 O3 , ZnO, ZnS, CdS, Pt/CdS, ZnTe,
ZrTiO4 , MoS2 , SnO2 , Sb2 O4 , Sn/SbO2 , CeO2 , WO3 , and Nb2 O5 .
10. Solar photon conversion [433]

The efcient and cost-effective direct conversion of solar photons into solar electricity and solar fuels is one of the most
important scientic and technological challenges of this century. At
least 20 TW of carbon-free energy (1.5 times the total amount of all
forms of energy consumed today globally), in the form of electricity
and liquid and gaseous fuels, are estimated to be required by 2050
to avoid the most serious consequences of global climate change
and to ensure an adequate global energy supply that will avoid
economic chaos. However, for solar energy to contribute a major
fraction of future carbon-free energy supplies, it must be priced
competitively with, or perhaps even be less costly than, energy from
fossil fuels, nuclear power and other renewable energy resources.
The challenge of delivering very low-cost solar fuels and electricity will require breakthrough advances in both fundamental and
applied sciences. These required advances include new concepts for
low-cost photovoltaic (PV) energy based on chemistry, solar water
splitting, redox catalysis for water oxidation and reduction, photoelectrochemical energy conversion, and photoinduced electron
transfer. Note that the total energy capacity at the end of 2009 was
approximately 7 GW-years (0.2% of global electricity usage). Thus,
there is potential for the PV industry to grow substantially in the
future (by a factor of 100300) for it to provide a signicant fraction of the total global electricity needs (currently approximately
3.5 TW).
Presently, solar-derived fuels are produced from biomass
(labeled as biofuels) and are generated through biological photosynthesis. The global production of liquid biofuels in 2009 was
approximately 1.6 million barrels/day, equivalent to a yearly
output of approximately 2.5 EJ (about 1.3% of global liquid fuel utilization). The direct conversion of solar photons to fuels produces
high-energy chemical products that are labeled as solar fuels; these
fuels can be produced through nonbiological approaches, which
are generally referred to as articial photosynthesis. The feedstocks
for articial photosynthesis are H2 O and CO2 , which react either as
coupled oxidationreduction reactions, as in biological photosynthesis, or by rst splitting H2 O into H2 and O2 and then reacting H2
with CO2 (or CO produced from CO2 ) in a second step to produce
fuels through the known chemical routes previously described such
as syngas, watergas shift reaction, or alcohol synthesis. The solar
generated H2 can itself be used as a gaseous fuel, such as in fuel
cells. However, currently, no solar-fuels industry exists. Signicant
21
12. Major challenges for the future

12.1. Scientic challenges
These challenges cover the design, preparation, evaluation, and
optimization of new catalytic materials, the probing/understanding
of catalyst behavior (activity and selectivity) at the molecular level,
the enhancement of technology transfer between academia and
industry (bridge the gap), the development of multifunctional reactors, combinatorial catalysis, high-throughput catalyst testing, the
characterisation of catalysts using highly improved physical and
chemical techniques, particularly used under working conditions
and simultaneously with several other techniques together [451],
heterogeneisation of homogeneous catalysts (vide supra Section
2.9), the coupling of chemical and engineering kinetics, and so forth.
12.2. Environmental challenges
Fig. 16. Major factors inuencing selectivity in catalytic reactions [455].
research and developments are required to create a solar-fuels

industry, which constitutes one of the key challenges for the future.
11. Green chemistry selectivity in catalysis

A new area of research emerged in the 1990s based on the 12
principles of green chemistry [434,435] including the atom economy, the use of reusable catalysts and the minimization of waste
[436]. The principle of green chemistry is that rather than using
every possible chemical process, only those that are environmentally benign should be used [437]. Within green chemistry, there
is an increasing interest in developing novel materials that can be
applied as heterogeneous catalysts for chemical processes, replacing effective but hazardous chemicals, such as H2 SO4 , HF and AlCl3 .
Processes using these novel compounds, such as zeolites, have very
high E-factors, a quantitative parameter that can be used to assess
the environmental acceptability of a process [438]. It corresponds
to the ratio of kilograms of waste divided by kilograms of product.
For example, the zeolites used in the petrochemical industry have
an E-factor of 0.1 (high greenness) and have been widely implemented in very large scale industrial processes because they can
easily be separated from the products and reused. Because of their
lack of toxicity, they constitute a prime example of green chemistry.
Moreover, a challenge for the XXIst century is the control of
technological processes in the chemical, petrochemical, and pharmaceutical industries to develop atom-economical, environmental
friendly processes without by-products [3,439441]. The chemical
and petrochemical industries have always attempted to improve
process efciency and reduce waste using heterogeneous catalysts
[293,442447]. High selectivity is the most important aspect of a
catalyst. The noble metal catalysts show high activity and selectivity, but suffer from several drawbacks, including sensitivity to
metal site poisoning, the limited abundance, and the environmental impact of these metals. As a result, the tendency now is to
replace the noble metal catalysts [199,201,447449]. In light of the
ubiquitous restrictions imposed by environmental and economical
legislation, use of nanostructured porous molecular sieves, which
can be very selective for the desired products at low temperature
and are recyclable, is one alternative to the use of traditional noble
metal catalysts. We have summarized in Fig. 16 the main factors
that inuence selectivity in catalysis and that must be taken into
account in all processes.
These challenges consist of minimizing and/or managing

by-products by converting them to useful products, replacing multistep processes by direct schemes to avoid exposure to dangerous
intermediates, reducing efuents (gases, solvents, salts), and using
sustainable sources of raw materials and energy supplies. The
development of biomass for raw chemical materials and energy
sources should become a key point for the future. The development of bioreneries is in its infancy; however, with reference to
the past the in petroleum industry, one may imagine that great
improvements will be developed with continuous research in this
eld.
12.3. Economical challenges
Economical challenges naturally correspond to the use of
cheaper, readily available raw materials, increased productivity,
decreased lag-time between discovery to commercialization, the
discovery novel catalytic reactions, the development of processes
that are more selective and intensive, the accelerated discovery of
new catalysts-based on non noble metals [199,201], and the evaluation and scale-up of processes.
12.4. Energy challenges
Energy challenges correspond to reduce energy consumption,
e.g. by favouring of hydrogen production as a source of energy
and as an important chemical material, to develop efcient watersplitting technologies, and to enhance uses [452] of biomass and
other renewable sources, such as solar, wind, hydroelectric, and
nuclear energies. All these technologies must be developed as alternative sources to fossil energies. One is still very far from replacing
fossil energies, and great effort is required on a short time scale. The
future will rely on solar energy and the implementation of efcient
methods for electrical energy storage [450,453]. However, significant scientic advancement is still required for the practical and
safe deployment of both of these technologies. In 2005, 7% of the
world energy use was derived from nuclear power (Fig. 13), 10% was
derived from biomass, 2% was derived from hydroelectric sources,
and a mere 1% of the energy consumed was obtained from alternate
renewable resources. Closer examination of the tiny 1% fraction
shows that both solar energy in the form of photovoltaics and wind
power are drastically underemployed (Fig. 13). These technologies,
of course, represent two renewable resources of an innite supply.
12.4.1. Challenges in automotive catalysis
Since the introduction of exhaust gas converters in cars in
1976 by Ford, many advances have been realized in reformulated
gasoline or diesel, in particulate emission/trapping control and in
22
Table 6
Major problems and challenges in automotive car industry.
Challenge
Drivers
Problem
Lean burn gasoline engine

Dry particulate emissions from diesel engines
Efciency higher by ca. 25%

DOC reduces SOF, HC, and CO; no
current catalyst/system to treat dry
soot
Direct decomposition or reduction of
NOx in O2 -rich atmosphere
NOx trapping; SOx tolerant traps

Catalyst to lower lightoff T of soot;
addition of Cu and Ce-organometallics
to fuel
Larger operating window for PM or
BM-catalysts, NH3 or urea SCR.
Diesel engine lean NOx
electronic devices to regulate the air/fuel ratio in the motors. The

