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A review of the catalytic hydrogenation of carbon

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Cite this: Catal. Sci. Technol., 2017,

dioxide into value-added hydrocarbons
7, 4580
Haiyan Yang,†a Chen Zhang,†a Peng Gao, *a Hui Wang,a Xiaopeng Li,a
Liangshu Zhong, a Wei Weiab and Yuhan Sun*ab

Received 12th July 2017,
Accepted 5th September 2017
DOI: 10.1039/c7cy01403a
rsc.li/catalysis
Chemical utilization of CO2 to chemicals and fuels is very attractive because it can not only alleviate global
warming caused by increasing atmospheric CO2 concentration but also offer a solution to replace dwin-
dling fossil fuels. Hydrogen is a high-energy material and can be used as the reagent for CO2 transforma-
tion. Moreover, when hydrogen originates directly from renewable energy, CO2 hydrogenation can also
provide an important approach for dealing with the intermittence of renewable sources by storing energy
in chemicals and fuels. Therefore, much attention has been paid to CO2 hydrogenation to various value-
added hydrocarbons, such as lower olefins, liquefied petroleum gas, gasoline, aromatics and so on. The fo-
cus of this perspective article is on the indirect and direct routes for production of hydrocarbons from CO2
hydrogenation and recent developments in catalyst design, catalytic performance and reaction mechanism.
In addition, a brief overview on CO2 hydrogenation to methanol is given, which is a critical process in the
indirect route involving conversion of CO2 into methanol and subsequent transformation into hydrocar-
bons. We also provide an overview of the challenges in and opportunities for future research associated
with CO2 hydrogenation to value-added hydrocarbons.

1. Introduction tractive because it can not only alleviate global warming

As a nontoxic, renewable and abundant carbon source, chem-
ical utilization of CO2 into value-added products is very at-
a
CAS Key Lab of Low-Carbon Conversion Science and Engineering, Shanghai Ad-
vanced Research Institute, Chinese Academy of Sciences, No. 99 Haike Road,
Zhangjiang Hi-Tech Park, Shanghai 201210, China. E-mail: gaopeng@sari.ac.cn,
sunyh@sari.ac.cn; Fax: +86 021 20608066; Tel: +86 021 20608002
b
School of Physical Science and Technology, ShanghaiTech University, Shanghai
201210, China
† These authors contributed equally to this work.
caused by increasing atmospheric CO2 concentration but also
offer a solution to replace dwindling fossil fuels.1–3 However,
CO2 is well known to be a very stable molecule (ΔfG298K =
−396 kJ mol−1), and the biggest obstacle for establishing in-
dustrial processes based on CO2 as a raw material is its low
energy level.4,5 Thus, a large energy input is required to trans-
form CO2. Hydrogen is a high-energy material and can be
used as the reagent for CO2 transformation. Moreover, re-
placement of part of the fossil fuel consumption by renew-
able energy sources (solar, wind, biomass and so on) is a

Haiyan Yang obtained her mas-
ter's degree in chemical engineer-
ing in 2016 from the CAS Key
Laboratory of Low-Carbon Con-
version Science and Engineering,
Shanghai Advanced Research In-
stitute, Chinese Academy of Sci-
ences. She is interested in de-
signing and synthesizing novel
nanocatalysts for catalytic con-
version of carbon dioxide or syn-
gas into value-added products.
Haiyan Yang
and well-defined heterogeneous catalysts.
Peng Gao was born in May 1987
in China. Dr Gao received his
PhD in chemical engineering and
technology in 2014 from the Uni-
versity of Chinese Academy of
Sciences. Currently, he is a pro-
fessor at the CAS Key Lab of
Low-Carbon Conversion Science
and Engineering, Shanghai Ad-
vanced Research Institute, Chi-
nese Academy of Sciences. His
research interests include CO2
Peng Gao conversion to chemicals and
fuels, Fischer–Tropsch synthesis

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Catalysis Science & Technology
central strategy for resource and energy efficiency. When hydrogen
originates directly from renewable energy, CO2 hydrogenation can
also provide an important approach for dealing with the intermit-
tence of renewable sources by storing energy in chemicals and
fuels. Therefore, much attention has been paid to CO2 hydrogena-
tion to various value-added hydrocarbons, such as liquefied petro-
leum gas (LPG, C30–C40), lower olefins (ethylene, propylene and
butylene, C2=–C4=), gasoline (C5–C11), aromatics and so on.
