CHEMSUSCHEM
MINIREVIEWS
DOI: 10.1002/cssc.201300797
Fischer–Tropsch Catalysts for the Production of
Hydrocarbon Fuels with High Selectivity
Qinghong Zhang, Kang Cheng, Jincan Kang, Weiping Deng, and Ye Wang*[a]
Fischer–Tropsch synthesis is a key reaction in the utilization of
non-petroleum carbon resources, such as methane (natural
gas, shale gas, and biogas), coal, and biomass, for the sustaina-
ble production of clean liquid fuels from synthesis gas. Selec-
tivity control is one of the biggest challenges in Fischer–
Tropsch synthesis. This Minireview focuses on the develop-
ment of new catalysts with controllable product selectivities.
Recent attempts to increase the selectivity to C5 + hydrocar-
bons by preparing catalysts with well-defined active phases or
with new supports or by optimizing the interaction between
the promoter and the active phase are briefly highlighted.
1. Introduction
The utilization of non-petroleum carbon resources, including
natural gas (also shale gas and biogas), coal, and renewable
biomass (in particular, the abundant and inedible lignocellulo-
sic biomass) for sustainable production of liquid fuels, has
become urgent because of the depletion of crude oil. The
direct transformation of coal, methane, or lignocellulosic bio-
mass into liquid fuels is very difficult. It is generally accepted
that the transformation of these non-petroleum carbon resour-
ces first into synthesis gas (syngas, CO + H2) by gasification and
then the conversion of syngas into liquid fuels through Fisch-
er–Tropsch (FT) synthesis is one of the most practicable routes.
FT synthesis, which was first reported about 90 years ago by
the German chemists Franz Fischer and Hans Tropsch, could
be expressed by Reactions (1) and (2).
ð2n þ 1Þ H2 þ n CO ! Cn H2nþ2 þ n H2 O
2n H2 þ n CO ! Cn H2n þ n H2 O
The liquid hydrocarbons produced by FT synthesis can be
free of sulfur, nitrogen, and aromatics and thus may easily
meet increasingly stringent environmental regulations. It has
[a] Prof. Dr. Q. Zhang, K. Cheng, Dr. J. Kang, Dr. W. Deng, Prof. Dr. Y. Wang
State Key Laboratory of Physical Chemistry of Solid Surfaces
Collaborative Innovation Center of Chemistry for Energy Materials
National Engineering Laboratory for Green Chemical
Productions of Alcohols, Ethers and Esters
College of Chemistry and Chemical Engineering
Xiamen University, Xiamen 361005 (P.R. China)
E-mail: wangye@xmu.edu.cn
This manuscript is part of a Special Issue on the 2nd International Sym-
posium on Chemistry of Energy Conversion and Storage. The Table of
Contents will appear here. This text will be updated once the Special
Issue has been assembled.
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Advances in developing bifunctional catalysts capable of cata-
lyzing both CO hydrogenation to heavier hydrocarbons and
hydrocracking/isomerization of heavier hydrocarbons are criti-
cally reviewed. It is demonstrated that the control of the sec-
ondary hydrocracking reactions by using core–shell nanostruc-
tures or solid-acid materials, such as mesoporous zeolites and
carbon nanotubes with acid functional groups, is an effective
strategy to tune the product selectivity of Fischer–Tropsch syn-
thesis. Very promising selectivities to gasoline- and diesel-
range hydrocarbons have been attained over some bifunction-
al catalysts.
been demonstrated that FT fuels produced from syngas are
more environmentally friendly than conventional petroleum-
based liquid fuels.[1–3] Under the current background of the
growing global demand for liquid fuels and increasing environ-
mental concerns, FT synthesis has received renewed interest in
recent years. In addition to conventional gas-to-liquid (GTL)
and coal-to-liquid (CTL) processes, the biomass-to-liquid (BTL)
process with FT synthesis as the core technology has also been
developed recently in industry.[4–6] At the same time, the devel-
opment of new catalysts and new reactor technologies has
also attracted considerable attention.[7–21]
However, some challenges still remain in catalysis for FT syn-
thesis. From a fundamental point of view, the control of selec-
tivity is one of the biggest challenges. Generally, the products
of FT synthesis follow the Anderson–Schulz–Flory (ASF) distri-
ð1Þ bution because of the polymerization mechanism. In brief, CO
undergoes dissociative or hydrogen-assisted dissociative chem-
ð2Þ
isorption on the surface of active metal phases (i.e., Ru, Co, or
Fe metal, or metal carbide nanoparticles) to form CHx (x = 0–3)
intermediates as the monomers for polymerization.[22] Coupling
between CHx monomers leads to chain growth and provides
CnHm intermediates. The CnHm intermediates with different
carbon numbers can then undergo hydrogenation or dehydro-
genation to yield paraffins or olefins as the final products.
According to the ASF distribution, ideally the molar fraction
(Mn) of the hydrocarbon product with a carbon number of n
depends only on the chain-growth probability (a), which is
a function of the rates of chain growth and chain termination,
determined by Equation (1).
Mn ¼ ð1aÞ an1 ð1Þ
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Typically, the product distribution is wide over conventional
FT catalysts. Lighter (C1–C4) hydrocarbons are expected with
a higher selectivity at a smaller a value, whereas higher selec-
tivity of heavier (C21 + ) hydrocarbons can be obtained at
a larger a value. However, as shown in Figure 1, the middle-
distillate products, which are usually the target products,
cannot be obtained with high selectivities. For example, the
maximum selectivity to gasoline-range (C5–C11) hydrocarbons is
approximately 45 % (a = 0.76) and that to diesel-range (C12–C20)
hydrocarbons is only approximately 30 % (a = 0.89).
Figure 1. Product selectivity in FT synthesis as a function of the chain
growth probability (a). The selectivity is expressed as the molar percentage
of a particular range of products on a carbon basis.
The widely distributed (C1–C80) hydrocarbon products ob-
tained from conventional FT catalysts must be subjected to fur-
ther refining to produce high-quality liquid fuels, such as gaso-
line, jet fuel, and diesel fuel.[23] To obtain high selectivity of
liquid fuels in the final products, it is necessary to increase the
selectivity to C5 + hydrocarbons and to decrease that to CH4
and C2–C4 paraffins. Many recent studies have shed light on
our understanding of the structure–performance relationships,
which are helpful for the rational design of efficient FT catalysts
with high C5 + selectivity.[7–17]
Ye Wang received his B.Sc. and M.Sc.
degrees from Nanjing University of
China and obtained his Ph.D. degree
in 1996 from the Tokyo Institute of
Technology in Japan. He worked as
a Research Associate at the Tokyo Insti-
tute of Technology, Tohoku University,
and Hiroshima University from 1996 to
2000 and was promoted to Associate
Professor at Hiroshima University in
2001. He became a full Professor of
Xiamen University in August 2001. He
is currently the Director of the Institute of Catalysis Science and
Technology of Xiamen University. His main research interests in-
clude heterogeneous catalysis for energy-related processes and se-
lective oxidation catalysis.
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Compared with the conventional two-stage process, that is,
FT synthesis followed by refining, the direct production of
high-quality liquid fuels from syngas would be more energy
and cost efficient. A one-stage process would increase the
competitiveness of FT technology for the production of liquid
fuels. In particular, the transformation of small-scale, remote
gas resources and scattered biomass resources without down-
stream hydrotreatment processes under extreme process con-
ditions would be of significant interest. Moreover, the deploy-
ment of FT plants with high-pressure H2 plants for hydrotreat-
ment on offshore platforms would raise serious safety con-
cerns.[24] Undoubtedly, the development of new FT catalysts
with high selectivity to a specific range of hydrocarbons is the
key to this one-stage process.
This Minireview focuses on recent advances in the develop-
ment of new FT catalysts for the selective production of hydro-
carbon fuels. Recent studies aimed at increasing the C5 + selec-
tivity are first highlighted. Then bifunctional catalysts or cata-
lytic systems that combine the catalytic phases (sites) for CO
hydrogenation and hydrocarbon hydrocracking and can direct-
ly produce gasoline- or diesel-range hydrocarbons with high
selectivities are critically reviewed.
2. Effort to Improve C5 + Selectivity
Many factors can influence catalytic behavior, including the
C5 + selectivity of a FT catalyst. Figure 2 lists some major factors
that can exert significant influence on product selectivity and
CO conversion activity. The effects of most of these factors on
catalytic behavior have been summarized in our previous
review articles.[13, 17] Herein, we highlight some recent studies
involving new concepts or new strategies to prepare FT cata-
lysts with increased C5 + selectivity.
Figure 2. Some major factors that influencing product selectivity in FT syn-
thesis.[13, 17]
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Concerning the chemical state of the active phase, the cur-
rent consensus is that metallic ruthenium and cobalt nanopar-
ticles are the active phases for ruthenium- and cobalt-based
catalysts, whereas the iron carbide phase is responsible for
chain growth for iron-based catalysts.[13, 17] For Ru- and Co-
based catalysts, it is accepted that the preparation of catalysts
containing Ru0 or Co0 nanoparticles (with high reducibility and
proper size) and keeping them in the metallic state during the
reaction are very important for obtaining a high C5 + selectivity.