initial three way catalysts for simultaneous CO oxidation, NO reduction, hydrocarbon total oxidation were improved further with the
use of Pd. Another presentation by R. Farrauto et al. [454] provides
details of the actual performances and of the future prospects. Only
some major issues are summarized in Table 6. Moreover, the development of highly active HDS, FCC, Naphtha catalysts is one of the
most urgent challenges in the petroleum industry not only to protect the environment but also to efciently utilize limited natural
resources.
13. Conclusions
As we have described in this review, our dependence on fossil fuels (coal, petroleum, and natural gas) is largely due to their
chemical energy being the most convenient and useful form of
transportable energy. However, the extensive use of fossil fuels
has dramatically inuenced the environment and peoples health,
while world reserves are diminishing inexorably, although new
elds are still being discovered and although methane hydrates
may provide a substitute for some time. This situation cannot last
for long, and substantial advances are urgently needed.
We have also shown that the solution to the challenge of clean
energy can arise from simple components: sunlight and water
[455]. Sunlight and water are innite resources and can provide the
required diversity of energy supplies. To store energy from sunlight,
water can be split to generate hydrogen, a clean and portable energy
carrier that can then be used to supply electricity when needed.
High-performance, light-weight batteries can be used to power
electric vehicles. However, such technological advances require
systems that are capable of producing electricity, breaking H2 O
bonds with the separation of H2 and O2 , and storing the energy
either in batteries or as molecular hydrogen. Currently, such systems pose formidable challenges in terms of the required materials,
efciency, cost, and design of practical devices.
The locus of activity in catalysis continues to move. In the
eighteenth and nineteenth centuries, major discoveries and developments were performed in Europe. In the twentieth century, both
Europe and the USA were the major contributors, although Japan
and Korea also provided important efforts and discoveries in the
second half of the century. For the twenty-rst century, China,
Korea, Japan and other Asian countries are expected to lead in the
eld of catalysis.
At the end of the last century, major large chemical industrial
companies have more or less abandoned large catalysis research
centres within their laboratories. They now rely on catalysts producers, institutes and/or academic researchers to discover new
catalysts or develop new technologies.
The development of surface, bulk and in situ characterisation
techniques [451], molecular modelling, and advanced synthesis
methods have transformed the preparation of solid catalysts and
the characterisation of their physical and chemical (catalytic) properties from an art into a science. Such a trend should and will
continue in the future with the new generations of scientists, engineers and researchers.
Acknowledgement
Support from CNRS France is gratefully acknowledged by I.
Fechete.
References
[1] American Chemical Society Report, Technology Vision 2020, the Chemical Industry, December 1996, http://www/chemicalvision2020.com/
pdfs/chem vision.pdf.
[2] A. Corma, Chemical Reviews 97 (1997) 2373.
[3] G.A. Somorjai, R.M. Rioux, Catalysis Today 100 (2005) 201.
[4] A. Kieboom, J. Moulijn, P. van Leeuwen, R. van Santen, Studies in Surface
Science and Catalysis 123 (2000) 3.
[5] B. Lindstrom, L. Petterson, CatTech 7 (2003) 130.
[6] J.N. Armor, Catalysis Today 163 (2010) 3.
[7] E. Jones, Industrial and Engineering Chemistry 42 (1950) 2208.
[8] Ya. Guerasimov, V. Dreving, E. Eriomin, A. Kiseliov, V. Lebedev, G. Pacehnkov,
Ashliguin Curso de Fisica Quimica, Tomo II, Editorial MIR, Moscow, 1971.
[9] H. Davy, Philosophical Transactions of the Royal Society 97 (1817) 45.
[10] A. Fusinieri, Giurnali Fisica 7 (1824) 371.
[11] J. Berzelius, Annales de chimie et de physique 61 (1836) 146.
[12] F. Fischer, H. Tropsch, Brennst.-Chem. 4 (1923) 276.
[13] F. Fischer, H. Tropsch, Brennst.-Chem. 7 (1926) 97.
[14] J.C. Vdrine, Catalysis Today 56 (2000) 455.
[15] A.D. McNaught, A. Wilkinson, IUPAC Compendium of Chemical Terminology,
2nd edition, British Royal Society of Chemistry, Cambridge, UK, 1997.
[16] J.H. Clark, D.J. Macquarrie, K. Wilson, Studies in Surface Science and Catalysis
129 (2000) 25.
[17] W. Holderich, M. Hesse, F. Naumann, Angewandte Chemie International Edition 27 (1988) 226.
[18] C.J. Plank, E.J. Rosinski, Chemical Engineering Progress Symposium Series 73
(1967) 26.
[19] J.J. Blazek, Oil and Gas Journal 69 (1971) 66.
[20] S.C. Eastwood, R.D. Drew, F.D. Hartzell, Oil and Gas Journal 60 (1962) 152.
[21] S.C. Eastwood, C.J. Plank, P.B. Weiss, 8th World Petr. Congr. 4 (1971) 245.
[22] A.W. Chester, W.E. Cormier Jr., W.A. Strover, US Patent 4,368,114 (1983).
[23] N.Y. Chen, A.B. Ketkar, D.M. Nace, A.Y. Kam, C.R. Kennedy, R.A. Ware, European
Patent Application (1986) 186446.
[24] C. Marcilly, J.M. Daves, F. Raatz, European Patent Application 278 (1988) 839,
assigned to IFP.
[25] N.Y. Chen, W. Grawood, F. Dwyer, Shape Selective Catalysis in Industrial Applications, Marcel Dekker, New York, 1995.
[26] R.M. Barrer, Advances in Chemistry Series 102 (1971) 1.
[27] S.M. Csicsery, ACS Monograph 171 (1976) 680.
[28] E.G. Derouane, in: M.S. Whittingham, A. Jacobson (Eds.), Intercalation Chemistry, Academic Press, New York, 1982, p. 101.
[29] E.G. Derouane, Z. Gabelica, Journal of Catalysis 65 (1980) 486.
[30] N.Y. Chen, S.J. Lucki, E.B. Mower, Journal of Catalysis 13 (1969) 329.
[31] R.M. Dessau, ACS Symposium Series 135 (1980) 123.
[32] P. Tynjala, T.T. Pakkanen, Journal of Molecular Catalysis A Chemical 122
(1997) 159.
[33] S. Inagaki, K. Kamino, E. Kikuchi, M. Matsukata, Applied Catalysis A General
318 (2007) 22.
[34] E. Dumitriu, I. Fechete, P. Caullet, H. Kessler, V. Hulea, C. Chelaru, T. Hulea, X.
Bourdon, Studies in Surface Science and Catalysis 142A (2001) 951.
[35] C. Brechtelsbauer, G. Emig, Applied Catalysis A General 161 (1997) 79.
[36] I. Fechete, A. Simon-Masseron, E. Dumitriu, D. Lutic, P. Caullet, H. Kessler,
Revue Roumaine de Chimie 53 (2008) 55.
[37] F.J. Llopis, G. Sastre, A. Corma, Journal of Catalysis 227 (2004) 227.
[38] I. Fechete, P. Caullet, E. Dumitriu, V. Hulea, H. Kessler, Applied Catalysis A
General 280 (2005) 245.
[39] E. Derouane, J.C. Vdrine, Journal of Molecular Catalysis 8 (1980) 479.
[40] J.C. Vdrine, A. Auroux, P. Dejaifve, V. Ducarme, H. Hoser, S.B. Zhou, Journal of
Catalysis 73 (1982) 147.
[41] E.G. Derouane, P. Dejaifve, Z. Gabelica, J.C. Vdrine, Faraday Discussions 72
(1982) 331.
[42] M.B. Sayed, J.C. Vdrine, Journal of Catalysis 101 (1986) 43.
[43] G. Coudurier, A. Auroux, J.C. Vdrine, R.D. Farlee, L. Abrams, R.D. Shannon,
Journal of Catalysis 108 (1987) 1.
[44] M.B. Sayed, A. Auroux, J.C. Vdrine, Journal of Catalysis 116 (1989) 1.

[45] J.C. Vdrine, in: R.K. Grasselli, J.F. Bradzil (Eds.), Solid State Chemistry in Catalysis, 249, ACS Symp. Ser., 1985, p. 257.
[46] J. Frilette, W.O. Haag, R.M. Lago, Journal of Catalysis 67 (1981) 218.
[47] E.G. Derouane, Journal of Catalysis 100 (1986) 541.
[48] E.G. Derouane, J.M. Andr, A.A. Lucas, Chemical Physics Letters 137 (1987)
336;
E.G. Derouane, Chemical Physics Letters 142 (1987) 200.
[49] E.G. Derouane, J.M. Andr, A.A. Lucas, Journal of Catalysis 110 (1988) 58.
[50] B.F. Mentzen, J.C. Vdrine, R. Khouzami, G. Coudurier, Comptes Rendus de
lAcadmie des Sciences Series II 305 (1987) 263.
[51] G.I. Panov, G.A. Sheveleva, A.S. Kharitonov, V.N. Romannikov, L.A. Vostrikova,
Applied Catalysis A General 82 (1992) 31.
[52] G.I. Panov, A.K. Uriarte, M.A. Rodkin, V.I. Sobolev, Catalysis Today 41 (1998)
365.
[53] G.I. Panov, CatTech 4 (2000) 18.
[54] L.V. Pirutko, S.V. Chernyavsky, A.K. Uriarte, G.I. Panov, Applied Catalysis A
General 227 (2002) 143.
[55] G.K.A. Dubkov, N.S. Ovanesyan, A.A. Shteinman, E.V. Starokon, G.I. Panov,
Journal of Catalysis 207 (2002) 341.
[56] T. Ren, L. Yan, X. Zhang, J. Suo, Applied Catalysis A General 244 (2003) 11.
[57] J.B. Taboada, E.J.M. Hensen, I.W.C.E. Arends, G. Mul, A.R. Overweg, Catalysis
Today 110 (2005) 221.
[58] D. Meloni, R. Monaci, E. Rombi, C. Guimon, H. Martinez, I. Fechete, E. Dumitriu,
Studies in Surface Science and Catalysis 142 (2002) 167.
[59] S. Grucarevic, V. Merz, Chemische Berichte 6 (1873) 60.
[60] P.H. Gore, in: G.A. Olah (Ed.), Friedel-Crafts and Related Reactions, vol. III, John
Wiley & Sons Inc, London, 1964, p. 1 (Part 1).
[61] G.A. Olah, Friedel-Crafts Chemistry, J. Wiley, New York, 1973.
[62] G. Sartori, R. Maggi, Chemical Reviews 106 (2006) 1077.
[63] E.G. Derouane, C.J. Dillon, D. Bethell, S.B. Derouane-Abd Hamid, Journal of
Catalysis 187 (1999) 209.
[64] E.G. Derouane, G. Crehan, C.J. Dillon, D. Bethell, H. He, S.B. Derouane-Abd
Hamid, Journal of Catalysis 194 (2000) 410.
[65] H.G. Franck, J.V. Standelhofer, Industrial Aromatic Chemistry, Springer, Berlin,
1988.
[66] J.S. Beck, W.O. Haag, in: G. Ertl, H. Knozinger, J. Weitkamp (Eds.), Handbook
of the Heterogeneous Catalysis, vol. 5, Wiley VCH, Weinheim, 1997, p. 2136.
[67] F. Alario, M. Guisnet, in: M. Guisnet, J.P. Gilson (Eds.), Zeolites for Cleaner
Technologies, Imperial College Press, London, 2002, p. 189.
[68] F.G. Dwyer, Studies in Surface Science and Catalysis 67 (1991) 179.
[69] Z. Zhu, Q. Chen, W. Zhu, D. Kong, C. Li, Catalysis Today 9395 (2004) 321.
[70] P. Ratnasamy, R.N. Bhat, S.K. Pokhriyal, Journal of Catalysis 119 (1989) 65.
[71] I. Benito, A. Del Riego, M. Martinea, Applied Catalysis A General 180 (1999)
175.
[72] A.M. Prakash, S.V.V. Chilukuri, R.P. Bagwe, S. Ashtekar, D.K. Chakrabarty,
Microporous Materials 6 (1996) 89.
[73] A. Blanco, J.M. Campelo, A. Garcia, D. Luna, J.M. Marinas, A.A. Romero, Journal
of Catalysis 137 (1992) 51.
[74] K.J.A. Raj, E.J.P. Malar, V.R. Vijayaraghavan, Journal of Molecular Catalysis A
Chemical 243 (2006) 99.
[75] M. Ghiaci, A. Abbaspur, M. Arshadi, B. Aghabarari, Applied Catalysis A General 316 (2007) 32.
[76] W.S. Wieland, R.J. Davis, J.M. Garcesy, Journal of Catalysis 173 (1998) 490.
[77] J.C. Vdrine, A. Auroux, G. Coudurier, P. Engelhard, J.P. Gallez, G. Szabo, in:
D. Olson, A. Bisio (Eds.), Proceedings 6th International Zeolite Confererence,
Butterworths, Guilford, 1984, p. 497.
[78] T. Nobusawa, J.C. Vdrine, Catalysis Science & Technology 1 (1991) 97.
[79] V. Ducarme, J.C. Vdrine, Applied Catalysis 17 (1985) 175.
[80] T.-C. Tsai, Applied Catalysis A General 301 (2006) 292.
[81] S. Amokrane, D. Nibou, Comptes Rendus de lAcadmie des Sciences 13 (2010)
538.
[82] I. Fechete, E. Gautron, E. Dumitriu, D. Lutic, P. Caullet, H. Kessler, Revue
Roumaine de Chimie 53 (2008) 49.
[83] V. Mavrodinova, M. Popova, Catalysis Communications 6 (2005) 247.
[84] B. Sulikowski, R. Rachwalik, Applied Catalysis A General 256 (2003) 173.
[85] Roldn, F.J. Romero, C. Jimnez, V. Borau, J.M. Marinas, Applied Catalysis A
General 266 (2004) 203.
[86] E. Dumitriu, C. Guimon, V. Hulea, D. Lutic, I. Fechete, Applied Catalysis A
General 237 (2002) 211.
[87] A. Krejc, S. Al-Khattaf, M. Ashraf Ali, M. Bejblov, J. Cejka,