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There are different possible routes to produce hydrocar-
bons from CO2 hydrogenation (Fig. 1). Two parallel reactions,
the synthesis of methanol (eqn (1)) and reverse water-gas
shift (eqn (2), RWGS), are typically present in the CO2 hydro-
genation process. The hydrocarbons could be directly pro-
duced from syngas (CO + H2) based on Fischer–Tropsch syn-
thesis (FTS) or indirectly via industrial methanol synthesis
and then converting methanol to a range of hydrocarbons
using the methanol-to-hydrocarbon (MTH) process, including
the methanol-to-olefin (MTO), methanol-to-propene (MTP),
Hui Wang obtained her BS de-
gree in chemical engineering
from Hunan Normal University.
She obtained her PhD degree in
physical chemistry from the In-
stitute of Coal Chemistry, CAS,
in 2006. She has been an assis-
tant professor in Shanghai Uni-
versity from 2006 to 2013, and
was promoted to professor in
Shanghai Advanced Research In-
stitute, CAS, in 2013. Her main
Hui Wang scientific interests are conversion
of carbon dioxide and syngas.
She was nominated for the “Outstanding Youth Contribution”
award in the 15th International Congress on Carbon Dioxide Uti-
lization (2017, China).
Wei Wei is a professor, institute
direct assistant and director of
the Center for Greenhouse Gas
and Environmental Engineering
at Shanghai Advanced Research
Institute, CAS. His main re-
search focus includes CO2 ac-
counting, capture, utilization
and storage, green chemistry
and environmental catalysis.
Prof Wei received the “Outstand-
ing Young Scientist” award in
Wei Wei the 13th International Congress
on Catalysis (2004, France) and
was nominated for the “Outstanding Youth Contribution” award
in the 10th International Congress on Carbon Dioxide Utilization
(2009, China).
This journal is © The Royal Society of Chemistry 2017
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Fig. 1 Details of the different possible routes to synthesize value-
added hydrocarbons (olefin, LPG, gasoline, aromatics and so on) from
CO2 hydrogenation.
and methanol-to-gasoline (MTG) processes. It had also been
reported that aromatic or lower paraffin (LPG) hydrocarbons
were synthesized from methanol or dimethyl ether (DME).6–8
In addition, various hydrocarbons could be indirectly pro-
duced from CO2 hydrogenation via CO2 hydrogenation to
methanol and MTH reactions. Recently, the direct route of
converting CO2 into hydrocarbons has been developed based
on FTS (CO2-FTS), via a two-step process with an initial re-
duction of CO2 to CO via the RWGS reaction followed by the
conversion of CO to hydrocarbons via FTS. The catalyst used
should be active in both RWGS and FTS reactions. It is also
possible to combine the catalysts for methanol and the zeo-
lites for MTH to have a direct one-step formation of hydrocar-
bons from CO2 hydrogenation.
CO2 + 3H2 ⇌ CH3OH + H2O ΔrH298K = − 49.5 kJ mol−1 (1)
CO2 + H2 ⇌ CO + H2O ΔrH298K = 41.2 kJ mol−1 (2)
Many excellent reviews have discussed the conversion of
CO2 as well as the catalytic hydrogenation of CO2.3,4,9–17 How-
ever, most of the reviews mainly focus on the general aspects
of CO2 applications and CO2 hydrogenation to various C1
Yuhan Sun received his PhD
from the Institute of Coal Chem-
istry of the Chinese Academy of
Sciences in 1989. He is now the
vice president of the preparatory
committee of Shanghai Advanced
Research Institute, CAS. Prof
Sun's main research interests in-
clude C1 chemistry on coal/natu-
ral gas-based synfuels and
chemicals, catalysis and engi-
neering for CO2 utilization, ap-
Yuhan Sun plication of nano-materials in
green chemistry and optical
films, etc. Prof Sun is also on the board of the Chemistry Society
of China and that of the Particle Society of China.
Catal. Sci. Technol., 2017, 7, 4580–4598 | 4581

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feedstocks (for example, methane, methanol, carbon monox-
ide, formic acid, etc.). Advances have been made in the past
decade, especially on the conversion of CO2 into C1
chemicals via heterogeneous catalysts. Due to the extreme in-
ertness of CO2 and a high C–C coupling barrier, it is still a
challenge to synthesize C2+ hydrocarbons (hydrocarbons with
more than two carbons) from CO2. Recently, more and more
researchers have focused on this area. Therefore, this crucial
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review tries to discuss the various approaches ultimately lead-
ing to production of hydrocarbons from CO2 hydrogenation
and provide a current understanding of catalyst design, cata-
lytic performance and reaction mechanism over various types
of heterogeneous catalysts with an emphasis on practical as-
pects. Additionally, a brief overview on the recent develop-
ments in CO2 hydrogenation to methanol is given because
methanol can be subsequently transformed into hydrocar-
bons over various zeolites using the MTH process in the indi-
rect route.