However, the strategy for how to prepare an iron-based cata-
lyst with high C5 + selectivity is not clear. Conventionally, iron
catalysts are derived from hematite (Fe2O3), magnetite (Fe3O4),
or precursors that could form these iron oxides after heat
treatment, followed by reductive treatment in H2 or syngas.
The catalysts undergo reconstruction at the initial reaction
stage, and a mixture of various iron species (including Fe3O4,
metallic Fe, and Fe carbides) is typically obtained at the steady
state.[11, 15, 25] A large fraction of iron may not function or even
function negatively for the formation of C5 + hydrocarbons.
Some recent studies have made efforts to control the active
iron phase or prepare well-defined iron-based catalysts.
Bao and co-workers prepared Fe2O3 nanoclusters inside and
outside carbon nanotubes (CNTs) with similar sizes and they
found that the Fe2O3 nanoclusters confined inside CNTs were
transformed into iron carbide species more efficiently.[26] The
ratio of the intensities of X-ray diffraction peaks ascribed to
iron carbide and Fe3O4 was about 4.5 for the confined iron cat-
alysts after the reaction steady state was achieved; this was
significantly higher than that (< 2.5) for the catalyst with iron
located outside the CNTs. The former catalyst exhibited signifi-
cantly higher C5 + selectivity than that of the latter. A similar
phenomenon was confirmed in a subsequent study by Dalai
and co-workers.[27]
In addition to the higher fraction of iron carbide species
over the catalysts with iron confined in CNTs, the following
confinement effects may also affect the product selectivity.[28]
First, the reactions confined in the CNTs may enhance the re-
adsorption of a-olefins and the chain-growth probability, thus
increasing the C5 + selectivity. Second, the space restriction
may prevent the iron species from aggregating under the reac-
tion conditions. Third, it has been demonstrated that CO could
be enriched inside the CNTs more than H2 because of the
stronger interaction of CO with the CNT interior surface; this
results in a higher CO/H2 ratio and favors C5 + selectivity.[28]
The synthesis of highly dispersed iron oxide nanoparticles
embedded in carbon spheres (denoted as Fe@C spheres) by
a hydrothermal cohydrolysis–carbonization process afforded
a catalyst with a high fraction of iron carbides after reduction
and a high C5 + selectivity.[29] After reduction in H2 at 673 K, the
size of the iron particles was about 7 nm inside the carbon
sphere with a diameter of about 5 mm. Mesopores existed
inside the carbon sphere, which ensured accessibility of the
embedded iron particles to syngas. Because the iron particles
were surrounded by carbon in the catalyst, the fraction of iron
carbides (mainly q-Fe3C and c-Fe5C2) reached 88 % in the re-
duced catalyst. A C5 + selectivity of 60 % could be attained in
the absence of any promoters; this was significantly higher
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than those of most other iron-based catalysts reported to date.
This catalyst was also quite stable during the reaction because
the confinement of iron species inside the carbon sphere
could avoid the sintering of iron species.
By using a chelate-assisted co-assembly methodology, highly
dispersed Fe2O3 nanoparticles encapsulated in mesoporous
carbon materials were successfully synthesized.[30] It is of inter-
est that the Fe2O3 nanoparticles are partially embedded in the
carbon framework with the remaining part exposed in the
mesopore channels. This unique semiexposure structure not
only provides an excellent exposed surface for catalysis, but
also prevents the aggregation of iron particles during the reac-
tion. This mesoporous iron–carbon nanocomposite exhibited
a C5 + selectivity of up to 68 %, which was better than other
promoter-free iron-based catalysts.
c-Fe5C2 has been proposed as an active phase for FT synthe-
sis.[25] A recent study has succeeded in the controlled synthesis
of c-Fe5C2 nanoparticles (  20 nm) by a low-temperature wet-
chemical route.[31] Bromide is a key inducing agent for the con-
version of [Fe(CO)5], which is the Fe precursor, into c-Fe5C2
nanoparticles in the synthetic process. Compared with the cat-
alyst derived from H2-reduced hematite, the c-Fe5C2 nanoparti-
cles showed higher catalytic activity for FT synthesis. More im-
portantly, the c-Fe5C2 nanoparticles exhibited significantly
higher C5 + selectivity than that of the H2-reduced hematite.
This result demonstrates again that c-Fe5C2 is an active phase
for both CO activation and chain growth.
In addition to the chemical state, the size of the active
phase is also a key factor that determined the catalytic behav-
ior, including C5 + selectivity. A number of recent studies have
pointed out that the size of Ru0, Co0, or c-Fe5C2 affects both
the CO conversion activity and the product selectivity.[32–41]
Over many catalysts based on Co and Ru, the turnover fre-
quency (TOF) for CO conversion and the C5 + selectivity in-
crease with increasing particle size to a critical point (6–10 nm,
depending on the catalyst and reaction conditions) and then
change insignificantly.[32, 34, 37, 39, 41] Thus, the preparation of cata-
lysts containing larger Co or Ru particles would favor the C5 +
selectivity. However, this means that most of the metal atoms
in the catalyst are not on the surface and are not available for
catalysis. The cost of cobalt or ruthenium is not low and may
become a problem for large-scale industrial processes.
To use cobalt more efficiently, Rothenberg and co-workers
recently proposed constraining cobalt on the outside (shell) of
the catalyst particle and replacing the core with a less expen-
sive material.[42] They prepared a core–shell-structured Fe@Co
catalyst by a two-step process. Magnetite nanoparticles with
a diameter of 7 nm were first synthesized, and then a cobalt
shell with a thickness of about 1 nm was coated onto the mag-
netite. The Fe@Co nanoparticles were then loaded onto nano-
sized Al2O3 and were used for FT synthesis. This core–shell-
structured catalyst provided approximately 40 % selectivity to
C5–C27 at 20 % CO conversion at 503 K and 3.2 MPa. The C5–C27
selectivity over this catalyst was still lower than that over a typi-
cal supported cobalt catalyst. The selectivity to CO2 was only
2 %, which was significantly lower than that for the iron-based
catalyst. Oxygenates and olefins were also formed with selec-
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tivities of 10 and 20 %, respectively, which were higher than 0.54 gCH2gcatalyst1 h1 was obtained with a C5 + selectivity of
those for the conventional cobalt-based catalyst. This implies 90 % over the 0.1 wt % Ru/30 wt % Co/SiC catalyst.[44]
that iron may interfere with the catalytic behavior of the core– However, the interaction between Co and chemically inert
shell-structured catalyst. More details of such bimetallic catalyt- SiC is too weak, leading to easier aggregation of Co particles.
ic systems with core–shell structures should be investigated in To overcome this problem, Pham-Huu and co-workers further
the future. Moreover, this strategy should also be applicable to developed a TiO2-decorated, SiC-supported Co catalyst and
the ruthenium-based catalyst. found that the introduction of TiO2 caused medium-strength
The choice of an appropriate support is also key to obtain- interactions between Co and the support, leading to higher
ing high FT performances, including C5 + selectivity. It is gener- dispersion (smaller size) of Co particles.[45] This catalyst showed
ally accepted that a balanced interaction between the support higher CO conversion and Co time yield (50.5 % and 7.5 
and the active metal is particularly important for FT synthesis. 105 molCO gCo s1) than those of Co/SiC without TiO2 decoration
An interaction that is too weak may lead to a poor dispersion (35.4 % and 5.3  105 molCO gCo s1), although the C5 + selectivity
of active metal, whereas an interaction that is too strong was almost the same (  92 %; Table 1).[45] A hierarchically struc-
would cause a low degree of reduction of the active metal. tured carbon material, that is, carbon nanofiber (CNF), directly
Both are detrimental to the CO conversion activity and C5 + se- grown on the surface of microfibers in carbon felt was also
lectivity. Many physicochemical properties of the support, such demonstrated to be a good support of cobalt nanoparticles for
as the mechanical strength, the thermal conductivity (heat dis- FT synthesis.[46] The efficient three-dimensional thermal conduc-
sipation ability), porous structure, and the acidity, are known tive network in this new type of support can offer an advant-
to affect the catalytic behavior. Most of these issues have been age of improved heat transfer, which is important for the
discussed in detail in our previous review.[13] highly exothermic FT reaction.