Applied Catalysis A
General 377 (2010) 99.
[88] V. Mavrodinova, M. Popova, R.M. Mihlyi, G. P-Borbly, Ch. Minchev,
[89] A.B. Halgeri, T.S.R. Prasada Rao, Studies in Surface Science and Catalysis 24
(1985) 667.
[90] N.M. Tukur, S. Al-Khattaf, Chemical Engineering Journal 166 (2011) 348.
[91] S. Zheng, A. Jentys, J.A. Lercher, Journal of Catalysis 241 (2006) 304.
[92] M. Guisnet, N.S. Gnep, S. Morin, Microporous and Mesoporous Materials
3536 (2000) 47.
[93] K.J. Chao, L.J. Leu, Zeolites 9 (1989) 193.
[94] A. Corma, F. Llopis, J.B. Monton, Studies in Surface Science and Catalysis 75
(1993) 1145.
[95] D. Fraenkel, M. Levy, Journal of Catalysis 118 (1989) 10.
[96] H. Xu, S. Pu, T. Inui, Catalysis Letters 41 (1996) 83.
[97] S. Namba, H. Ohta, J.H. Kim, T. Yashima, Studies in Surface Science and Catalysis 75 (1993) 279.
23
[98] J. Kim, T. Kunieda, M. Niwa, Journal of Catalysis 173 (1998) 433.