2. Indirect conversion of CO2 into
hydrocarbons
The two main indirect routes towards CO2 hydrogenation
into hydrocarbons involve (i) conversion of CO2 into metha-
nol and subsequent transformation into hydrocarbons (ole-
fins, LPG, gasoline, aromatics and so on) in a separate stage
and (ii) conversion of CO2 into CO via RWGS; hydrocarbons
are then synthesized using the modified FTS process based
on two-stage reactors. Generally, the catalysts active in metha-
nol synthesis or FTS reactions are also active in RWGS.3,15
Thus, this step is integrated in these processes and will be
discussed in related sections.
2.1. CO2 hydrogenation to methanol
Beginning in the 1920s, the production of methanol from
syngas on an industrial scale was introduced by BASF in Ger-
many. The Cu/ZnO/Al2O3 catalyst system is employed in the
industrial synthesis of methanol at approximately 6 MPa and
250 °C, and has been widely studied for over 40 years in in-
dustry.18 As an alternative feedstock, CO2 replaced by CO is
considered as an effective way for CO2 utilization in metha-
nol production.19 Different from methanol synthesis from
syngas, the formation of water vapor is inevitable in direct
CO2 hydrogenation, which inhibits the reaction strongly and
leads to serious catalyst deactivation.20,21 In addition, other
by-products such as CO and hydrocarbons are formed during
the hydrogenation of CO2. Therefore, an efficient catalyst is
needed to improve catalytic stability and avoid the formation
of undesired by-products for methanol synthesis, which re-
quires continuous optimization of the catalyst system or de-
velopment of a new catalyst system.
A wide variety of heterogeneous catalysts have been evalu-
ated in the conversion of CO2 and H2 into methanol. Gener-
ally, methanol catalysts can be classified into three catego-
ries: (i) Cu-based catalysts, which are mainly modified
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methanol catalysts for CO hydrogenation, and Cu species
constitute the main active component of the catalytic system;
(ii) catalysts with noble metals such as Pd and Pt as active
components; (iii) oxygen-deficient materials used as active
sites. The reaction mechanism of this kind of catalyst is dif-
ferent from those of the two kinds of catalytic systems men-
tioned above, for example, the In2O3/ZrO2 catalytic system.
2.1.1. Cu-based catalysts. In view of the significantly lower
selectivity to methanol, catalytic activity and stability, copper
alone is not efficient in the synthesis of methanol from
CO2.22,23 An appropriate support not only affects the forma-
tion and stabilization of the active phase of the catalysts but
also is capable of tuning the interactions between the major
component and the promoter. Whether as a catalyst for CO2
hydrogenation to methanol in industry or as a model catalyst
for theoretical research, Cu/ZnO and further modified cata-
lysts remain the focus of current research.24,25 The main rea-
sons for this are that ZnO can improve the dispersion and
stabilization of copper, and the lattice oxygen vacancies and
an electron pair in ZnO are active for methanol synthesis.26
More recently, the formation and properties of Cu–ZnOx
active sites have been discussed in more depth. Lunkenbein
et al. utilized a thermal stimulus using an electron beam to
transform the industrial Cu/ZnO catalyst structure into Cu
NPs surrounded by metastable “graphitic-like” ZnO after re-
ductive activation.27 The GL ZnO is kinetically stabilized by
interacting with the defective and curved Cu surface under-
neath. Defects could play a key role in the stability of the
ZnO overlayer and may lead to the presence of some ZnOx
species acting as a cocatalyst in methanol synthesis, illustrat-
ing that the migration of Zn to the Cu surface is closely re-
lated to the formation of a stable Cu–ZnO interface and Cu–
ZnOx active sites in the process of reduction and evaluation.
Similar conclusions are emerging in Tisseraud's latest re-
search, wherein he designed a core–shell Cu@ZnOx catalyst
that allows maximizing the Cu–ZnO contacts and favors a
large diffusion of Zn into Cu to cover the metallic Cu surface
with the oxygen-deficient CuxZn(1−x)Oy active phase for metha-
nol (Fig. 2).28 Sun et al. also found that a Cu–Zn active nano-
alloy layer was formed on the Cu–ZnO nanoclusters, which
reduced the activation energy of CO adsorption. The surface
alloy layer and Cu–ZnO sites play a cooperative catalytic role
in dimethyl ether synthesis via syngas.29 The experimental
and geometrical approach also proved that the methanol for-
mation rate is a linear function of the Zn that has migrated
into Cu. In summary, it is widely accepted that the active site
for methanol synthesis is a Cu–Zn surface alloy and a
CuxZn(1−x)Oy active phase formed by atomic diffusion of Zn
from ZnO to the metallic Cu surface.