Recently, silicon carbide (b-SiC) with medium specific surface Promoters play important roles in FT synthesis, particularly
area (20–40 m2 g1) has received attention as a new support for the Fe- and Co-based catalysts. Conventionally, promoters
for FT catalysts capable of providing very high C5 + selectivities are introduced by stepwise impregnation or co-impregnation
(> 90 %).[43–45] It is well known that FT synthesis is a strongly methods. However, such a method cannot ensure the direct
exothermic reaction and usually CO conversion has to be limit- contact of promoters with the active metal nanoparticles. Re-
ed to < 50 %. b-SiC possesses high thermal conductivity, show- cently, Regalbuto and co-workers proposed a new strategy for
ing unique features for FT synthesis under reaction conditions preparing manganese-modified, supported cobalt cata-
for higher CO conversions, which are severe for most of the FT lysts.[47, 48] Mn is known to be capable of increasing the C5 + se-
catalysts reported to date. The comparison between Co/SiC lectivity and the CO conversion activity for both iron- and
and Co/Al2O3 (Co content = 30 wt %) showed that at medium cobalt-based catalysts.[6, 10, 13] Mn may also increase the fraction
conversions (< 50 %) the two catalysts displayed similar C5 + se- of olefins in light (C2–C4) hydrocarbons.[13] Regalbuto and co-
lectivities. However, when the CO conversion was increased to workers used a preparation strategy known as strong electro-
70–80 %, the C5 + selectivity over Co/SiC was sustained at 88 %, static adsorption (SEA) to introduce Mn species selectively
whereas that over Co/Al2O3 decreased to 52 % (Table 1).[43] The onto the Co3O4 particles loaded on TiO2.[47] Scanning tunneling
lower selectivity of the Co/Al2O3 catalyst could be attributed to electron energy-loss spectroscopy (STEM-EELS) provided
the presence of a local hot spot generated under the severe a clear image of the surrounding of the Co3O4 particles
reaction conditions. The addition of 0.1 wt % Ru to the Co/SiC (20 nm) by a shell of MnO2 in the calcined Mn/Co/TiO2 cata-
catalyst could further enhance the C5 + selectivity to > 90 % at lyst prepared by the SEA technique.[48] On the other hand, in
high CO conversions.[44] For example, at 503 K and a GHSV of the catalyst prepared by the impregnation method, MnO2 was
2850 h1, 91 % C5 + selectivity was obtained with 67 % CO con- mainly located on TiO2, which was separated from the Co3O4
version (Table 1). At 508 K, a steady-state reaction rate of particles. The Mn/Co/TiO2 catalyst prepared by the SEA tech-
nique exhibited significantly higher C5 + selectivity than the
catalyst prepared by impregnation. The introduction of Mn by
Table 1. Catalytic performances of cobalt catalysts loaded on b-SiC with the SEA technique had significant positive effects on product
and without modification for FT synthesis.
selectivity; the selectivity to CH4 decreased and that to C5 + hy-
Catalyst T Conv. Selectivity [%] drocarbons increased. The ratios of olefins to paraffins in C2,
[K] [%] CH4 C2–C4 C5 + C4, and C6 hydrocarbons were also increased by the addition of
30 wt % Co/SiC[a] 509  71 7 4 88 Mn. These results clearly show that the enhanced contact be-
30 wt % Co/Al2O3[a] 511  77 25 13 52 tween the promoter and the active phase is crucial.
30 wt % Co/0.1 wt % Ru/SiC[b] 503 67 6 2.7 91
10 wt % Co/SiC[c] 488 26.9 2.9 1.6 95.5
10 wt % Co/TiO2–SiC[c] 488 33.9 3.2 1.5 95.3 3. Bifunctional Catalysts for Selective Produc-
10 wt % Co/SiC[c] 503 35.4 5.4 2.9 91.6
10 wt % Co/TiO2–SiC[c] 503 50.5 5.9 2.2 91.7
tion of Gasoline- and Diesel-Range Hydro-
carbons
[a] From Ref. [43]; reaction conditions: P = 4 MPa, H2/CO = 2, gas hourly
space velocity (GHSV) = 330 h1. [b] GHSV [standard temperature and A number of studies have pointed out that the catalytic behav-
pressure (STP)] = 2850 h1. [c] From Ref. [45]; reaction conditions: P = ior of an FT catalyst is a complicated interplay of many factors.
4 MPa, H2/CO = 2, GHSV (STP) = 2850 h1.
Some key insights into the effects of various factors on catalyt-

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ic performances have already been accumulated for catalyst
design. By controlling the chemical state of active species,
tuning the size and the microenvironment of active species,
and incorporating proper promoters with correct locations, we
may optimize the C5 + selectivity and the CO conversion activi-
ty. However, to obtain controlled product distributions, particu-
larly higher selectivity to middle-distillate hydrocarbons, such
as gasoline or diesel fuel, new strategies are required. Here-
after, we focus on recent advances in tuning the product distri-
butions by using bifunctional catalysts. The key idea for the bi-
functional catalytic system is illustrated in Figure 3.[49] In brief,
Figure 3. Schematic illustration of the strategy for using a bifunctional cata-
lytic system with CO hydrogenation (conventional FT) and hydrocarbon hy-
drocracking/isomerization functions.
the catalytic system contains both the active metal (Co, Fe car-
bide, or Ru nanoparticles) for the CO hydrogenation reaction
(the primary reaction), over which heavier (C5 + ) hydrocarbons
could be produced, and the acid site for secondary reactions,
including the hydrocracking and/or isomerization of heavier
hydrocarbons to middle-distillate products. By tuning the sec-
ondary reaction, we can expect to obtain high selectivity to
C5–C11 (gasoline range) or C10–C20 (diesel range) hydrocarbons.
3.1. Microporous zeolite-based bifunctional catalysts
Acidic zeolites have been exploited to construct the bifunc-
tional FT catalyst. By using a dual-bed reactor configuration
with an acidic zeolite downstream from a conventional FT cata-
lyst (either in the same reactor or in two different reactors; Fig-
ure 4 a) or by using a hybrid catalyst containing both compo-
Figure 4. Representative bifunctional FT catalytic systems: a) Dual-bed reac-
tor configuration, b) hybrid catalyst, c) core–shell-structured catalyst.
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nents (Figure 4 b), syngas can be directly transformed into C5–
C11 hydrocarbons with good selectivity owing to the catalytic
function of acidic zeolite in the hydrocracking/isomerization re-
actions.[13, 14, 50]
For the development of efficient hybrid catalysts, the follow-
ing issues should be considered: First, the optimum reaction
conditions for FT synthesis and hydrocracking/isomerization re-
actions may be different. For example, cobalt-based catalysts
typically work for the selective formation of C5 + hydrocarbons
at temperatures lower than those for hydrocracking reactions.
Suitable reaction conditions with balanced performances
should be selected. Second, intimate contact between the FT
active center and the acid site is required to perform the two
types of reactions smoothly. However, the direct contact of
two catalysts may cause problems. For example, the hybrid
catalyst composed of an alkali-metal-promoted fused iron cata-
lyst and H-ZSM-5 deactivated quickly because of the migration
of alkali metal from the iron catalyst to zeolite.[51] Thus, the
design of hybrid catalysts with active sites on the nano- or mo-
lecular scale is crucial. Third, the deactivation of zeolite may be
faster because of carbon deposition on acid sites, whereas the
frequent regeneration of the catalyst would be costly. Increas-
ing the catalyst stability is a key issue. Several studies showed
that a hybrid catalyst with a suitable combination of different
components might have been beneficial to catalyst stability
because the coexistence of an acid zeolite with the conven-
tional FT catalyst might have inhibited deactivation of the FT
catalyst by simultaneous hydrocracking of waxes.[52]
The spatial arrangement of the two components, which cat-
alyze the two reactions in a tandem manner, can exert a signifi-
cant effect on the process efficiency. To increase the efficiency
of the tandem reactions, Tsubaki and co-workers successfully
designed a kind of core–shell-structured bifunctional cata-
lyst.[53, 54] This kind of hybrid catalyst designed on the nanoscale
has shown promising performances for the conversion of
syngas into isoparaffins.[53, 55–60, 62–65] Conceptually, the heavier
hydrocarbons formed on the core, which is a conventional FT
catalyst, have to diffuse out through the shell, which is a zeolite
(Figure 4 c). Thus, this core–shell configuration can increase the
efficiency of secondary reactions.
The synthesis of such core–shell-structured bifunctional FT
catalysts is a key point. Tsubaki and co-workers developed a hy-
drothermal method for preparing the core–shell structured cat-
alyst.[53, 55–59] In brief, a conventional FT catalyst pellet was
added to the zeolite precursor solution, which contained sili-
con and aluminum sources and a template for zeolite synthe-
sis. Then, the mixture was subjected to hydrothermal synthesis.