[99] A.K. Aboul-Gheit, S.M. Abdel-Hamid, F.M. Abdel-Hay, Applied Catalysis A
General 93 (1993) 131.
[100] B. Adair, C. Chen, K. Wan, M.E. Davis, Microporous Materials 7 (1996) 261.
[101] R. Wendelbo, R. Roqul-Malherbe, Microporous Materials 10 (1997) 231.
[102] P. Wu, T. Komatsu, T. Yashima, Microporous and Mesoporous Materials 22
(1998) 343.
[103] M.K. Rubin, P. Chu, US Patent 4,954,325 (1990).
[104] S.T. Wilson, B.M. Lok, C.A. Messina, T.R. Cannan, E.M. Flanigen, Journal of the
American Chemical Society 104 (1982) 1146.
[105] S.T. Wilson, B.M. Lok, E.M. Flanigen, US Patent 4,310,440 (1982).
[106] W.M. Meier, D.H. Olson, Atlas of Zeolite Structure Types, 2nd edition, Butterworths, 1987.
[107] B.F. Mentzen, J.C. Vdrine, R. Khouzami, Comptes Rendus de lAcadmie des
Sciences Series II 304 (1987) 11.
[108] R. Khouzami, G. Coudurier, B.F. Mentzen, J.C. Vdrine, in: P.J. Grobet, et al.
(Eds.), Innovation in Zeolite Material Science, vol. 37, Studies in Surface Science and Catalysis, 1987, p. 355.
[109] J.C. Vdrine, G. Coudurier, B.F. Mentzen, in: W.H. Flank, T.E. Whyte (Eds.),
Prospective in Molecular Sieve Science, vol. 368, ACS Symposium Series,
Washington, 1988, p. 66.
[110] R. Szostak, Molecular Sieves, Van Nostrand Reinhold Catalysis Ser, New York,
1989.
[111] B.M. Lok, C.A. Messina, R.L. Patton, R.T. Gajek, T.R. Cannan, E.M. Flanigen,
Journal of the American Chemical Society 106 (1984) 6092.
[112] J.A. Martens, M. Martens, P. Grobet, P.A. Jacobs, Studies in Surface Science and
Catalysis 37 (1988) 97.
[113] R.J. Pellet, P.K. Coughlin, M.T. Staniulis, G.N. Long, J.A. Rabo, US Patent
4,842,714 (1989).
[114] G.C. Edwards, J.P. Gilson, C.V. McDaniel, US Patent 4,681,864 (1987).
[115] S. Cheng, Catalysis Today 49 (1999) 303.
[116] Y. Ma, W. Tong, H. Zhou, S.L. Suib, Microporous and Mesoporous Materials 37
(2000) 243.
[117] F. Marme, G. Coudurier, J.C. Vdrine, Studies in Surface Science and Catalysis
121 (1999) 171.
[118] A. Dyer, T. Gallardo, C.W. Roberts, Studies in Surface Science and Catalysis 49A
(1998) 389.
[119] A. Galarneau, A. Barodawalla, T.J. Pinnavaia, Nature 374 (1995) 529.
[120] A. Cleareld, Chemical Reviews 88 (1988) 125.
[121] R.P. Bontchev, S. Liu, J.L. Krumhansl, J. Voigt, T.M. Nenoff, Chemistry of Materials 15 (2003) 3669.
[122] B.F. Hoskins, R. Robson, Journal of the American Chemical Society 111 (1989)
5962.
[123] M. Eddaoudi, H. Li, O.M. Yagi, Journal of the American Chemical Society 122
(2000) 1391.
[124] S. Kitagawa, K. Uemura, Chemical Society Reviews 34 (2005) 109.
[125] M. Eddaoudi, J. Kim, M. O Keeffe, O.M. Yaghi, Journal of the American Chemical
Society 124 (2002) 376.
[126] M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M.O. Keeffe, O.M. Yaghi,
Science 295 (2002) 469.
[127] G. Ferey, Chemical Society Reviews 37 (2008) 191.
[128] G. Frey, C. Mellot-Draznieks, C. Serre, F. Millange, Accounts of Chemical
Research 38 (2005) 217.
[129] K. Uemuraa, R. Matsudab, S. Kitagawa, Journal of Solid State Chemistry 178
(2005) 2420.
[130] L. Josien, A. Simon-Masseron, V. Gramlich, J. Patarin, L. Rouleau, ChemistryA European Journal 9 (2003) 856.
[131] A. Corma, H. Garca, F.X. Llabrs i Xamena, Chemical Reviews 110 (2010) 4606.
[132] D. Farruseng, S. Aguado, C. Pinel, Angewandte Chemie International Edition
48 (2009) 7502.
[133] M. Ranocchiari, J.A. van Bokhoven, Physical Chemistry Chemical Physics 13
(2011) 6388.
[134] A. Dhakshinamoorthy, M. Alvaro, H. Garcia, Catalysis Science & Technology 1
(2011) 856.
[135] I. Mueller, M. Schubert, F. Teich, H. Puetter, K. Schierle-Arndt, J. Pastr, Journal
of Materials Chemistry 16 (2006) 626.
[136] D.S. Su, R. Schlgl, ChemSusChem 3 (2010) 136.
[137] T. Ladrak, S. Smulders, O. Roubeau, S.J. Tent, P. Gamez, J. Reedik, European
Journal of Inorganic Chemistry (2010) 3804.
[138] M. Hartmann, Angewandte Chemie International Edition 43 (2004) 5880.
[139] D. Verboekend, J. Prez-Ramrez, Catalysis Science & Technology 1 (2011) 879.
[140] J. Lee, Y. Park, P. Kim, H. Kim, J. Yi, Journal of Materials Chemistry 14 (2004)
1050.
[141] A. Karlsson, M. Stcker, R. Schmidt, Microporous and Mesoporous Materials
27 (1999) 181.
[142] M. Kruk, M. Jarnoniec, S.H. Joo, R. Ryoo, Journal of Physical Chemistry B 107
(2003) 2205.
[143] B. Van Der Voort, P.I. Ravikovitch, K.P. De Jong, M. Benjelloun, E. Van Bavel, A.H.
Janssen, M. Benjellouen, E. Van Bavel, P. Cool, B.M. Weckhuysen, E.F. Vansant,
Chemical Communications (2002) 1010.
[144] B. van der Voort, P.I. Ravikovitch, K.P. de Jong, M. Benjelloun, E. van Bavel,
A.H. Janssen, A.V. Neimark, B.M. Weckhuysen, E.F. Vansant, Journal of Physical
Chemistry B 106 (2002) 5873.
[145] C. Yu, J. Fan, B. Tain, D. Zhao, G.D. Stucky, Advanced Materials 14 (2002) 1742.
[146] J. Prez-Ramirez, C.H. Christensen, K. Egeblad, C.H. Christensen, J.C. Groen,
Chemical Society Reviews 37 (2008) 2530.
24
[147] W.J.J. Stevens, V. Meynen, E. Bruijn, O.I. Lebedev, G. Van Tendeloo, P. Cool, E.F.
Vansant, Microporous and Mesoporous Materials 110 (2008) 77.
[148] M. Chiesa, V. Meynen, S. Van Doorslaer, P. Cool, E.F. Vansant, Journal of the
American Chemical Society 128 (2006) 8955.
[149] J. Wang, W. Yue, W. Zhou, M.O. Coppens, Microporous and Mesoporous Materials 120 (2009) 19.
[150] A. Sakthivel, S.J. Huang, W.-H. Chen, Z.-H. Lan, K.-H. Chen, S.-W. Kim, R. Ryoo,
A.S.T. Chiang, S.B. Liu, Chemistry of Materials 16 (2004) 3168.
[151] Y. Tao, H. Kanoh, K. Kaneko, Journal of the American Chemical Society 125
(2003) 6044.
[152] A.H. Janssen, I. Schmidt, C.J.H. Jacobsen, A.J. Koster, K.P. de Jong, Microporous
and Mesoporous Materials 65 (2003) 59.
[153] J. Garcia-Martinez, D. Carloz-Amoros, A. Linares-Solano, Y.S. Lin, Microporous
[154] S. Iijima, Nature 354 (1991) 56.
[155] X. Pan, X. Bao, Accounts of Chemical Research 44 (2011) 553.
[156] T. Charinpanitkul, P. Lorturn, W. Ratismith, N. Viriya-empikul, G. Tumcharern,
J. Wilcox, Materials Research Bulletin 46 (2011) 1604;
X.-J. Wu, F. Zhu, C. Mu, Y. Liang, L. Xu, Q. Chen, R. Chen, D. Xu, Coordination
Chemistry Reviews 254 (2010) 1135.
[157] R. Leary, A. Westwood, Carbon 49 (2011) 741.
[158] K. Chizari, I. Janowska, M. Houll, I. Florea, O. Ersen, T. Romero, P. Bernhardt, M.-J. Ledoux, C. Pham-Huu, Applied Catalysis A General 380 (2010)
72.
[159] J. Amadou, K. Chizari, M. Houll, I. Janowska, O. Ersen, D. Bgin, C. Pham-Huu,
Catalysis Today 138 (2008) 62.
[160] M. Becher, M. Haluska, M. Hirscher, A. Quintel, V. Skakalova, U. DettlaffWeglikovska, X. Chen, M. Hulman, Y. Choi, S. Roth, V. Meregalli, M. Parrinello,
R. Strbel, L. Jrissen, M.M. Kappes, J. Fink, A. Zttel, I. Stepanek, P. Bernier,
Comptes Rendus Physique 4 (2003) 1055.
[161] C.-C. Huang, N.-W. Pu, C.-A. Wang, J.-C. Huang, Y. Sung, M.-D. Ger, Separation
and Purication Technology 82 (2011) 210.
[162] X.-Y. Xue, C.-H. Ma, C.-X. Cui, L.-L. Xing, Solid State Sciences 13 (2011) 1526.
[163] I. Lpez-Corral, E. Germn, M.A. Volpe, G.P. Brizuela, A. Juan, International
Journal of Hydrogen Energy 35 (2010) 2377;
I. Janowska, O. Ersen, T. Jacob, P. Vennegues, D. Begin, M.-J. Ledoux, C. PhamHuu, Applied Catalysis A General 371 (2009) 22.
[164] Y. Shi, L. Wen, F. Li, H.-M. Cheng, Journal of Power Sources 196 (2011) 8610.
[165] G.L. Luque, M.I. Rojas, G.A. Rivas, E.P.M. Leiva, Electrochimica Acta 56 (2010)
523.
[166] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli, J.S. Beck, Nature 359 (1992)
710.
[167] M. Linden, S. Schacht, F. Schueth, A. Steel, K. Unger, Journal of Porous Materials
5 (1998) 177.
[168] J.S. Beck, C. Vartuli, W. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, T.W.
Chu, D.H. Olson, E.W. Sheppard, S.B. McCullen, J.B. Higgins, J.L. Schlenker,
Journal of the American Chemical Society 114 (1992) 10834.
[169] M. Froba, K. Kohn, B. Bouffaud, O. Richard, G.V. Tendeloo, Materials Research
Society Symposium Proceedings (1999) 547.
[170] T. Yanagisawa, T. Schimizu, K. Kuroda, C. Kato, Bulletin of the Chemical Society
of Japan 63 (1990) 988.
[171] S. Inagaki, Y. Fukushima, K. Kuroda, Journal of the Chemical Society, Chemical
Communications 22 (1993) 680.
[172] D.Y. Zhao, J.L. Feng, Q.S. Hao, G. Frederickson, B.F. Chemelka, G.D. Stucky,
Science 279 (1998) 548.
[173] D. Zhao, Q. Huo, J. Feng, B.F. Chmelka, G.D. Stucky, Journal of the American
Chemical Society 120 (1998) 6024.
[174] R. Ryoo, C.H. Ko, M. Kruk, V. Antochuck, M. Jaroniec, Journal of Physical Chemistry B 104 (2000) 11465.
[175] A. Galerneau, H. Cambon, T. Martin, L.C. De Menorval, D. Brunel, F. Di Renzo,
F. Fajula, Studies in Surface Science and Catalysis 141 (2002) 395.
[176] P.T. Tanev, T.J. Pinnavaia, Science 267 (1995) 865.
[177] S.A. Bagshaw, E. Prouzetr, T.J. Pinnavaia, Science 269 (1995) 1242.
[178] T. Kimura, T. Kamata, M. Fuziwara, Y. Takamao, M. Kaneda, Y. Sakamoto, O.
Terasaki, Y. Sugihara, K. Kuroda, Angewandte Chemie International Edition
39 (2000) 3855.
[179] H.-M. Kao, J.-D. Wu, C.-C. Cheng, A.S.T. Chiang, Microporous and Mesoporous
Materials 88 (2006) 319.
[180] M.J. Kim, R. Ryoo, Chemistry of Materials 11 (1998) 487.
[181] J.C. Jansen, Z. Shan, L. Marchese, W. Zhou, N. Puil, T. Maschmeyer, Chemical
Communications (2001) 713.
[182] S. Inagaki, Y. Guan, Y. Fukushima, T. Oshuna, O. Terasaki, Journal of the American Chemical Society 121 (1999) 9611.
[183] T. Sefa, G. Ozin, H. Grondey, M. Kruk, M. Jaroniec, Surface Science and Catalysis
141 (2002) 1.
[184] O. Muth, C. Schellbach, M. Froeba, Chemical Communications (2001) 2032.
[185] S. Jun, S. Joo, R. Ryoo, M. Kruk, M. Jaroniec, Z. Liu, T. Ohsuna, O. Terasaki, Journal
of the American Chemical Society 122 (2000) 10712.
[186] S.H. Joo, R. Ryoo, M. Kruk, M. Jaroniec, Journal of Physical Chemistry B 106
(2002) 4640.
[187] T. Tsoncheva, J. Rosenholm, M. Linden, F. Kleitz, M. Tiemann, L. Ivanova, M.
Dimitrov, D. Paneva, I. Mitov, C. Minchev, Microporous and Mesoporous Materials 112 (2008) 327.
[188] L. Lizama, M. Prez, T. Klimova, Studies in Surface Science and Catalysis 174B
(2008) 1251.
[189] F. Boubekr, A. Davidson, S. Casale, P. Massiani, Microporous and Mesoporous