To further increase the activity and stability of the Cu/ZnO
catalyst, different modifiers are used as stabilizers and pro-
moters. Toyir et al. found that the promoting effect of Ga2O3
was strongly associated with Ga2O3 particle size.30 Small
Ga2O3 particles favor the formation of an intermediate state
of copper between Cu0 and Cu2+, probably Cu+. Li et al. pro-
posed that the introduction of Ga3+ into the Cu/ZnO catalyst
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Fig. 2 General scheme for methanol synthesis over Cu/ZnO-based
catalysts.28
precursor facilitated the deep reduction of ZnO to Zn0 by the
establishment of an electronic heterojunction of ZnO–
MGa2O4 (M = Zn or Cu).31 The reduced Zn0 when in contact
with Cu nanoparticles can form CuZn bimetallic species.
Therefore, doping with Ga3+ promoted the formation of a
CuZn bimetallic active phase at the interface to enhance the
activity and selectivity to methanol. Martin et al. discovered
that the introduction of small amounts of a noble metal like
Au significantly promoted the electronic stabilization of Cu0
and stabilized the interface between Cu and ZnO.32
Because of the high stability under reducing or oxidizing
atmospheres, zirconia has also been deemed as an excellent
promoter or support for the methanol synthesis catalyst.33,34
ZrO2 added on Cu-based catalysts could increase the surface
area and improve Cu particle dispersion. Moreover, the crys-
tal types of Zr influence the performance of the catalyst. Sam-
son et al. presented that ZrO2 is of great importance in the
catalytic performance of Cu/ZrO2.35 The results showed that
only the oxygen vacancy in t-ZrO2 was conducive to the pro-
Fig. 3 Methanol formation rate as a function of t-ZrO2 content.35
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motion of copper atoms into the ZrO2 lattice and formation
of stable Cu+ (Fig. 3). Additionally, the incorporation of Cu+
or Cu2+ ions into the ZrO2 network compensated for the neg-
ative charge of vacancies and further contributed to the stabi-
lization of the t-ZrO2. The Cu–ZrO2 interface site containing
oxygen vacancies for methanol formation derived from this
enhanced Cu/t-ZrO2 interaction would improve the yield and
selectivity of methanol.
2.1.2. Noble metal catalysts. In the noble metal series, Pd-
based catalysts are the most commonly used owing to their
considerable activity and selectivity for hydrogenation of CO2
to methanol. Bahruji et al. investigated structure activity–rela-
tionships for CO2 hydrogenation on Pd/ZnO catalysts pre-
pared by different methods. The results proved that the PdZn
alloy formed during the reaction or high temperature pre-
reduction greatly reduced CO production by RWGS reaction
and became the active site for methanol synthesis (Fig. 4).36
In addition, the smaller PdZn alloy particle size, less surface
metallic Pd content and higher surface area of PdZn alloy
were beneficial to increase the methanol selectivity. Hartadi
et al. first explored the effect of total pressure and influence
of CO on Au/ZnO catalysts.37 Compared with industrial Cu/
ZnO/Al2O3 catalysts, high temperature and high pressure were
beneficial to the increase in methanol yield, inhibiting the
relative activity of the RWGS reaction and improving the se-
lectivity to methanol and conversion of CO2. Increasing the
CO concentration resulted in the decreasing of methanol for-
mation rate, and the rate of CO2 hydrogenation (in CO2/H2
mixtures) on Au/ZnO was considerably higher than that of
CO hydrogenation (in CO/H2 mixtures). Therefore, CO2 is ‘di-
rectly’ hydrogenated to CH3OH and not converted to CO in
the first step, followed by hydrogenation of adsorbed CO.
Frauenheim and Xiao investigated CO2 hydrogenation on
AgIJ111)/ZnOIJ0001 _) surfaces via first principles calculations.38
The calculation results showed that the addition of
ZnOIJ0001 _) substrate to Ag(111) made the Ag's d-band states
exceed the Fermi level. The binding ability between the
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Fig. 4 CO2 conversion and CH3OH and CO selectivity as a function of reaction temperature (150–300 °C) on 5% Pd ZnO catalysts prepared by
the sol immobilisation method. The catalyst was reduced at (a) 150 °C to form Pd/ZnO and at (b) 400 °C to form the PdZn/ZnO catalyst.36

supported Ag(111) monolayer and the CO2 molecule signifi-
cantly improved, and CO2 reduction in the subsequent hydro-
genation process was optimized as well. Therefore, the strong
metal–support interaction between Ag and ZnO is of para-
mount importance to increase the catalytic activity. It was
proved that Ga can also act as an active component for meth-
anol synthesis from CO2 hydrogenation. Studt et al. and
Sharafutdinov et al. presented a detailed study of the rela-
tionship between active components and product distribu-
tion in intermetallic Ni–Ga catalysts.39,40 Their results show
that the Ni5Ga3 phase is favorable for methane generation
and increasing methanol selectivity. However, whether the
CH4 stems from the presence of the Ni-rich Ni3Ga phase or
small pure Ni particles or it is produced on the adjacent Ni–
Ni sites on the surface of Ni5Ga3 still remains to be clarified.