The time for crystallization of the zeolite could be used to
adjust the thickness of the zeolite shell surrounding the FT cat-
alyst. Pretreatment of the FT catalyst may also be needed to
make the surface of FT catalyst easier to coat with some zeo-
lites, such as H-beta.[59] Catalytic studies showed that the coat-
ing of H-ZSM-5 on 10 wt % Co/SiO2 suppressed the formation
of C11 + hydrocarbons, whereas the production of hydrocarbons
up to C20 occurred over the physically mixed hybrid catalyst
under the same reaction conditions.[55, 56] CO conversions over
Co/SiO2 and the physically mixed hybrid catalyst were almost
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the same (94–98 %), whereas they became slightly lower
(85 %) over catalysts with the Co/SiO2 core and H-ZSM-5
shell.[56] The ratio of isoparaffins to n-paraffins (denoted as Ciso/
Cn) increased from 0.49 to 1.88 upon increasing the thickness
of the zeolite shell from 0 to about 24 mm. However, the selec-
tivity to CH4, which is an undesirable product, also increased
with the thickness of the zeolite shell. A recent study pointed
out that, in such a core–shell-structured bifunctional catalyst,
part of cobalt species might also exist in the shell of H-ZSM-5
zeolite and might be encapsulated by H-ZSM-5.[60]
Over the Co/Al2O3@H-beta bifunctional catalyst, the selectivi-
ty to C5–C11 could reach 60–70 % with a Ciso/Cn ratio of more
than 2 under reaction conditions of 533–538 K and 1 MPa of
syngas (H2/CO = 2).[53, 59] These results are considerably better
than those obtained over a physical mixture of H-ZSM-5- or H-
beta with Co/Al2O3.
A core–shell-structured bifunctional FT catalyst containing
Co/ZrO2, which exhibited a higher selectivity to C5 + hydrocar-
bons,[61] as the core and H-ZSM-5 as the shell has also been
successfully synthesized by the hydrothermal method.[62] This
Co/ZrO2@H-ZSM-5 catalyst showed better selectivities to C5–C11
isoparaffins (23–25 %) than the physical mixture of Co/ZrO2
and H-ZSM-5 (17 %), although CO conversions were lower over
the core–shell catalyst.[62]
However, there are several limitations to using the hydro-
thermal method to construct the core–shell catalyst. First, this
method is not easy for some zeolites, such as H-Y and H-
beta.[63] Second, the strongly alkaline conditions used for zeo-
lite synthesis and the vulnerability of the FT core catalyst (par-
ticularly that with the SiO2 support, which can be destroyed in
alkaline medium) further increase the difficulty of this method.
Recently, Tsubaki and co-workers proposed two new strat-
egies to prepare core–shell-structured catalysts.[63] One strategy
is the stepwise hydrothermal synthesis technique, in which
zeolite silicalite-1 is used as the first intermediate layer coated
on the Co/SiO2 pellets, and then the acidic H-ZSM-5 shell
grows on the intermediate layer. The coating of silicalite-
1 onto Co/SiO2 could be performed by hydrothermal synthesis
under close to neutral conditions. The intermediate layer
cannot only protect the core catalyst from damage in the sub-
sequent hydrothermal synthesis but also facilitate the forma-
tion of the outside catalytic H-ZSM-5 shell.[64] The other strat-
egy is a physically adhesive method, in which the zeolite pow-
ders are directly and uniformly pasted onto the Co/SiO2 core
catalyst surface by using a silica sol (Ludox) as an adhesive.[63]
Both strategies have been demonstrated to provide core–
shell bifunctional catalysts that are efficient for the conversion
of syngas to isoparaffins. Under the reaction conditions dis-
played in Table 2, the Ciso/Cn ratio and the selectivity to C11 +
were 0.12 and 15.3 %, respectively, over the Co/SiO2 catalyst.[63]
The use of Co/SiO2@H-ZSM-5 catalysts prepared by stepwise
hydrothermal synthesis and physical adhesion techniques in-
creased the Ciso/Cn ratios to 0.99 and 0.92, respectively. At the
same time, the C11 + selectivities decreased to 0.4 and 1.2 %
(Table 2). These values clearly suggest the role of the zeolite
shell in the hydrocracking and isomerization of the long-chain
hydrocarbons formed on the core catalyst. The thickness of
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Table 2. Catalytic performances of Co/SiO2@H-ZSM-5 catalysts prepared
by different methods for FT synthesis.[a]
Catalyst[b] Preparation method Conv. Selectivity[c] [%]
[%] Cn Ciso C11 +
Co/SiO2 – 99.2 88 11 15
Co/SiO2 + H-ZSM-5 physical mixing 98.5 53 10 8.2
Co/SiO2@H-ZSM-5-HT stepwise hydrothermal 97.7 50 49 0.4
Co/SiO2@H-ZSM-5-PA physical adhesion 99.1 48 44 1.2
Co/SiO2@H-ZSM-5-PA[d] physical adhesion 99.3 35 51 0.3
[a] From Ref. [63]; reaction conditions: T = 553 K, P = 1.0 MPa, H2/CO = 2,
W(Co/SiO2)/F(syngas) = 10 g h mol1. [b] The weight increment after the
introduction of zeolite was 25 %. [c] Cn : normal paraffins; Ciso : isoparaffins;
C11 + : hydrocarbons with a carbon number of  11. The other products
are olefins. [d] The weight increment after the introduction of zeolite was
60 %.
the zeolite shell can be easily regulated by using the physical
adhesion method. Increasing the thickness of the zeolite shell
(or zeolite weight in the core–shell bifunctional catalyst)
causes a further increase in the Ciso/Cn ratio (Table 2) and also
an increase in the selectivity to olefins.
A core–shell-structured bifunctional catalyst containing
a fused iron core and H-ZSM-5 shell has also been synthesized
through the hydrothermal method.[65] To obtain a compact
shell, the hydrothermal synthesis should be performed twice
by using the resulting product after the first round of hydro-
thermal synthesis as the core catalyst. The thickness of the
shell was about 3 mm. Similar to those observed for cobalt-
based bifunctional catalysts, the heavier hydrocarbons were
significantly suppressed by using the fused-Fe@H-ZSM-5 cata-
lyst.[65] The selectivity to C5–C11 was about 50 % over this cata-
lyst. The Ciso/Cn ratio (in C4 + ) was 4.17, whereas almost no iso-
paraffins were formed over fused iron alone and the Ciso/Cn
ratio was 2.31 over the physical mixture of fused iron and H-
ZSM-5 under the following reaction conditions: T = 573 K, P =
1.0 MPa, H2/CO = 1, W (catalyst weight)/F (total flow rate) =
10 g h mol1.
Qiao and co-workers succeeded in preparing a core–shell
Raney Fe@H-ZSM-5 bifunctional catalyst through the hydro-
thermal synthesis approach using Fe50Al50 alloy as the starting
material for the core catalyst and tetrapropylammonium hy-
droxide (TPAOH) as the template for the hydrothermal synthe-
sis of the H-ZSM-5 shell.[66] TPAOH also functioned as a base for
the dealumination of the Fe–Al alloy, and the leached Al spe-
cies could be directly utilized as the Al source for zeolite syn-
thesis. By using this intriguing preparation strategy, the core–
shell structure containing the H-ZSM-5 shell with a Si/Al ratio
of about 63 and a thickness of about 4.1 mm enclosing the iron
core was obtained. This core–shell catalyst (denoted as R-
Fe@HZSM-5) showed a higher CO conversion than the Raney
Fe alone (denoted as R-Fe) and the physical mixture of R-Fe
and H-ZSM-5 (denoted as R-Fe-HZSM-5). A C5–C11 selectivity of
71 % and a Ciso/Cn ratio of 1.9 were obtained over the core–
shell catalyst at 543 K (Figure 5). These values are significantly
higher than those over R-Fe and a physical mixture of R-Fe
and H-ZSM-5 (Figure 5). Furthermore, the presence of the H-
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Figure 5. Catalytic performances of R-Fe, a physical mixture of R-Fe and H-
ZSM-5 (R-Fe-HZSM-5), and a core–shell-structured catalyst with R-Fe as the
core and H-ZSM-5 as the shell (R-Fe@HZSM-5) for FT synthesis.[66] a) CO con-
version and Ciso/Cn ; b) product selectivity in hydrocarbons. Reaction condi-
tions: T = 543 K, P = 2.0 MPa, H2/CO = 2.0, W(Fe)/F(H2+CO) = 10 g h mol1,
time on stream = 148–150 h.
ZSM-5 shell enclosing the R-Fe core not only decreased the se-
lectivity to heavier (C12 + ) hydrocarbons, but also decreased
those to CH4 and C2–C4 hydrocarbons and contributed to the
increase in the C5–C11 selectivity (Figure 5 b).
Characterization revealed that the fractions of Hgg carbide
(c-Fe2C5) species in the catalysts after the reaction increased in
the sequence R-Fe (24.5 %) < R-Fe-HZSM-5 (28.4 %) < R-
Fe@HZSM-5 (42.1 %), whereas the fractions of Fe3O4 changed
in the opposite direction.[66] Thus, the presence of the H-ZSM-5
shell also modified the chemical state of the Fe core catalyst to
increase the fraction of c-Fe2C5 species and decrease that of
Fe3O4. It is known that c-Fe2C5 is the active phase for FT syn-
thesis.[25, 31] Concerning the nature of the role of the H-ZSM-5
shell on influencing the chemical state of Fe, it was proposed
that H2O, which was formed as a byproduct of FT synthesis
and was likely to be responsible for the oxidation of iron car-
bide species to Fe3O4 during the reaction, might be preferen-
tially adsorbed onto H-ZSM-5.