Materials 141 (2011) 157.
[190] N. El Hassan, A. Davidson, P. Da Costa, G. Djega-Mariadassou, Catalysis Today
137 (2008) 191.
[191] S. Jun, R. Ryoo, Journal of Catalysis 195 (2000) 237.
[192] X. Hu, M.L. Foo, G.K. Chuah, Journal of Catalysis 195 (2000) 412.
[193] C.W. Lee, D.H. Ahn, B. Wang, J.S. Hwang, S.E. Park, Microporous and Mesoporous Materials 4445 (2001) 587.
[194] W.H. Zhang, J.L. Shi, L.Z. Wang, D.S. Yan, Materials Letters 46 (2000) 35.
[195] W.S. Ahn, D.H. Lee, T.J. Kim, J.H. Kim, G. Seo, R. Ryoo, Applied Catalysis A
General 181 (1999) 39.
[196] R. Burch, N. Cruise, D. Gleeson, S.C. Tsang, Chemical Communications (1996)
951.
[197] P. van der Voort, M. Mathieu, M. Morey, G.D. Stucky, E.F. Vansant, Studies in
Surface Science and Catalysis 117 (1998) 333.
[198] T. Maschmeyer, F. Rey, G. Sankar, J.M. Thomas, Nature 378 (1995) 159.
[199] A. Boulaoued, I. Fechete, B. Donnio, M. Bernard, P. Turek, F. Garin, Microporous
[200] W. Zhao, L. Kong, Y. Luo, Q. Li, Microporous and Mesoporous Materials 100
(2007) 111.
[201] I. Fechete, B. Donnio, O. Ersen, T. Dintzer, A. Djeddi, F. Garin, Applied Surface
Science 257 (2011) 2791.
[202] I. Eswaramoorthi, A.K. Dalai, Microporous and Mesoporous Materials 93
(2006) 1.
[203] Y. Shao, L. Wang, J. Zhang, M. Anpo, Journal of Photochemistry and Photobiology A: Chemistry 180 (2006) 59.
[204] M. Pirouzmand, M.M. Amini, N. Safari, Journal of Colloid and Interface Science
319 (2008) 199.
[205] J.F. Bengoa, M.V. Cagnoli, N.G. Gallegos, A.M. Alvarez, L.V. Mogni, M.S.
Moreno, S.G. Marchetti, Microporous and Mesoporous Materials 84 (2005)
153.
[206] A. De Stefanis, S. Kaciulis, L. Pandol, Microporous and Mesoporous Materials
99 (2007) 140.
[207] Q. Zhang, Y. Wang, S. Itsuki, T. Shishido, K. Takehira, Journal of Molecular
Catalysis A Chemical 188 (2002) 189.
[208] . Szegedi, Z. Knya, D. Mhn, E. Solymr, G. Pl-Borbly, Z.E. Horvth, L.P.
Bir, I. Kiricsi, Applied Catalysis A General 272 (2004) 257.
[209] M. Santhosh Kumar, J. Perez-Ramrez, M.N. Debbagh, B. Smarsly, U. Bentrup,
A. Bruckner, Applied Catalysis B Environmental 62 (2006) 244.
[210] Y. Zhang, F. Gao, H. Wan, C. Wu, Y. Kong, X. Wu, B. Zhao, L. Dong, Y. Chen,
Microporous and Mesoporous Materials 113 (2008) 393.
[211] P. Van Der Voort, E.F. Vansant, Microporous and Mesoporous Materials 38
(2000) 385.
[212] K. Anas, K.K. Mohammed Yusuff, Applied Catalysis A General 264 (2004)
213.
[213] O. Collart, P. Van Der Voort, E.F. Vansant, E. Gustin, A. Bouwen, D. Schoemaker,
R. Ramachandra Rao, B.M. Weckhuysen, R.A. Schoonheydt, Physical Chemistry
Chemical Physics 1 (1999) 4099.
[214] M. Yonemitsu, Y. Tanaka, M. Iwamoto, Chemistry of Materials 9 (1997) 2679.
[215] M. Yonemitsu, Y. Tanaka, M. Iwamoto, Journal of Catalysis 178 (1998) 207.
[216] A. Sayari, Chemistry of Materials 8 (1996) 1840.
[217] T. Linssen, K.L. Cassiers, P. Cool, E.F. Vansant, Microporous and Mesoporous
Materials 103 (2004) 121.
[218] J. Panpranot, J. Goodwin Jr., A. Sayari, Catalysis Today 77 (2002) 269.
[219] Y. Wang, M. Noguschi, Y. Ohtsuka, Catalysis Today 68 (2001) 3.
[220] K. Soni, B.S. Rana, A.K. Sinha, A. Bhaumik, M. Nandi, M. Kumar, G.M. Dhar,
Applied Catalysis B Environmental 90 (2009) 55.
[221] A. Wang, Y. Wang, T. Kabe, Y.Y. Chen, A. Ishihara, W.H. Qian, P.J. Yao, Journal
of Catalysis 210 (2002) 269.
[222] T. Klimova, M. Calderon, J. Ramirez, Applied Catalysis A General 225 (2002)
1.
[223] A. Prabhu, L. Kumaresan, M. Palanichamy, V. Murugesan, Applied Catalysis A
General 360 (2009) 59.
[224] K.C. Park, D.J. Yim, S.K. Ihm, Catalysis Today 74 (2002) 281.
[225] A.M. Liu, K. Hidajat, S. Kawi, Journal of Molecular Catalysis A Chemical 168
(2001) 303.
[226] S.G. Shyu, S.W. Cheng, D.L. Tzou, Chemical Communications (1999) 2337.
[227] R.S. Mulukutla, T. Shido, K. Asakura, T. Kogure, Y. Iwasawa, Applied Catalysis
A General 228 (2002) 305.
[228] V.R. Choudhary, S.K. Jana, N.S. Patil, Tetrahedron Letters 43 (2002) 1105.
[229] V.R. Choudhary, S.K. Jana, Journal of Molecular Catalysis A Chemical 184
(2002) 247.
[230] T. Ookoshi, M. Onaka, Chemical Communications (1998) 2399.
[231] M. Anpo, M. Takeuchi, K. Ikeue, S. Dohshi, Curr Opin, Solid State & Materials
Science 6 (2002) 381.
[232] D.H. Zhang, H.B. Li, G.D. Li, J.S. Chen, Dalton Transactions 47 (2009) 10527.
[233] X. Huang, W. Dong, G. Wang, M. Yang, L. Tan, Y. Feng, X. Zhang, Journal of
Colloid and Interface Science 359 (2011) 40.
[234] T. Ikariya, I.D. Gridnev, Topics in Catalysis 53 (2010) 894.
[235] P.L. Anelli, B. Czech, F. Monatanari, S. Quici, Journal of the American Chemical
Society 106 (1984) 861.
[236] S. Calogero, D. Lanari, M. Orr, O. Piermatti, F. Pizzo, L. Vaccaro, Journal of
Catalysis 282 (2011) 112.
[237] J.M. Thomas, T. Maschmeyer, B.F.G. Johnoson, D.S. Shephard, Journal of Molecular Catalysis A Chemical 141 (1999) 139.

[238] E.L. Margelefsky, R.K. Zeidan, M.E. Davis, Chemical Society Reviews 37 (2008)
1118.
[239] H.H. Kung, M.C. Kung, Catalysis Today 148 (2009) 2.
[240] S. Shylesh, W.R. Thiel, ChemCatChem 3 (2011) 278.
[241] R. Raja, J.M. Thomas, M.D. Jones, B.F.G. Johnson, D.E.W. Vaughan, Journal of
the American Chemical Society 125 (2003) 14982.
[242] P. Yu, J. He, C. Guo, Chemical Communications 5 (2008) 2355.
[243] J.M. Fraile, J.L. Garcia, J.A. Mayoral, M. Roldan, Organic Letters 9 (2007)
731.
[244] S. Vijaikumar, A. Dhakshinamoorthy, K. Pitchumani, Applied Catalysis A
General 340 (2008) 25.
[245] J. Zakzeski, P.C.A. Bruijnincx, A.L. Jongerius, B. Weckhuysen, Chemical Reviews
110 (2010) 3552.
[246] Q. Zhang, W. Deng, Y. Wang, Chemical Communications 47 (2011) 9275.
[247] G.W. Huber, S. Iborra, A. Corma, Chemical Reviews 106 (2006) 4044.
[248] J. Zakzeski, B.M. Weckhuysen, ChemSusChem 4 (2011) 369.
[249] P. Gallezot, Catalysis Today 124 (2007) 76.
[250] S. Van de Vyver, J. Geboers, P.A. Jacobs, B.F. Sels, ChemCatChem 3 (2011) 82.
[251] O.L. Dhepe, A. Fukuoka, ChemSusChem 1 (2008) 965.
[252] A. Fukuoka, P.L. Dhepe, Angewandte Chemie International Edition 45 (2006)
5161.
[253] C. Luo, S. Wang, H. Liu, Angewandte Chemie International Edition 46 (2007)
7636.
[254] N. Ji, T. Zhang, M. Zheng, A. Wang, H. Wang, X. Wang, J.G. Chen, Angewandte
Chemie International Edition 47 (2008) 8510.
[255] X. Tan, W. Deng, M. Liu, Q. Zhang, Y. Wang, Chemical Communications (2009)
7179.
[256] M. Liu, W. Deng, Q. Zhang, Y. Wang, Y. Wang, Chemical Communications 47
(2011) 9717.
[257] M.V. Twigg, Catalyst Handbook, 2nd edition, Manson Publishing Ltd, 1996.
Bunluesin,
R.J.
Gorte,
G.W.
Graham,
Applied
[258] T.
B
Environmental
15
(1998)
Catalysis
107.
[259] J.M. Zalc, V. Sokolovskii, D.G. Lofer, Journal of Catalysis 206 (2002) 169.
[260] E. Xue, M.O. OKeeffe, J.R.H. Ross, Catalysis Today 30 (1996) 107.
[261] H. Zhao, Y. Hu, J. Li, Journal of Molecular Catalysis A Chemical 149 (1999)
141.
[262] Y. Li, Q. Fu, M. Flytzani-Stephanopoulos, Applied Catalysis B Environmental
27 (2000) 179.
[263] Y. Schuurman, C. Marquez-Alvarez, V.C.H. Kroll, C. Mirodatos, Catalysis Today
46 (1998) 185.
[264] N.E. Amadeo, M. Laborde, International Journal of Hydrogen Energy 20 (1995)
949.
[265] Y. Tanaka, T. Utaka, R. Kikuchi, K. Sasaki, K. Eguchi, Applied Catalysis A
General (2002) 6032.
[266] A. Basinska,
F. Domka, Applied Catalysis A General 179 (1999) 241.
nski,
L. Kepi
F. Domka, Applied Catalysis A General 183 (1999)
[267] A. Basinska,
143.
[268] F. Boccuzzi, A. Chiorino, M. Manzoli, D. Andreeva, T. Tabakova, Journal of
Catalysis 188 (1999) 176.
[269] D.C. Grenoble, M.M. Estadt, D.F. Ollis, Journal of Catalysis 67 (1981) 90.
[270] C. Serre, F. Garin, G. Belot, G. Maire, Journal of Catalysis 141 (1993) 1.
[271] A. Le Valant, A. Garron, N. Bion, D. Duprez, F. Epron, International Journal of
Hydrogen Energy 36 (2011) 311.
[272] A. Haryanto, S. Fernando, N. Murali, S. Adhikari, Energy and Fuels 19 (2005)
2098.
[273] S. Velu, N. Satoh, C.S. Gopinath, K. Suzuki, Catalysis Letters 82 (2002) 145.
[274] G.A. Deluga, J.R. Salge, L.D. Schmidt, X.E. Verykios, Science 303 (2004) 993.
[275] M.C. Snchez-Snchez, R.M. Navarro, J.L.G. Fierro, International Journal of
Hydrogen Energy 32 (2007) 1462.
[276] E. Cavallaro, Energy and Fuels 14 (2000) 1195.
[277] A.N. Fatsikostas, X.E. Verykios, Journal of Catalysis 225 (2004) 439.
[278] J. Llorca, J.P.R. de la Piscina, J. Sales, N. Homs, Chemical Communications
(2001) 641.
[279] P. Jena, Journal of Physical Chemistry Letters 2 (2011) 206.
[280] P.V. Kamat, Journal of Physical Chemistry Letters 2 (2011) 242.
[281] X. Chen, S. Shen, L. Guo, S.S. Mao, Chemical Reviews 110 (2010) 6503.
[282] M.A. Pena, J.L.G. Fierro, Chemical Reviews 101 (2001) 1981.
[283] G.P. van der Laan, PhD thesis, University of Groningen, The Netherlands, 1999.
[284] J.M. Thomas, W.J. Thomas, Principle and Practice of Heterogeneous Catalysis,
VCH Publishers, New York, 1997.
[285] K. Thampi, J. Kiwi, M. Graetzel, Nature 327 (1987) 506.
[286] M. Vannice et al., US 4,042,614, Exxon (1976).
[287] S. Plecha et al., US 6,117,814, Exxon (2000).
[288] J. Bao, J. He, Y. Zhang, Y. Yoneyama, N. Tsubaki, Angewandte Chemie International Edition 47 (2008) 353.
[289] J. Kang, K. Cheng, L. Zhang, Q. Zhang, J. Ding, W. Hua, Y. Lou, Q. Zhai, Y. Wang,
Angewandte Chemie International Edition 50 (2011) 5200.
[290] J. Kang, S. Zhang, Q. Zhang, Y. Wang, Angewandte Chemie International Edition 48 (2009) 2565.
[291] W. Chen, Z. Fan, X. Pan, X. Bao, Journal of the American Chemical Society 130
(2008) 9414.
[292] G. Yu, B. Sun, Y. Pei, S. Xie, S. Yan, M. Qiao, K. Fan, X. Zhang, B. Zong, Journal
of the American Chemical Society 132 (2010) 935.
[293] S. Brunet, D. Mey, G. Prot, C. Bouchy, F. Diehl, Applied Catalysis A General
278 (2005) 143.
25
[294] C. Song, Catalysis Today 86 (2003) 211.