2.1.3. Other catalytic systems. Apart from the traditional
Cu-based catalysts and noble metal catalysts, many CO2 hy-
drogenation catalysts based on new reaction mechanisms
and catalytic structures have been developed in recent years.
Ge et al. investigated methanol synthesis from CO2 hydroge-
nation on the defective In2O3IJ110) surface with surface oxy-
gen vacancies via periodic DFT calculations (Fig. 5).41 The
surprising calculation results show that the methanol forma-
tion mechanism on the D4 surface with the Ov4 oxygen

Fig. 5 Potential energy surfaces for CO2 hydrogenation to methanol on the D4 defective In2O3IJ110) surface.41

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defective site is quite different from that of copper-based cat-
alysts mentioned earlier, and the Ov4 oxygen defective site is
found to be more favorable for CO2 activation and hydroge-
nation. Typically, the Ov4 oxygen defective site on the
In2O3IJ110) surface assists CO2 activation and hydrogenation
and also stabilizes the key intermediates involved in metha-
nol formation. Martin et al. prepared the In2O3/ZrO2 catalyst
and achieved the methanol generation mechanism proposed
by Ge et al. successfully.42 ZrO2 was added to make and stabi-
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lize the most thermodynamically unstable Ov4 oxygen defec-
tive site cycle. The catalysts show excellent methanol selectiv-
ity (∼100%) and stability (1000 h) in the hydrogenation of
CO2 to methanol (Fig. 6). This strongly contrasts with the
conventional Cu/ZnO/Al2O3 catalyst, which is unselective and
experiences rapid deactivation.
2.2. Methanol to hydrocarbons
The MTH process over acid zeolite catalysts, first discovered
by Mobil Research Laboratories in 1976, has been extensively
investigated in recent years.43 Methanol or its dehydration
product dimethyl ether (DME) can be used as a feed to pro-
duce several different classes of hydrocarbons, including
lower olefins, gasoline-range hydrocarbons, branched al-
kanes, and aromatics. The selectivity to any of these classes
of compounds is determined both by the zeolite topology and
the operating conditions used. The key of the MTH process is
to control product selectivity and increase the catalytic stabil-
ity by developing high-performance catalysts and optimizing
reaction conditions. Recently, the catalytic materials, mecha-
nism, active intermediates and deactivation and commercial
projects of MTH have been reviewed in detail.8,44–46 There-
fore, the catalyst and reaction mechanism of MTH are briefly
introduced in the following.
2.2.1. Catalysts. The behaviors of zeolite catalysts are
based on their shape-selectivity, dimensional structure, sta-
bility and acidity properties with the possibility of modifica-
tion under controlled conditions. Literature data have shown
that medium-pore zeolite/microporous materials generate
C5–C11 hydrocarbons, while small-pore molecular sieves yield
Fig. 6 (a) Methanol STY and selectivity for CO2 hydrogenation over bulk In2O3, In2O3/ZrO2 (9 wt% In), and the benchmark Cu/ZnO/Al2O3 catalyst
at various temperatures. (b) Evolution of the methanol STY with time on stream (TOS) over In2O3/ZrO2 and Cu/ZnO/Al2O3.42
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C2–C4 hydrocarbons. A number of attempts were devoted to
selectively synthesizing light olefins from methanol, not only
on medium-pore zeolites but also on small-pore zeolites. A
range of catalysts are employed, especially with respect to
ZSM-5 (MTG directed) and SAPO-34 molecular sieves (MTO
directed). SAPO-34 molecular sieves exhibit great potential to
obtain high selectivity for light olefins owing to their mild
acidity. The preparation conditions, the size and structure of
the pores, and cation exchange as well as the distribution of
acid sites are of mounting importance for the catalytic perfor-
mance for synthesizing methanol to lower olefins.47,48 In
2009, a semi-commercial demonstration unit in Feluy, Bel-
gium, processing up to 10 tonnes per day of methanol feed
was brought on-stream, and in 2011 the construction of a
295 kt per year plant in Nanjing, China, was announced. Re-
searchers at the Dalian Institute of Chemical Physics devel-
oped a similar process using SAPO-34, and a 600 kt per year
(ethene + propene) plant was started in 2010.49
The MTG process is also among the MTH technologies
with industrial interest. Catalysts based on H-ZSM-5 or its
modified analogs were the main materials given preference
by the researchers, with numerous literature studies docu-
mented. In 1985, the MTG process was commercialized in
New Zealand, where Mobil, in a partnership with the New
Zealand government, built a 14 500 bpd plant based on natu-
ral gas converted through synthesis gas into methanol. Issues
related to the role of catalyst topology, acidity properties, re-
action parameters and their effects on catalytic activity, selec-
tivity and catalyst lifetime have been critically covered in the
literature review by Galadima and Muraza.50
2.2.2. Reaction mechanism. Mechanistic studies have been
at the core of MTH research. Several reviews that extensively
cover early research on the mechanism can be found in the
literature.8,46,47,51 Stöcker highlights the milestones of this
development during the past decade before 1990.47 He fo-
cused mainly on the chemistry and mechanism of these reac-
tions, especially the possible mechanistic proposals for the
formation of the first C–C bond. He also briefly summarized
the relevant mechanism, such as the oxonium ylide mecha-
nism, carbine mechanism, carbocationic mechanism, free
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radical mechanism, hydrocarbon pool mechanism and so on.