ZSM-5 microspheres containing well-dispersed uniform
Fe3O4 nanoparticles inside the sphere were synthesized by an
in situ crystallization route.[67] In this route, a Fe3O4@SiO2 com-
posite with Fe3O4 nanoparticles (  10 nm) confined in SiO2
pores was used as the precursor and then the hydrothermal
synthesis was performed. The incomplete dissolution of the
Fe3O4@SiO2 composite in a low-alkaline solution during the hy-
drothermal synthesis could retain the Fe3O4 nanoparticles.
Characterization revealed that the microspheres of zeolites
with diameters of 6–9 mm were composed of concentric nano-
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rod-like ZSM-5 crystals with Fe3O4 nanoparticles dispersed be-
tween these nanorods. This Fe3O4@ZSM-5 species was investi-
gated for FT synthesis after reduction. The C5–C12 selectivity
was 44.6 % at a CO conversion of 87 % after 110 h of reaction.
The selectivity to C13–C20 was low (3.2 %), and no C21 + could be
detected, indicating the role of the ZSM-5 zeolite in the hydro-
cracking of heavier hydrocarbons. However, this catalyst exhib-
ited a higher CH4 selectivity (16 %).
Zeolite-supported FT metal catalysts are simple bifunctional
catalysts. A few early studies already pointed out that the use
of zeolites with strong acidity such as H-ZSM-5 as the supports
could increase the selectivity to gasoline-range hydrocarbons
with a large fraction of branched products.[68–70] Several param-
eters play key roles in controlling the product selectivity in
these zeolite-supported catalysts. First, the acidity is undoubt-
edly a key factor. Compared with HY and H-mordenite, the use
of H-ZSM-5 as a support for a cobalt catalyst showed higher
selectivity to gasoline-range hydrocarbons owing to its stron-
ger acidity.[68]
Second, in addition to the acidity, the pore structure of zeo-
lites also plays a significant role in determining the product
distribution. For example, among cobalt catalysts loaded on
different zeolites, including H-ZSM-5, H-ZSM-11, H-ZSM-12, and
H-ZSM-34, the Co/H-ZSM-12 catalyst was more efficient for the
formation of gasoline-range hydrocarbons, whereas a larger
fraction of heavier n-paraffins remained over the Co/H-ZSM-34
catalyst, although the former catalyst exhibited a weaker acidi-
ty.[69] This is possibly because of the difference in the pore
structure of zeolites; H-ZSM-12 had pore channels (0.57 
0.61 nm) that were larger than those of H-ZSM-34 (  0.50 nm).
The accessibility of the acid sites located inside the zeolite
pores is crucial for secondary reactions of the primary FT
products.
Third, the location of cobalt on/in the zeolite also affects the
catalytic properties. Previous attempts to load Co onto zeolites
through impregnation or an ion-exchange method easily led
to the formation of Co2 + ions located in the ion-exchanging
position or inside the small pores of zeolites; these Co2 + ions
were difficult to reduce and useless for FT synthesis.[70] More-
over, these Co2 + ions in ion-exchanging positions may affect
the acidity of zeolites, playing a negative role in the hydro-
cracking reactions. The introduction of a precipitation step
before reduction or the exploitation of strong reducing agents
(e.g., NaBH4) could increase the fraction of cobalt nanoparticles
in the catalyst.[71, 72] The premodification of zeolites with Al2O3
could alleviate interactions between the Co precursor and zeo-
lites to facilitate the reduction of Co species. A 7.5 wt % Co–
0.19 wt % Ru/Al2O3-bound ZSM-12 catalyst, which was devel-
oped by using a strategy developed by Chevron[24] for consid-
eration in commercial applications, exhibited selectivities to
CH4, C2–C4, C5–C20, and C21 + of 9.9, 7.6, 77.6, and 4.6 %, respec-
tively, with a CO conversion of about 40 % under the following
reaction conditions: T = 493 K, P = 2 MPa, H2/CO = 2.[24] This cat-
alyst was relatively stable or at least not significantly different
to conventional cobalt-based FT catalysts.
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3.2. Mesoporous zeolite-based bifunctional catalysts
As described above, a bifunctional catalyst composed of an FT
catalyst or an active metal and a zeolite catalyzes the produc-
tion of C5–C11 (in particular isoparaffins), that is, gasoline-range
hydrocarbons. Considerable progress has been achieved in
recent years. However, the effective control of product selectiv-
ity is still challenging. One key problem for the use of zeolites
is the diffusion limitation. Although low CH4 selectivity has
been observed over a few catalysts based on zeolites, diffusion
limitation usually leads to high CH4 and C2–C4 selectivities.
A couple of reasons may explain these undesirable products.
First, the diffusion limitation may cause higher local H2/CO
ratios on the active metal surface because H2 diffuses more
quickly than CO. This would lead to a higher selectivity to
lighter hydrocarbons. Second, for the bifunctional catalysts, the
primary hydrocarbon products formed on the FT active metals
would migrate into the micropores of zeolites, where the acid
sites are located and secondary hydrocracking/isomerization
occurs, and the products must diffuse out of the micropores.
The slow transportation of products inside the long micropores
may cause over-cracking, leading to higher selectivity to lighter
hydrocarbons. Furthermore, most acid sites are located inside
the narrow and long micropores, and this would increase the
difficulty in accessing these acid sites by primary heavier hy-
drocarbons, which decreases the efficiency of secondary reac-
tions. Bessell once proposed that only the external acid sites
and the internal acid sites close to the pore mouth could readi-
ly be accessed by the primary hydrocarbon products formed
on active metals typically located outside the micropores.[69]
Therefore, to tune the secondary hydrocracking reactions by
utilizing new solid-acid materials is key to decreasing the selec-
tivities to C1–C4 and increasing that to C5–C11 hydrocarbons.
Zeolites with hierarchical porous structures, particularly mes-
oporous zeolites containing both micro- and mesopores, have
attracted considerable attention as a new type of promising
catalytic materials in recent years.[73–81] These materials com-
bine the advantages of conventional microporous zeolites,
which possess strongly acidic catalytic functions, shape-selec-
tive features, and high stability at high temperatures owing to
the crystalline structure, and mesoporous materials with effi-
cient mass transportation. Mesoporous zeolites have demon-
strated improved performances in many catalytic reactions,
particularly acid-catalyzed reactions. For example, a hierarchical
Y zeolite has demonstrated improved product distributions in
the hydrocracking of heavy hydrocarbons, decreasing the se-
lectivities to CH4 and light hydrocarbons and increasing those
to kerosene and diesel.[82] Mesoporous zeolites may be expect-
ed to provide improved product selectivity when they are uti-
lized for the construction of bifunctional FT catalysts.
There are two general routes to synthesize mesoporous zeo-
lites.[73–81] One route is in situ synthesis with templates for both
micro- and mesopores. The other route is post-synthetic treat-
ment, by creating mesopores in conventional crystalline zeo-
lites with different treatments (e.g., hydrothermal treatment,
alkaline treatment, or other chemical treatments) to dissolve
the silicon or aluminum atoms from the zeolite framework.
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Our group has used mesoporous ZSM-5 and mesoporous
beta (denoted as meso-ZSM-5 and meso-beta) prepared by
a simple alkaline treatment method, that is, treating H-ZSM-5
or beta in aqueous solutions of NaOH with appropriate con-
centrations, to fabricate bifunctional FT catalysts.[83, 84] Charac-
terization by argon adsorption and TEM clarified that the hier-
archical ZSM-5 and beta zeolites prepared by this technique
contained both micropores with a size of about 0.55 or
0.67 nm, which is typical for ZSM-5 or beta, and mesopores
with sizes ranging from about 3 to 12 nm. The size of meso-
pores depends on the concentration of the aqueous NaOH so-
lution used for posttreatment.
The meso-ZSM-5 and meso-beta samples with different sizes
of mesopores have been utilized for FT synthesis.[83, 84] Rutheni-
um was chosen as the active metal in our work. Despite the
higher price of ruthenium compared with cobalt and iron,
ruthenium-based catalysts are suitable for fundamental re-
search to obtain clear-cut information about the effects of
mesoporosity and the acidity of the hierarchical zeolites be-
cause ruthenium precursors can be easily reduced to Ru0 and
the size of Ru0 particles can be controlled facilely over meso-
ZSM-5 or meso-beta with different pore sizes. Ruthenium
nanoparticles were loaded onto meso-ZSM-5 or meso-beta by
a simple impregnation process using RuCl3, followed by calci-
nation, and H2 reduction at 573 K. The reduction degree of
ruthenium species was > 85 % in all these samples. As an ex-
ample, the sizes of the mesopores and Ru nanoparticles for
the Ru/meso-ZSM-5 series of catalysts with meso-ZSM-5 pre-
pared by using different concentrations of NaOH (denoted as
Ru/meso-ZSM-5-x m, in which x m denotes the NaOH concen-
tration) are displayed in Table 3.[83] TEM studies showed that
the mean sizes of Ru nanoparticles in these samples were
almost the same, ranging from 6.5 to 7.2 nm. This was further
confirmed by the dispersion of Ru particles measured by using
the H2O2 titration technique.