[295] T.G. Kaufmann, A. Kaldor, G.F. Stuntz, M.C. Kerby, L.L. Ansell, Catalysis Today
62 (2000) 77.
[296] F.M. Collins, A.R. Lucy, C. Sharp, Journal of Molecular Catalysis A Chemical
117 (1997) 397.
[297] A. Rabion, F. Fajula, J.R. Bernard, V. Hulea, US Patent 0,102,252 (2003).
[298] F. Figueras, J. Palomique, S. Loridant, C. Fche, N. Essayem, G. Gelbard, Journal
of Catalysis 226 (2004) 25.
[299] A.L. Maciuca, C.-E. Ciocan, E. Dumitriu, F. Fajula, V. Hulea, Catalysis Today 138
(2008) 33.
[300] Y. Kanda, T. Aizawa, T. Koboyashi, Y. Vemichi, S. Namba, M. Sugioka, Applied
Catalysis B Environmental 77 (2007) 117.
[301] M. Sugioka, L. Andalaluna, S. Morishita, T. Kurosaka, Catalysis Today 39 (1997)
61.
[302] H. Topse, B.S. Clausen, F.E. Massoth, in: J.R. Anderson, M. Boudard (Eds.),
Catalysis Science and Technology, vol. 11, Springer, Berlin, 1996.
[303] K. Kabe, A. Ishihara, W. Qian, Hydrodesulfurization and Hydrodenitrogenation, Kodansha, Tokyo, 1999.
[304] B.S. Clausen, S. Mrup, H. Topse, R. Candia, J. Phys. Colloq. 37 (1976) C6C249.
[305] H. Topse, B.S. Clausen, R. Candia, C. Wivel, S. Mrup, Journal of Catalysis 68
(1981) 433.
[306] C. Wivel, R. Candia, B.S. Clausen, M. Mrup, H. Topse, Journal of Catalysis 68
(1982) 453.
[307] H. Topse, B.S. Clausen, R. Candia, C. Wivel, S. Mrup, Bulletin des Societes
Chimiques Belges 90 (1981) 1189.
[308] R. Candia, O. Srensen, J. Villadsen, N. Topse, B.S. Clausen, H. Topse, Bulletin
des Societes Chimiques Belges 93 (1984) 763.
[309] J.A.R. van Veen, E. Gerkema, A.M. van der Kraan, A. Knoester, Journal of the
Chemical Society, Chemical Communications (1987) 1684.
[310] Y. Ohta, T. Shimizu, T. Honna, M. Yamada, Studies in Surface Science and
Catalysis 127 (1999) 161.
[311] T. Shimizu, K. Hiroshima, T. Honna, T. Mochizuki, M. Yamada, Catalysis Today
45 (1998) 271.
[312] L. Medici, R. Prins, Journal of Catalysis 163 (1996) 38.
[313] T. Fujikawa, Catalysis Surveys from Asia 10 (2006) 89.
[314] T. Fujikawa, M. Kato, H. Kimura, K. Kiriyama, M. Hashimoto, N. Nakajima,
Journal of the Japan Petroleum Institute 48 (2005) 106.
[315] T. Fujikawa, M. Kato, T. Ebihara, K. Hagiwara, T. Kubota, Y. Okamoto, Journal
of the Japan Petroleum Institute 48 (2005) 114.
[316] J.A. Bergwerff, M. Jansen, B.R.G. Leliveld, T. Visser, K.P. De Jong, B.M. Weckhuysen, Journal of Catalysis 243 (2006) 292.
[317] D. Mey, S. Brunet, C. Canaff, F. Maug, C. Bouchy, F. Diehl, Journal of Catalysis
227 (2004) 43.
[318] S. Hatanaka, T. Miyama, H. Seki, S. Hikita, EP 0736589 A1 (1996).
[319] C. Flego, V. Arrigoni, M. Ferrari, R. Riva, L. Zanibelli, Catalysis Today 65 (2001)
265.
[320] G. Muralidhar, F.E. Massoth, J. Shabtai, Journal of Catalysis 85 (1984) 44.
[321] M. Toba, Y. Miki, T. Matsui, M. Harada, Y. Yoshimura, Applied Catalysis B
Environmental 70 (2007) 542.
[322] V. La Parola, G. Deganello, A.M. Venecia, Applied Catalysis A General 260
(2004) 237.
[323] K.S. Rawat, M.S. Rana, G. Murali Dhar, Studies in Surface Science and Catalysis
135 (1998) 307.
[324] R. Navarro, B. Pawelec, J.L.G. Fierro, P.T. Vasudevan, J.F. Cambra, M.B. Guemez,
P.L. Arias, Fuel Processing Technology 61 (1999) 73.
[325] P.E. Dai, J.H. Lunsford, Journal of Catalysis 64 (1980) 173.
[326] T. Tatsumi, M. Tanigushi, S. Yasuda, Y. Ishii, T. Murata, M. Hidai, Applied
Catalysis A General 139 (1996) L5.
[327] M. Alibouri, S.M. Ghoreishi, H.R. Aghabozang, Journal of Supercritical Fluids
49 (2009) 230.
[328] Y. Fan, G. Shi, H. Liu, X. Bao, Fuel 90 (2011) 1717.
[329] Y. Huang, Z. Zhou, Y. Qi, X. Li, Z. Cheng, W. Yuan, Chemical Engineering Journal
172 (2011) 444.
[330] M.M. Hossain, M.A. Al-Salih, M.A. Shalabi, T. Kimura, T. Inui, Applied Catalysis
A General 274 (2004) 43.
[331] T. Kimura, K. Al-Nawad, S.A. Ali, Y. Suzuki, H. Hamid, T. Inui, Proceedings of
the 220th ACS National Meeting, Washington, August 2024, 2000.
[332] S.A. Ali, M.E. Biswas, T. Yoneda, T. Miura, S.H. Hamid, E. Iwamatsu, H. Al-Suaibi,
Catalysis Science & Technology 127 (1998) 407.
[333] J. Lee, A. Ishihara, F. Dumeignil, K. Miyazaki, Y. Oomori, E.W. Qian, T. Kabe,
Journal of Molecular Catalysis A Chemical 209 (2004) 155.
[334] X. Li, A. Wang, Z. Sun, C. Li, J. Ren, B. Zhao, Y. Wang, Y. Chan, Y. Hu, Applied
Catalysis A General 254 (2003) 319.
[335] Y. Yoshimura, H. Yasuda, T. Sato, N. Kijima, T. Kameoka, Applied Catalysis A
General 207 (2001) 303.
[336] M. Sugioka, F. Sado, T. Kurosaka, X. Wang, Catalysis Today 45 (1998) 327.
[337] J.P. Greeley, S. Zaczepinski, T.R. Halbert, G.B. Brignac, A.R. Gentry, R.L. Kraus,
Am. Chem. Soc. Prepr. Div. Pet. Chem 45 (2000) 357.
[338] B.B. Garland, T.R. Halbert, J.P. Greeley, R.A. Demmin, T.J. Davis, World Rening
10 (2000) 14.
[339] G.J. Antos, R.B. Solari, R. Monque, Studies in Surface Science and Catalysis 106
(1997) 27.
[340] R.M. Jao, I.J. Leu, J.R. Chang, Applied Catalysis A General 135 (1996) 301.
[341] J. Gislason, Oil and Gas Journal 99 (2002) 74.
[342] Q. Debuisschert, J.-L. Nocca, C. Jean-Paul, Proceed. Interf. 2002 Conference,
Budapest, September 1920, 2002, p. 133.
26
[343] N.H. Sweed, R. Demmin, H. Ryu, Hydrocarbon Engineering 7 (2002) 19.