Among these, the hydrocarbon pool mechanism has been
widely accepted (Fig. 7).8,51–53
2.3. Modified Fischer–Tropsch synthesis
A typical FTS is the catalytic conversion of syngas to a mix-
ture of predominantly linear alkanes and alkenes (eqn (3)
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and (4)), and a wide distribution of hydrocarbons with differ-
ent chain lengths is produced, which can be described by the
Anderson–Schulz–Flory (ASF) model (Fig. 8).20,21,54,55 Lower
olefins (C2=–C4=) – generally referring to ethylene, propylene
and butylene – could be directly produced from syngas, the
so-called FTO or Fischer–Tropsch to olefin process.56 The ASF
model predicts a maximum C2–C4 hydrocarbon fraction of
about 56.7%, including C2=–C4= olefins and C20–C40 paraffins,
and an undesired methane fraction of about 29.2%.56,57
Therefore, iron and cobalt based catalysts, which are of com-
mercial interest in FTS, should be modified in order to mini-
mize the formation of alkanes (especially CH4) and increase
selectivity to C2–C4 olefins. Recently, it was reported that
iron-based Fischer–Tropsch catalysts promoted by sulfur and
sodium exhibited excellent selective formation of lower ole-
fins (61%) at 340 °C, 2 MPa, and H2/CO = 1.58 Zhong et al.
showed that under mild reaction conditions (250 °C, 0.1
MPa, H2/CO = 2), cobalt carbide quadrangular nanoprisms
catalyzed the FTO conversion of syngas with high selectivity
for the production of lower olefins (60.8%) while generating
little methane (5%), which deviated markedly from the classi-
cal ASF distribution.57 They have demonstrated that preferen-
tially exposed {101} and {020} facets play a critical role during
syngas conversion in that they favor olefin production and in-
hibit methane formation (Fig. 9).
Parrafins: nCO + (2n + 1)H2 → CnH2n+2 + nH2O (3)
Olefins: nCO + 2nH2 → CnH2n + nH2O (4)
The high-octane gasoline components (C5–C11), which con-
sist of (predominantly iso-) paraffins, aromatics (predomi-
nantly methyl-substituted), naphthenes, and olefins, can also
be obtained from FTS. Bifunctional FTS catalysts that couple
Co nanoparticles for CO hydrogenation and mesoporous zeo-
Fig. 7 Mechanism of the catalytic conversion of methanol to
hydrocarbons.8
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Fig. 8 Product distribution according to the Anderson–Schulz–Flory
(ASF) model.
lites for hydrocracking/isomerization reactions turned out to
be promising for the direct production of gasoline-range hy-
drocarbons from syngas.60 The selectivity for C5–C11 hydro-
carbons could reach about 70% with a ratio of isoparaffins to
n-paraffins of approximately 2.3 over this catalyst. This C5–
C11 selectivity is far beyond the maximum value (around
45%) expected from the ASF distribution. Additionally, Plana-
Pallejà et al. investigated the effect of acidic properties on
ZSM-5 zeolites to evaluate changes in product selectivity dur-
ing FTS over a physical mixture of the iron-based FTS catalyst
and zeolites with different Si/Al ratios.61 Higher acidity (lower
Si/Al ratio) in the pristine zeolite was responsible for cracking
of heavy hydrocarbons and the formation of heavier aromatic
products, while a higher Si/Al ratio resulted in a higher selec-
tivity towards gasoline-range products (isoparaffins and
olefins).