Catalytic studies showed that the use of meso-ZSM-5 instead
of conventional H-ZSM-5 for the loading of Ru nanoparticles
significantly decreased the selectivities to CH4 and C2–C4 and
increased that to C5–C11 hydrocarbons (Figure 6 a). The selectiv-
ity also depended on the concentration of NaOH used for the
Table 3. Average sizes of mesopores and ruthenium nanoparticles for the
Ru/meso-ZSM-5 series of catalysts.
Catalyst[a] Size of mesopores Mean size of Ru [nm]
[nm] from TEM from Ru dispersion[b]
Ru/H-ZSM-5 – 6.5 6.9
Ru/meso-ZSM-5-0.1 m 3.8 7.2 5.7
Ru/meso-ZSM-5-0.3 m 4.2 7.0 7.3
Ru/meso-ZSM-5-0.5 m 5.2 6.6 6.3
Ru/meso-ZSM-5-1.0 m 6.1 7.0 5.7
Ru/meso-ZSM-5-1.5 m 7.2 7.1 6.3
[a] Ru loading was 3.0 wt %; the concentration after meso-ZSM-5 denotes
the concentration of NaOH used for the preparation of meso-ZSM-5.
[b] Calculated by using the following equation: mean size of Ru = 1.32/Ru
dispersion, and the Ru dispersion was evaluated by the H2–O2 titration
technique.
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lar acidities clearly indicates that the presence of mesopores

Figure 6. Catalytic behavior of Ru nanoparticles loaded on meso-ZSM-5 pre-
pared by treating H-ZSM-5 with different concentrations of NaOH.[83] a) Prod-
uct selectivity; b) CO conversion and Ciso/Cn. Reaction conditions: T = 533 K,
P = 2.0 MPa, H2/CO = 1.0, W = 0.50 g, F = 20 mL min1.
preparation of meso-ZSM-5. At an appropriate con-
centration of NaOH (0.5 or 1.0 m), the selectivity of
CH4 decreased to about 5 %. At the same time, the
C5–C11 selectivity increased to about 80 %, which was
markedly higher than that expected from the ASF
distribution (maximum  45 %). CO conversion also
increased when meso-ZSM-5 was used instead of H-
ZSM-5, probably owing to enhanced mass transport
favors the selective formation of C5–C11 hydrocarbons
(Table 4).[83] A further comparison of catalysts with the same
size of mesopores but different acidities reveals that Ru/meso-
ZSM-5, which has a medium acidity, exhibits a better C5–C11 se-
lectivity. When Na-ZSM-5, with only weak Lewis acidity, is used
as the support, a higher selectivity of heavier (C12 + ) hydrocar-
bons (27 %) and a lower Ciso/Cn ratio (0.8) are obtained; this in-
dicates that hydrocracking and isomerization cannot occur effi-
ciently over this catalyst. On the other hand, over other cata-
lysts displayed in Table 4, the C12 + selectivity was lower than
1 % and the Ciso/Cn was higher than 2.0.
To confirm the hydrocracking reaction over the Ru/meso-
ZSM-5 catalyst, which only possessed medium acidity, we have
performed hydrocracking of n-hexadecane, which is a model
of heavier hydrocarbons, over the catalysts listed in Table 4
under reaction conditions similar to those used for FT synthe-
sis.[83] The results show that, except for Ru/Na-ZSM-5, which ex-
hibits a lower n-hexadecane conversion because of its weaker
acidity, the other catalysts displayed in Table 4 are all very effi-
cient for the hydrocracking reaction. Furthermore, catalysts
with larger mesopores and medium acidity favor selective hy-
drocracking to produce C5–C11 hydrocarbons.
These results clearly demonstrate that the control of the sec-
ondary hydrocracking reactions can significantly change the
product selectivity of a bifunctional FT catalyst. The hierarchical
porous structure and suitable acidity of the mesoporous zeo-
Table 4. Catalytic behavior of ruthenium nanoparticles loaded on meso-ZSM-5 sam-
ples with different mesopore sizes and acidities for CO hydrogenation and for n-hexa-
decane hydrocracking.
Catalyst[a] Mesopore Conv. Selectivity [%]
(acidity) [%] C1–C4 C5–C11 C12 +
I) hydrogenation of CO [b]

(Figure 6 b). The Ciso/Cn ratio was maintained at ap- Ru/Na-ZSM-5 none (weak) 25 21 52 27
proximately 2.5–2.7 (Figure 6 b)—a higher value to Ru/H-ZSM-5 none (strong) 25 52 47 0.7
ensure the quality of gasoline under NaOH concen- Ru/meso-ZSM-5-0.1 m 3.8 nm 27 30 69 0.7
(medium)
trations of  1.0 m. Ru/H-meso-ZSM-5-0.1 m 3.8 nm 33 41 59 0
The effects of mesoporosity and the acidity of (strong)
meso-ZSM-5 on the catalytic behavior are discussed Ru/meso-ZSM-5-0.5 m 5.0 nm 30 21 79 0.5
in more detail. Na + ions have been exchanged into (medium)
Ru/H-meso-ZSM-5-0.5 m 5.0 nm 26 30 70 0
the cationic sites in the meso-ZSM-5 samples during (strong)
NaOH treatment, leading to the decreased acidity. II) hydrocracking of n-hexadecane[c]
The ion exchange of Na + in meso-ZSM-5 samples Ru/Na-ZSM-5 none (weak) 37 44 55 1.2
with NH4 + followed by drying and calcination (the Ru/H-ZSM-5 none (strong) 99 64 36 0.1
Ru/meso-ZSM-5-0.1 m 3.8 nm 95 38 61 2.3
obtained samples are denoted as H-meso-ZSM-5) (medium)
could recover or partially recover the strong Brønsted Ru/H-meso-ZSM-5-0.1 m 3.8 nm > 99 45 54 0
acidity, as evidenced by NH3 temperature-pro- (strong)
grammed desorption (TPD) and pyridine-adsorbed Ru/meso-ZSM-5-0.5 m 5.0 nm > 99 36 64 0
(medium)
FTIR studies.[83] Further studies also suggest that acid Ru/H-meso-ZSM-5-0.5 m 5.0 nm > 99 39 61 0.3
sites with medium strength exist over meso-ZSM-5 or (strong)
meso-beta with mainly Na + at the ion-exchanging
[a] Ru loading was 3.0 wt %; the concentration after meso-ZSM-5 denotes the concen-
position, and these acid sites may stem from the Al tration of NaOH used for the preparation of meso-ZSM-5. [b] Reaction conditions for
species moving outside the framework during the al- CO hydrogenation: T = 533 K, P = 2 MPa, H2/CO = 1.0, F = 20 mL min1, W = 0.50 g.
kaline treatment.[83, 84] A comparison of Ru/meso-ZSM- [c] Reaction conditions for n-hexadecane hydrocracking: T = 533 K, P(H2) = 2 MPa, F =
20 mL min1, feed of n-hexadecane = 0.010–0.045 mL min1, W = 0.50 g.
5 catalysts with different sizes of mesopores but simi-

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lite contribute to enhancing the C5–C11 selectivity in the hydro-
cracking of primary hydrocarbons formed on Ru nanoparticles,
and thus, result in highly selective bifunctional FT catalysts for
the production of gasoline-range hydrocarbons.
Similar results have also been obtained for mesoporous
beta-supported Ru catalysts.[84] A Ru/meso-beta catalyst con-
taining Ru nanoparticles with a mean size of 7.1 nm loaded on
a meso-beta-0.15 m sample provided a C5–C11 selectivity of
77 % and a Ciso/Cn ratio of 2.7. The use of H-meso-beta-0.15 m
with a stronger acidity as the support for Ru nanoparticles
(mean Ru diameter = 7.2 nm) resulted in a slightly lower C5–C11
selectivity (67 %), but the Ciso/Cn ratio increased to about 3.5.[84]
Recently, two other groups also studied mesoporous zeolite-
supported cobalt nanoparticles for FT synthesis.[85–88] Rangel
and co-workers investigated the catalytic performance of
a meso-beta-supported cobalt catalyst.[85] Compared with Co/
beta, the CO conversion was slightly higher over Co/meso-
beta. The selectivity to CH4 became slightly lower (22–23.6 %)
and that to C6 + became slightly higher (44 %–57.8 %) over the
Co/meso-beta catalyst.