[344] J.A. Salazar, L.M. Cabera, E. Palmisano, W.J. Garcia, R.B. Solari, US Patent
5,770,047 to Intevep S.A. (1998).
[345] J.A. Salazar, N.P. Martinez, J.A. Perez, Meeting RFG specications, Hydrocarbon
Engineering 3 (1998) 48.
[346] J. Gentry, T. Khanmamedov, R.W. Wytcherley, Hydrocarbon Engineering 7
(2002) 43.
[347] J. Gislason, Hydrocarbon Engineering 7 (2002) 39.
[348] D. French, J. Shah, P. Johnson, Hydrocarbon Engineering 7 (2002) 37.
[349] K.L. Rock, R.M. Foley, World Rening 9 (1999) 23.
[350] G. Centi, F. Cavani, F. Trirro, Selective Oxidation by Heterogeneous Catalysis,
Kluwer Academic/Plenum Publisbers, New York, 2001.
[351] V. Hulea, F. Fajula, J. Bousquet, Journal of Catalysis 198 (2001) 179.
[352] V. Hulea, A.-L. Maciuca, A.-M. Cojocariu, C.-E. Ciocan, E. Dumitriu, Comptes
Rendus Chimie 12 (2009) 723.
[353] T. Sakakura, J.C. Choi, H. Yasuda, Chemical Reviews 107 (2007) 2365.
[354] M. Prettre, Ch. Eichner, M. Perrin, Transactions of the Faraday Society 42
(1946) 335.
[355] E.H. van Broekhoven, F.R. Mas Cabr, P. Bogaard, G. Klaver, M. Vonhof, US
Patent 5,986,158 (1999).
[356] A. Horvth, G. Steer, O. Geszti, A. Kienneman, A. Pietraszek, L. Guczi, Catalysis
Today 169 (2011) 102.
[357] N. Bespalko, A.-C. Roger, J. Bussi, Applied Catalysis A General 407 (2011)
204.
[358] G. Centi, L. Perathoner, Catalysis Today 148 (2009) 191.
[359] T. Kakamuto, Energy Conversion and Management 36 (1995) 661.
[360] Y.X. Pan, C.-J. Liu, Q. Ge, Journal of Catalysis 272 (2010) 227.
[361] H. Li, H. Yang, H. Li, Journal of Catalysis 251 (2007) 233.
[362] L. Yin, S. Wang, H. Lu, J. Ding, R. Mosta, Z. Hao, Chemical Engineering Journal
131 (2007) 123.
[363] S. Ozkara-Aydinoglu, E. Ozensoy, A.E. Aksoylu, International Journal of Hydrogen Energy 34 (2009) 9711.
[364] J. Cheng, W. Huang, Fuel Processing Technology 91 (2010) 72.
[365] H. Jiang, H. Li, Y. Zhang, Journal of Chemical Technology and Biotechnology
35 (2007) 72.
[366] M. Minutillo, A. Perna, Intern, Journ. of Hydrog, Energy 35 (2010) 7012.
[367] A. Corma, M.I. Juan-Rajadell, J.M. Lopez-Nieto, A. Martinez, C. Martinez,
[368] J. Weitkamp, Y. Traa, Catalysis Today 49 (1999) 193.
[369] F. Cardona, N.G. Gnep, M. Guisnet, G. Szabo, P. Nascimento, Applied Catalysis
A General 128 (1995) 243.
[370] P. Wang, D. Wang, C. Xu, J. Liu, J. Gao, Catalysis Today 125 (2007) 263.
[371] R. Gounder, E. Iglesia, Journal of Catalysis 277 (2011) 36.
[372] E.A. Mamedov, V. Cortes Corberan, Applied Catalysis A General 127 (1995)
1.
[373] J. Scwank, K. Balakrishnan, A. Sachdev, Studies in Surface Science and Catalysis
75 (1993) 905.
[374] K. Weissrmel, H.J. Arpe, Industrial Organic Chemistry, 4th edition, Wiley-VCH,
2003.
[375] Y.H. Tauq-Yap, F. Rezaei, A.A. Rownaghi, Industrial and Engineering Chemistry Research 48 (2009) 7517.
[376] G. Centi, F. Trir, J.R. Ebner, V.M. Franchetti, Chemical Reviews 88 (1988)
55.
[377] Y. Zhang-Lin, M. Forissier, J.C. Volta, Journal of Catalysis 145 (1993) 267.
[378] M.T. Sananes, G.J. Hutchings, J.C. Volta, Journal of Catalysis 154 (1995) 253.
[379] G.W. Clouston, S.R. Bare, H. Kung, K. Birkeland, G.K. Bethke, R. Harlow, N.
Herron, P.L. Lee, Science 275 (1997) 191.
[380] G. Landi, L. Lisi, G. Russo, Journal of Molecular Catalysis A Chemical 239
(2005) 172.
[381] T. Ushikubo, K. Oshima, T. Ihara, H. Amatsu, US Patent 5,534,650 (1996),
Assigned to Mitsubishi Chemical Co.
[382] T. Ushikubo, K. Oshima, A. Kayou, A.M. Hatano, Studies in Surface Science and
Catalysis 112 (1997) 473.
[383] T. Ushikubo, K. Oshima, A. Kayou, M. Vaarkamp, M. Hatano, Journal of Catalysis
169 (1997) 394.
[384] J.C. Vdrine, E.K. Novakova, in: J.L.G. Fierro (Ed.), Metal Oxides: Chemistry and
Applications, Marcel Dekker, New York, 2005, p. 413.
[385] G.S. Patience, J.M. Lpez-Nieto, Applied Catalysis A General 376 (2010) 4
(special issue).
[386] F. Luck, Catalysis Today 53 (1999) 81.
[387] L. Oliviero, J. Barbier Jr., D. Duprez, Applied Catalysis B Environmental 40
(2003) 163.
[388] Q. Huang, Z. Meng, R. Zhou, Applied Catalysis B Environmental 115116
(2012) 179.
[389] P. Dg, L. Pinard, P. Magnoux, M. Guisnet, Comptes Rendus de lAcadmie
des Sciences Series II 4 (2001) 41.
[390] T.T. Shen, C.E. Schmidt, T.R. Card, Assessment and Control of VOC Emission
from Waste Water Treatment and Disposal Facilities, Van Nostrand Reinhold,
New York, 1993.
[391] S. Wang, H.M. Ang, M.O. Tade, Environment International 33 (2007) 694.
[392] S. Somokawa, T. Hagiwara, K. Fujii, M. Kojima, T. Shinoda, Applied Catalysis A
General 409410 (2011) 209.
[393] S. Azalim, M. Franco, R. Brahmi, J.-M. Giraudon, J.-F. Lamonier, Journal of
Hazardous Materials 188 (2011) 422.
[394] R. Bonelli, C. Lucarelli, T. Pasini, L.F. Liotta, S. Zacchini, S. Albonetti, Applied
Catalysis A General 400 (2011) 54.
[395] J.J. Spivey, Industrial and Engineering Chemistry Research 26 (1987) 2165.
[396] S. Minic, S. Scir, C. Crisafulli, R. Maggiore, S. Galvagno, Applied Catalysis B
Environmental 28 (2000) 245.
[397] S. Minic, S. Scir, C. Crisafulli, S. Galvagno, Applied Catalysis 34 (2001) 277.
[398] S. Scir, S. Minic, C. Crisafulli, S. Galvagno, Catalysis Communications 2
(2001) 229.
[399] A. Trovarelli, Catalysis Reviews Science and Engineering 38 (1996) 439.
[400] A. Trovarelli, C. de Leitenburg, M. Boaro, G. Dolcetti, Catalysis Today 50 (1999)
353.
[401] Y. Li, Q. Fu, M. Flytzani-Stephanopoulos, Applied Catalysis 27 (2000) 179.
[402] T. Bunluesin, R.J. Gorte, Applied Catalysis B Environmental 15 (1998) 107.
[403] S.C. Kim, W.G. Shim, Applied Catalysis B Environmental 92 (2009) 429.
[404] S.K. Ihm, Y.D. Jun, D.C. Kim, K.E. Jeong, Catalysis Today 9395 (2004) 149.
[405] W.G. Shim, J.W. Lee, S.C. Kim, Applied Catalysis B Environmental 84 (2008)
133.
[406] S. Huang, C. Zhang, H. He, Catalysis Today 139 (2008) 15.
[407] Y. Yazawa, H. Yoshida, N. Takgi, S. Komai, A. Satsuma, T. Hattori, Applied
[408] R. Burch, P.K. Loader, F.J. Urbano, Catalysis Today 27 (1996) 243.
[409] K. Muto, N. Katada, M. Niwa, Applied Catalysis 134 (1996) 203.
[410] T.R. Baldwin, R. Burch, Applied Catalysis 66 (1990) 337.
[411] Y. Yazawa, H. Yoshida, N. Takagi, S. Komai, A. Satsuma, T. Hattori, Journal of
Catalysis 187 (1999) 15.
[412] P. Briot, M. Primet, Applied Catalysis 68 (1991) 301.
[413] C.A. Muller, M. Maciejewski, R.A. Koeppel, A. Maiker, Journal of Catalysis 166
(1997) 36.
[414] P. Papaefthimiou, T. Ioannides, X.E. Verykios, Applied Catalysis B Environmental 13 (1997) 175.
[415] R.J. Farrauto, M.C. Hobson, T. Kennelly, E.M. Waterman, Applied Catalysis A
General 81 (1992) 227.
[416] M. Lyubovsky, L. Pfefferle, Applied Catalysis 173 (1998) 107.
[417] O. Demoulin, G. Rupprechter, I. Seunier, B. Le Clef, M. Navez, P. Ruiz, Journal
of Physical Chemistry B 109 (2005) 20454.
[418] S.E. Braslavsky, K.N. Houk, Pure and Applied Chemistry 60 (1988) 1055.
[419] J.W. Verhoven, Pure and Applied Chemistry 68 (1996) 2223.
[420] H.G. Kim, D.W. Hwang, J. Kim, Y.G. Kim, J.S. Lee, Chemical Communications
(1999) 1077.
[421] C.D. Lindstrom, X.-Y. Zhu, Chemical Reviews 106 (2006) 4281.
[422] J.-M. Herrmann, Heterogeneous photocatalysis: state of the art and present
applications, Topics in Catalysis 34 (2005) 49; Titania-based true heterogeneous photocatalysis, in: A. Seidel (Ed.), Photocatalysis, KirkOthmer
Encyclopedia of Chemical Technology, vol. 19, 5th edition, Wiley & Sons, 2006,
p. 73; Photocatalysis fundamentals revisited to avoid several misconceptions,
Applied Catalysis B Environmental 99 (2010) 461.
[423] A. Fujishima, X. Zhang, Titanium dioxide photocatalysis: present situation and
future approaches, Comptes Rendus Chimie 9 (2006) 750.
[424] H. Assa, E. Puzenat, A. Plassais, J.-M. Herrmann, C. Haehnel, C. Guillard,
Applied Catalysis B Environmental 107 (2011) 18;
C. Sarantopoulos, E. Puzenat, C. Guillard, J.-M. Herrmann, A.N. Gleizes, Applied
[425] A.L. Linsebigler, G. Lu, J.T. Yates Jr., Chemical Reviews 95 (1995) 735.
[426] M. Yagi, M. Kaneko, Chemical Reviews 101 (2001) 21.
[427] C. Cheng, P. Lei, H. Ji, W. Ma, J. Chao, H. Hidaka, N. Serpone, Environmental
Science and Technology 38 (2004) 329.
[428] M. Fernandez-Garca, A. Martnez-Arias, J.C. Hanson, J.A. Rodriguez, Chemical
Reviews 104 (2004) 4063.
[429] T.L. Thompson, J.T. Yates Jr., Chemical Reviews 106 (2006) 4428.
[430] F.X. Llabres, P. Calza, C. Lamberti, C. Prestipino, A. Damin, S. Bordiga, E.
Pelizzetti, A. Zecchina, Journal of the American Chemical Society 125 (2003)
2264.
[431] P. Calza, C. Paze, E. Pelizzetti, A. Zecchina, Chemical Communications (2001)
2130.
[432] E. Reddy, B. Sun, P. Smirniotis, Journal of Physical Chemistry B 108 (2004)
19198.
[433] A.J. Nozik, J.R. Miller, Chemical Reviews 110 (2010) 6443.
[434] P. Anastas, N. Eghbali, Chemical Society Reviews 39 (2009) 301.
[435] P. Anastas, ChemSusChem 2 (2009) 391.
[436] P. Anastas, S.E. Beach, Green Chemistry Letters and Reviews 1 (2007) 9.
[437] P. Anastas, Green Chemistry Letters and Reviews 1 (2007) 3.
[438] R.A. Sheldon, Comptes Rendus de lAcadmie des Sciences Paris 3 (2000)
541.
[439] G.A. Somorjai, H. Frei, J.Y. Park, Journal of the American Chemical Society 131
(2009) 16589.
[440] U.K. Singh, M.A. Vannice, Applied Catalysis A General 213 (2001) 1.
[441] I. Fechete, V. Jouikov, Electrochimica Acta 53 (2008) 7107.
[442] D. Teschner, L. Pirault-Roy, D. Naud, M. Guerin, Z. Paal, Applied Catalysis 252
(2003) 421.
[443] D. Tichit, D. Lutic, B. Coq, R. Durand, R. Teissier, Journal of Catalysis 219 (2003)
167.
[444] Y.H. Chin, W.E. Alvarez, D.E. Resasco, Catalysis Today 62 (2000) 159.
[445] Y.P. Khitev, Y.G. Kolyagin, I.I. Ivanova, O.A. Ponomareva, F. Thibault-Starzyk,
J.-P. Gilson, C. Fernandez, F. Fajula, Microporous and Mesoporous Materials
146 (2011) 201.
[446] A. Djeddi, I. Fechete, F. Garin, Catalysis Communications 17 (2012) 173.
[447] A. Djeddi, I. Fechete, F. Garin, Applied Catalysis A General 413414 (2012)
340.