3. Direct conversion of CO2 into
hydrocarbons
CO2 can be also hydrogenated to hydrocarbons by a direct
route. Compared with the indirect route, the direct route is
more economical and environmentally benign. The direct
CO2 hydrogenation (CO2-FTS) is often described as the com-
bination of the reduction of CO2 to CO via RWGS reaction
and subsequent hydrogenation of CO to hydrocarbons via
FTS. More recently, the direct and highly selective conversion
of CO2 into value-added hydrocarbons can be achieved by
combining the catalysts for CO2 hydrogenation to methanol
with the zeolites for MTH.
3.1. CO2-based Fischer–Tropsch synthesis via CO
intermediates
A highly attractive route of direct CO2 hydrogenation has
been postulated to be a two-step process (RWGS and FTS)
over the same catalyst.62–65 Thus, the CO2-FTS reaction
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Fig. 9 TEM characterization of the CoMn catalysts at the steady stage of reaction. (a and b) Low-resolution TEM images; (c and e) high-resolution
images of Co2C nanoprisms with exposed facets of (101), (−101) and (020); (d) distance (length) of the lattice fringes; (f) the Co2C nanoprism model
with four rectangular faces and two rhomboid faces.59
requires the presence of a bifunctional catalyst that combines
RWGS with Fischer–Tropsch chain growth activity. Compared
with CO hydrogenation, the degree of hydrogenation of
surface-adsorbed intermediates in CO2-based FTS is higher
due to the slower adsorption rate of CO2, leading to lower
CO2 conversion and more ready formation of a fairly large
fraction of CH4. Consequently, the main challenge is associ-
ated with the development of catalysts not only with high ac-
tivity but also with high selectivity to value-added hydrocar-
bon products, such as short-chain olefins and long-chain
hydrocarbons.
Catalysts used with CO2 hydrogenation have been based
on catalysts for CO hydrogenation so far, and catalyst compo-
nent is analogous to that for FTS. Different kinds of FTS cata-
lysts with different catalytic selectivities have been developed
for the selective production of various hydrocarbons. Cata-
lysts such as Fe, Co, Ru and Ni supported on SiO2, γ-Al2O3,
TiO2, and carbon nanomaterials have been comprehensively
investigated in the CO2 conversion to hydrocarbons.62,66
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Among them, iron-based and cobalt-based catalysts are
widely used in the CO2-FTS reaction owing to significant frac-
tions of C2+ hydrocarbons produced on them.
3.1.1. Iron-based catalysts. Since the products derived
from FTS are endowed with a tremendous environmental
value, CO2-FTS with iron catalysts has been addressed in a
number of investigations. Iron catalysts have showed great
promise in converting CO to value-added hydrocarbons and
proved to be the preferred catalyst candidate for the CO2-FTS
process, attributed to their excellent ability to catalyze both
RWGS and FTS processes as well as the highly olefinic nature
of the yield products.67 The range of conversion levels and se-
lectivity of production can be explained by the different prep-
aration techniques, different promoters, supports and experi-
mental conditions.
Promoters. Despite the fact that iron-based catalysts are
able to transform CO2 with a much higher affinity for long-
chain hydrocarbons, it should be pointed out that the
unpromoted catalysts still present a high selectivity to non-
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desired products such as CH4 and may deactivate rapidly.65,67
Therefore, promoters urgently need to fine-tune and optimize
the product distribution and enhance the stability of cata-
lysts. A variety of promoters incorporated onto iron-catalysts
for hydrocarbon formation from CO2 hydrogenation have
been reported.68–74
It is well known that CO2 conversion is favored by alkaline
addition. It has been reported that potassium, as a promoter
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for iron-based catalysts, influenced significantly the catalyst's
overall performance.65,68,75–77 The incorporation of potassium
not only increases the CO2 conversion but also leads to a signif-
icant shift in olefin production as well as longer chain hydro-
carbons. Visconti et al. investigated the effect of K-loading on
the activity and the selectivity of the adopted iron catalyst.78
They noticed that high K-loadings made possible the chain
growth process and the formation of primary olefins. It is de-
duced that the remarkable catalytic performance properties in
the presence of K are attributable to the increase in the ability
of CO2 chemisorption while impeding H2 adsorption, which in-
creases the probability of C–C bond formation.68 Wang et al.
investigated the effects of modification by alkali metals like Li,
Na, K, Cs on the performance of CO2 hydrogenation; they ob-
served that the K-modified Fe/ZrO2 catalyst with an appropriate
K content (0.5–1.0 wt%) outperformed other alkali metals in
the synthesis of C2–C4.79 In a word, potassium is an effective
promoter for the iron catalyst in the enhancement of selectivity
to olefins and long-chain hydrocarbons.