Sartipi et al. performed detailed studies on mesoporous
ZSM-5-supported Co (Co loading = 10 wt %) catalysts for FT
synthesis.[86–88] They prepared meso-H-ZSM-5 samples by post-
treating ZSM-5 with either NaOH or TPAOH. The treatment
with TPAOH, a mild base, caused mild desilication in ZSM-5,
leading to the generation of mesoporosity with pores of 4–
8 nm, whereas treatment with NaOH under the same condi-
tions caused severe desilication, generating larger mesopores
with wider distributions (15–32 nm).[86] CO conversion was
higher over Co/meso-H-ZSM-5, in particular over that prepared
by TPAOH treatment, than that over Co/H-ZSM-5, and deactiva-
tion was alleviated over the former catalyst.[86, 87] The introduc-
tion of mesoporosity into H-ZSM-5 can provide suitable meso-
porous surfaces to disperse Co nanoparticles efficiently and to
create Co sites in close vicinity to acid sites. The mean size of
Co nanoparticles decreased from 13–14 nm over Co/H-ZSM-5
to 7–8 nm over Co/meso-H-ZSM-5-ZSM-5.[87] Cobalt particles
were primarily inhomogeneously distributed on the external
surfaces of H-ZSM-5, whereas they were homogeneously dis-
persed on meso-H-ZSM-5 and some of the cobalt particles
were located inside the mesopores. These homogeneously dis-
persed cobalt particles might lead to higher CO conversion
and improved stability for the Co/H-meso-ZSM-5 catalyst.
Concerning the product selectivity, similar to the phenomen-
on observed for the supported Ru catalysts,[83] the use of
meso-H-ZSM-5 to replace H-ZSM-5 as the support for Co parti-
cles decreased the selectivity to CH4 and increased that to C5–
C11 hydrocarbons, although the degrees of changes were not
so significant relative to those of Ru-based catalysts.[86, 87] The
selectivity to CH4 decreased from 21 % for Co/H-ZSM-5 to 18 %
for Co/meso-H-ZSM-5 and that to C5–C11 hydrocarbons in-
creased from 50 to 58 % at the same time under the following
reaction conditions: T = 513 K, P = 1.5 MPa, H2/CO = 2.[87] The
selectivity improvement over the Co/meso-H-ZSM-5 catalyst
could be attributed to enhanced diffusion of both reactants
and products. The enhanced diffusion of products could avoid
the over-exposure of hydrocarbon products to strong acid
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www.chemsuschem.org
sites and suppress over-cracking. On the other hand, the en-
hanced diffusion of reactants may keep the local H2/CO ratio
at the catalyst particle closer to that in bulk syngas and avoid
a higher local H2/CO ratio.[86]
Sartipi et al. further compared three kinds of hierarchical
zeolites, namely, meso-H-ZSM-5, delaminated MWW (ITQ-2),
and meso-H-USY, as supports for cobalt catalysts (Co content =
20 wt %) for FT synthesis.[88] SiO2 was also used as a reference.
The CO conversion activities for Co/meso-H-USY and Co/meso-
H-ZSM-5 were similar and higher than those for Co/ITQ-2 and
Co/SiO2. This could be explained by the difference in cobalt
dispersions in these catalysts. In other words, the first two cat-
alysts consisted of smaller cobalt nanoparticles with higher dis-
persions. Co/SiO2 provided a high selectivity (  50 %) to C21 +
hydrocarbons at 513 K and 1.5 MPa (H2/CO = 1). As expected,
the production of C21 + hydrocarbons was significantly sup-
pressed over zeolite-based catalysts owing to secondary hydro-
cracking reactions. The C21 + selectivity decreased to 12 % over
Co/meso-H-USY and < 5 % over the Co/meso-H-ZSM-5 and Co/
ITQ-2 catalysts. The C5–C11 selectivity was the highest (  55 %)
over the Co/meso-H-ZSM-5 catalyst, whereas the C5–C11 selec-
tivities over Co/ITQ-2 and Co/meso-H-USY were about 40 %.
Characterization results suggested that meso-H-USY exhibit-
ed a lower density of acid sites and its acidity was also weaker
than the other two zeolites. On the other hand, meso-H-ZSM-5
had the strongest acidity. These results suggest that, in addi-
tion to the mesoporous structure described above, the acid
density and acid strength of the mesoporous zeolites are also
essential factors to tune the product selectivities for FT
synthesis.
3.3. CNTs with acid functional groups and other solid-acid-
based bifunctional catalysts
The product selectivity of FT synthesis can be regulated by
tuning the secondary reactions over bifunctional catalysts.
Thus, the following question may arise: can we obtain mainly
C10–C20, the diesel-range hydrocarbons, by using another type
of solid-acid material as the support? To answer this question,
we have examined the catalytic performances of ruthenium
nanoparticles loaded on several types of supports. We found
that the use of CNTs as the support could provide an outstand-
ing selectivity to C10–C20 hydrocarbons (Figure 7).[89] The C10–C20
selectivity of 60 % is considerably higher than that expected
from the ASF distribution (maximum:  35 %). Compared with
the conventional SiO2 support, the use of CNTs as a support
for Ru nanoparticles significantly decreased the selectivity to
heavier hydrocarbons (C21 + ). The C21 + selectivity was also
markedly suppressed when using H-form zeolites (H-Y, H-mor-
denite, H-beta, and H-ZSM-5) as the supports because of the
secondary hydrocracking reaction on the acid sites, as de-
scribed above. These H-form zeolite-based catalysts showed
higher selectivity to C5–C11 hydrocarbons. The selectivity to
light (C1–C4) hydrocarbons was also higher over these zeolite-
based catalysts. On the other hand, the selectivities to undesir-
able CH4 (8.3 %) and lighter hydrocarbons (C2–C4 : 9.1 %) were
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MINIREVIEWS
Figure 7. Catalytic behavior of Ru nanoparticles loaded on several kinds of
supports for FT synthesis.[89] a) CO conversion; b) product selectivity. Reac-
tion conditions: T = 533 K, P = 2.0 MPa, H2/CO = 1.0, W = 0.50 g,
F = 20 mL min1.
not significantly enhanced when CNTs were used as the sup-
port.
The pretreatment of CNTs with concentrated HNO3 is crucial
for obtaining higher C10–C20 selectivity. CNTs after HNO3 pre-
treatment were used to load Ru by using an impregnation
method. The Ru catalyst loaded on CNTs without HNO3 pre-
treatment provided very high selectivities to CH4 and C2–C4 hy-
drocarbons, possibly because of the effect of remaining Ni,
which was used as a catalyst for the synthesis of CNTs. Induc-
tively coupled plasma (ICP) measurements confirmed that no
Ni remained in the CNTs when HNO3 with concentrations of
37–68 wt % was used for pretreatment. However, the product
selectivities depended on the concentration of HNO3 used for
CNT pretreatment (Figure 8). A higher concentration of HNO3
led to a higher C10–C20 selectivity. The mean sizes of Ru nano-
particles over these catalysts were almost the same (6.2–
6.4 nm), as confirmed by TEM measurements. The NH3-TPD
studies suggested that pretreatment with concentrated HNO3
led to the generation of acid sites on the CNT surfaces. The
acidities may correspond to the oxygen-containing functional
groups generated on the surfaces of CNTs after pretreatment
with HNO3. A small fraction of acid sites with medium strength
was also observed over the CNTs pretreated with concentrated
HNO3 (68 wt %).[89] These sites might be related to the oxygen-
ated groups on the defective sites of CNTs generated by con-
centrated HNO3.[90] Some acid sites still remained after loading
of the ruthenium nanoparticles.[89] These observations indicate
that the acid groups on CNTs generated by HNO3 pretreatment
may catalyze the very mild hydrocracking of heavier hydrocar-
bons, selectively producing C10–C20 hydrocarbons.
Moreover, H2-TPD studies suggested that the Ru/CNT and
Ru/zeolite catalysts possessed higher concentrations of ad-
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
Figure 8. Catalytic performances of Ru nanoparticles loaded on CNTs pre-
treated by different concentrations of HNO3.[89] a) CO conversion. b) Product
selectivity. Reaction conditions: T = 533 K, P = 2.0 MPa, H2/CO = 1.0,
W = 0.50 g, F = 20 mL min1.
sorbed hydrogen species.[89] It is known that the unique prop-
erties of CNTs in H2 adsorption and spillover may improve the
catalytic performances of CNT-based catalysts for hydrogena-
tion reactions.[90, 91] As these catalysts with higher surface con-
centrations of adsorbed hydrogen species show lower C21 + se-
lectivities, it is reasonable to speculate that the spillover H spe-
cies on the surfaces of these catalysts may enhance the hydro-
cracking of C21 + hydrocarbons.
In addition to the acidity, the size of Ru nanoparticles also
exerts influences on the activity and selectivity of the Ru/CNT
catalysts. To understand the effect of Ru particle size, the Ru/
CNT catalysts with mean sizes of Ru particles ranging from 2.3
to 9.2 nm were prepared.[41, 89] TEM measurements revealed
that Ru nanoparticles were mostly located outside the CNTs in
these catalysts. It was confirmed that the mean size of Ru par-
ticles did not undergo significant changes after FT reactions.