[448] R. Ohnishi, M. Katayama, K. Takanabe, J. Kubota, K. Domen, Electrochimica
Acta 55 (2010) 5393.
[449] A. de Lucas-Consuegra, A. Caravaca, J. Gonzalez-Cobos, J.L. Valverde, F. Dorado,
Catalysis Communications 15 (2011) 6.
[450] G.A. Somorjai, Angewandte Chemie International Edition (2008) 9212.
[451] M. Che, J.C. Vdrine, Characterization of Solid Materials and Heterogeneous
Catalysts: From Structure to Surface Reactivity, J. Wiley-VCH, Weinheim,
2012.
27
[452] M.G. Walter, E.L. Warren, J.R. McKone, S.W. Boettcher, Q. Mi, E.A. Santori, N.S.
Lewis, Chemical Reviews 110 (2010) 6446.
[453] A.C. Dillon, Chemical Reviews 110 (2010) 6856.
[454] B. Farrauto, Abstract Commun, in: 6th European Conference Paul Sabatier
on CatalysisCatalytic Materials for Energy: Past, Present and Future, 2629th
September, Klingenthal, France, 2011.
[455] J. Bisquert, Journal of Physical Chemistry Letters 2 (2011) 270.

Lectura 0. Past, Present and Future of Heterogeneous Catalysis

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lectura 0. Past, Present and Future of Heterogeneous Catalysis

Uploaded by

Copyright:

Available Formats

Catalysis Today 189 (2012) 227

Contents lists available at SciVerse ScienceDirect

The past, present and future of heterogeneous catalysis

Corresponding author. Tel.: +33 144275514.

I. Fechete et al. / Catalysis Today 189 (2012) 227

and less-capital-incentive processes and the use of cheaper feed

Friedel & Crafts

of a molecular-level understanding of catalyst function, surface sensitive spectroscopies, in situ/operando characterisation

I. Fechete et al. / Catalysis Today 189 (2012) 227

Fig. 1. Framework of Faujasite (FAU) zeolite (Y or X-Type Si/Al = 2.5 or 1).

I. Fechete et al. / Catalysis Today 189 (2012) 227

The reactant selectivity, results in the exclusion of molecules too

corresponding transition state would require more space than is

Fig. 3. Principe of connement A and anti-connement C, dimensionality [4749].

I. Fechete et al. / Catalysis Today 189 (2012) 227

6-di-isopropyl-naphthalene compounds that are intermediates

I. Fechete et al. / Catalysis Today 189 (2012) 227

of the catalyst, as already discussed. At variance, the use of H-BEA

H3 PO4 , HF) to Lewis acids (metal halides) and further to solid

I. Fechete et al. / Catalysis Today 189 (2012) 227

pore system. The crystallized materials consist of alternating AlO2

I. Fechete et al. / Catalysis Today 189 (2012) 227

the structure type. According to Martens [112], even the highly

Descriptions of the structures and porosities of several MOFs are

2.4. Layered double hydroxides (LDHs)

Fig. 11. Schematic behavior observed upon adsorption, desorption of guest

I. Fechete et al. / Catalysis Today 189 (2012) 227

but well for ne chemistry under more gentle reaction conditions.

Hierarchical and mesoporous zeolites and mesoporous oxides

I. Fechete et al. / Catalysis Today 189 (2012) 227

2.8. Mesoporous materials

I. Fechete et al. / Catalysis Today 189 (2012) 227

ee from virtually zero to values ca. 40% in the reaction of methyl

I. Fechete et al. / Catalysis Today 189 (2012) 227

3.3. Biomass as a source of raw materials and future energy

renewable energies is vital. Some prospects are presented in

3.2. Perspectives with natural gas (NG)

H0 298 (kJ mol1 )

CO2 (dry) reforming

Autothermal reforming (ATR)

Catalytic partial oxidation (CPO)

The main chemical products from natural gas are summarized

I. Fechete et al. / Catalysis Today 189 (2012) 227

Energy consumption (GJ/t)

Source: IFP Energies Nouvelles.

I. Fechete et al. / Catalysis Today 189 (2012) 227

With South America

From FAOSTA, FAPRI.

reneries will be used to produce heat, electricity, transports, and

change in the Gibbs free energy as a function of temperature and the

Wood for paper

Wood for board

Wood for fuel

Source: IFP Energies Nouvelles, D. Lorne, Panorama 2010 Source: FAOSTAT.

I. Fechete et al. / Catalysis Today 189 (2012) 227

followed a trail of increasing hydrogen content. A major bottleneck

I. Fechete et al. / Catalysis Today 189 (2012) 227

5. Challenges for reneries

5.1. FischerTropsch synthesis (FT)

Recent developments in coreshell-structured catalysts that

I. Fechete et al. / Catalysis Today 189 (2012) 227

changes in the climate. The energy sector, which is the largest

fertilizers and plastics), salicylic acid (a pharmaceutical ingredient)

7. Activation and upgrading of light alkanes