The catalytic results for these catalysts at a short contact time
(W/F = 0.15 s g mL1), during which CO conversions were lower
than 8 %, have been analyzed to obtain the intrinsic rates of
CO conversion.[41] The TOF, that is, the moles of CO converted
per second per mole of surface Ru, increased significantly from
about 0.05 to  0.2 s1 as the mean size of Ru particles in-
creased from 2.3 to 6.3 nm, and a further increase in the mean
size of Ru only slightly changed the TOF (Figure 9).[41] The C5 +
selectivity gradually increased from about 70 to 80 %, whereas
the CH4 and C2–C4 selectivities gradually decreased as the
mean size of the Ru particles increased from 2.3 to 9.2 nm. The
selectivity to C10–C20 hydrocarbons also increased slightly with
the mean size of Ru particles. Compared with that at a longer
contact time (W/F = 1.5 s g mL1), the C10–C20 selectivity at
a short contact time (W/F = 0.15 s g mL1) is significantly lower
because of the formation of C21 + hydrocarbons. The increase
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CHEMSUSCHEM
MINIREVIEWS
Figure 9. Catalytic behavior of Ru/CNT with different mean sizes of Ru at
a shorter contact time.[41] a) TOF for CO conversion; b) product selectivity.
Reaction conditions: T = 533 K, P = 2.0 MPa, H2/CO = 1.0, W = 0.050 g,
F = 20 mL min1.
in the contact time decreased the selectivity to C21 + and in-
creased that to C10–C20 hydrocarbons. This observation cannot
be explained by the effect of water because it has been report-
ed that a higher pressure of H2O formed at a longer contact
time may favor the formation of heavier hydrocarbons over
Ru-based catalysts.[92] This supports the occurrence of the mild
hydrocracking of C21 + hydrocarbons as a secondary reaction
over Ru/CNT catalysts.
In addition to zeolites and CNTs with acid functional groups
described above, a few other types of solid-acid materials have
also been used for the construction of bifunctional FT catalysts.
For examples, Li and co-workers found that the incorporation
of aluminum into the framework of SBA-16, which is a mesopo-
rous silica with a cage-like structure, enhanced the acidity and
changed the product selectivity of the supported cobalt cata-
lysts.[93] The selectivity to C5–C12 increased to about 60 % over
the Co/Al-SBA-16 (Co content = 15 wt %) catalyst with a Si/Al
ratio of 10, whereas it was < 40 % over Co/SBA-16 under the
following reaction conditions: T = 493 K, P = 1.0 MPa, H2/CO =
2. At the same time, the selectivity to C13 + hydrocarbons de-
creased from about 40 % for the Co/SBA-16 catalyst to about
15 % for the Co/Al-SBA-16 catalyst. The CO conversion de-
creased from 40 to 27 % and the ratio of olefins to n-paraffins
increased from 0.19 to 0.77. The Ciso/Cn ratio increased slightly
from 0.05 to 0.14. Compared with SiO2, the use a porous mont-
morillonite heterostructure (PCH) as the support for Co nano-
particles (Co content = 20 wt %) can also provide higher selec-
tivity to C5–C12 and lower selectivity to C21 + owing to the acidi-
ty of the PCH material.[94]
 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.chemsuschem.org
4. Summary and Outlook
The transformation of non-petroleum carbon resources, such
as methane (natural gas, shale gas, and biogas), coal, and bio-
mass, through synthesis gas is one of the most practicable
routes for the sustainable production of liquid fuels. FT synthe-
sis is a key reaction in this route. Selectivity control is one of
the biggest challenges in FT synthesis. Many recent studies
have contributed to understanding the key factors that deter-
mine the catalytic behavior of a FT catalyst, particularly the CO
conversion activity and selectivity to C5 + hydrocarbons. Efforts
have been made to increase the C5 + selectivity by preparing
catalysts with well-defined active phases, with new supports,
or by optimizing interactions between the promoter and the
active phase. Particular progress has been achieved for Fe-
based catalysts. Several strategies have been proposed to pre-
pare catalysts with higher fractions of c-Fe5C2 species or even
with sole c-Fe5C2 nanoparticles, which are different from con-
ventional Fe-based catalysts containing mixtures of Fe3O4, met-
allic Fe, and Fe carbide species under reaction conditions.
These new well-defined c-Fe5C2-based catalysts exhibit excel-
lent C5 + selectivity in the absence of any promoters.
We have demonstrated that bifunctional catalysts capable of
catalyzing both CO hydrogenation to heavier hydrocarbons
and hydrocracking/isomerization of the heavier hydrocarbons
are very promising for the production of middle-distillate
liquid fuels. The use of an acid zeolite in combination with
a conventional FT catalyst or a FT-active metal could catalyze
the production of gasoline-range (C5–C11) hydrocarbons with
a high Ciso/Cn ratio. In addition to conventional hybrid catalysts,
which are typically physical mixtures of a FT catalyst and zeo-
lite, several types of new zeolite-based bifunctional catalysts
have been developed. First, the preparation of core–shell-struc-
tured catalysts with a FT catalyst as the core and a zeolite as
the shell enhanced the efficiency of secondary reactions, and
thus, increased the C5–C11 selectivity and Ciso/Cn ratio. A few
recent studies also suggested that the presence of a zeolite
shell might have modified the core catalyst and contributed
further to improving the product selectivity. For example, the
presence of an H-ZSM-5 shell can increase the fraction of c-
Fe5C2 in the core catalyst (R-Fe) and decrease the CH4 and C2–
C4 selectivities of the bifunctional catalyst.[66] Second, the direct
loading of an active FT metal onto a zeolite is a simple way to
prepare a bifunctional catalyst, but the active metal particles
located on the external surface of zeolites are poorly dispersed
and a larger part of the acid sites inside the long micropores
cannot be used effectively. Diffusion limitation inside the mi-
cropores can also cause high selectivities to undesirable CH4
and C2–C4 hydrocarbons. The utilization of mesoporous zeolites
can overcome the disadvantages of zeolites. The use of a meso-
porous zeolite instead of a microporous zeolite significantly in-
creases the selectivity to C5–C11 hydrocarbons and decreases
those to CH4 and C2–C4 hydrocarbons. The C5–C11 selectivity
over the mesoporous zeolite-supported Ru or Co catalyst can
be significantly higher than the maximum value (  45 %) ex-
pected from ASF distribution. A recent study indicated that the
use of mesoporous zeolite was probably the best approach to
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CHEMSUSCHEM
MINIREVIEWS
construct the bifunctional catalysts.[60] In addition to zeolite-
based bifunctional catalysts, Ru nanoparticles loaded on CNTs
containing acidic functional groups generated by HNO3 pre-
treatment have shown unique performances in the selective
formation of C10–C20 hydrocarbons. Both the spillover hydro-
gen species and the acidic functional groups on CNTs have
been proposed to contribute to the mild hydrocracking of
heavier hydrocarbons.
In short, control of the secondary hydrocracking reactions
by using new solid-acid materials with tailored porosity and
acidity is a very useful strategy to tune the product selectivity
of FT synthesis. By using this strategy, excellent selectivities to
C5–C11 (  80 %) and C10–C20 (  60 %) hydrocarbons have been
achieved over mesoporous ZSM-5- and CNT-supported Ru cat-
alysts. Future studies are needed to further improve the selec-
tivity to liquid fuels under industrially relevant conditions. The
catalyst cost should also be considered. In this context, the de-
velopment of more selective and highly stable Fe- or Co-based
bi- or multifunctional catalysts should be future research tar-
gets. Furthermore, the design of core–shell-structured bimetal-
lic active phases with highly active and selective metals in the
shell and less expensive metals in the core (e.g., Fe@Co and
Fe@Ru) is also a useful strategy. New multifunctional catalytic
systems composed of this type of active phase and solid-acid
materials will make interesting targets.
Acknowledgements
We gratefully acknowledge financial support from the National
Basic Research Program of China (nos. 2013CB933102 and
2010CB732303), the National Natural Science Foundation of
China (nos. 21173174, 21161130522, 21033006, and 20923004),
and the Program for Changjiang Scholars and Innovative Re-
search Team in University (no. IRT1036).
Keywords: carbon nanotubes · heterogeneous catalysis ·
hydrocarbons · transition metals · zeolites
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Received: August 1, 2013
Published online on && &&, 0000
ChemSusChem 0000, 00, 1 – 15 &14&
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MINIREVIEWS
Split personality: Bifunctional catalysts Q. Zhang, K. Cheng, J. Kang, W. Deng,
containing both active metal (metal car- Y. Wang*
bide) nanoparticles for CO hydrogena-
&& – &&
tion and acid sites for hydrocracking/
isomerization are very promising for the Fischer–Tropsch Catalysts for the
selective production of gasoline or Production of Hydrocarbon Fuels with
diesel fuel (see picture). The control of High Selectivity
secondary reactions by using new solid-
acid materials, such as mesoporous zeo-
lites, leads to outstanding product
selectivity.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 0000, 00, 1 – 15 &15&
These are not the final page numbers! ÞÞ