The addition of sodium is essential to tailor the olefin pro-
duction, as commented before,73,80,81 since it can obviously
promote the surface basicity of the catalysts, which is favored
for olefin production. In addition, increasing the Na content
can greatly improve the carbonization degrees of the iron cat-
alysts.73,81 Recently, Wei et al. also found that the combina-
tion of a Na–Fe3O4 CO2-FTS catalyst with an HZSM-5 zeolite
into a multifunctional catalyst can shift product distribution
towards high-octane gasoline-range isoparaffins and aro-
matics.82 The selectivity for gasoline-range (C5–C11) hydrocar-
bons among all hydrocarbons was up to 78% at a CO2 conver-
sion of 22%, while methane selectivity was 4% under the
Fig. 10 Reaction scheme for CO2 hydrogenation to gasoline-range hydrocarbons.82
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reaction conditions of 320 °C, 30 bar, H2/CO2 = 1, and 4000
ml h−1 gcat−1. The Na–Fe3O4/HZSM-5 multifunctional catalyst
enables RWGS over Fe3O4 sites, α-olefin synthesis over Fe5C2
sites, and oligomerization/aromatization/isomerization over
zeolite acid sites (Fig. 10).
Copper has also been widely used to modify iron-cata-
lysts.70,77,83,84 Herranz et al. indicated that addition of Cu
made reducibility of the iron oxide more facile, leading to a
significant increment in CO2 conversion without altering
product selectivity.84 The reason for the effects may be that
the introduction of Cu is able to provide active sites for
dissociatively adsorbing hydrogen once reduced to its metal-
lic form. Recently, Choi et al. reported a new catalyst, which
was prepared by reduction of delafossite CuFeO2 followed by
in situ carburization to its active phase (Hägg carbide).85 The
catalytic performances of various catalysts derived from
Fe2O3, CuFe2O4, and CuFeO2-12 precursors are provided in
Fig. 11. It was obvious that the catalyst derived from CuFeO2-
12 not only produced C5+ hydrocarbons with a high selectivity
of 65% but also greatly restrained the formation of CH4 to 2–
3%, which reflected a record-breaking selectivity for CO2
hydrogenation.
Incorporation of manganese into iron-catalysts is able to
suppress the formation of CH4 while increasing the ratio of
olefin/paraffin during CO2 hydrogenation.69,71 It was reported
that Mn promoted catalyst reduction, dispersion and carburi-
zation of the precursor as well as increased the catalyst's sur-
face basicity. However, the positive effect of Mn is valid only
in a limited concentration range due to the possible blockage
of active iron sites at high Mn loadings.71 Therefore, the
amount of Mn employed on catalysts should be appropriate.
The positive role of ceria is connected with its good low-
temperature RWGS activity. The size of CeO2 domains and
the order of catalyst impregnation with ceria influence the ac-
tivity and selectivity towards C2–C5 olefins.86,87 For the Fe/
Mn/K catalysts, promotion by Ce results in an about 22% in-
crease in CO2 conversion and 5% increase in olefin on ac-
count of a promotion of RWGS activity compared to the cata-
lysts without Ce.86
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Fig. 11 (a) Fe time yield (FTY) against time on stream for catalysts derived from Fe2O3, CuFe2O4, and CuFeO2-12 precursors (reaction conditions:
300 °C, 10 bar, 1800 ml h−1 gcat−1, H2/CO2 = 3). (b) Product selectivity on CO-free basis.85

Some other promoters, like Cr and Zn, have also been ap- constitution and structure of the iron catalyst changes from
plied to the iron catalysts. It was reported that promotion of the initial synthesis run, Riedel et al. concluded that the pro-
Fe with Cr and Zn increased the conversion of CO2.76 More- cess of FTS was composed of episodes with distinct kinetic
over, Zn could increase the surface and improve the basicity regimes, and these episodes were closely associated with the
of catalysts as well as offer high selectivity for C2–C4 catalyst transformations in structure and composition, as
alkenes.70,88 shown in Fig. 12.92 The iron phases of the reduced catalyst
Supports. Supporting materials play crucial roles in CO2 before reaction mainly consist of α-Fe and Fe3O4. As time
hydrogenation to hydrocarbons. Iron-based catalysts dis- goes by, the Fe3O4 and Fe2O3 phases are consumed and a
persed on various supports, such as γ-Al2O3, SiO2, TiO2, ZrO2, new amorphous, probably oxidic iron phase emerges, which
and MOFs have been examined extensively.75,76,89 Among the appears to be active for the RWGS reaction. FTS activity starts
supports used in iron catalysts, many researchers considered with the formation of Fe5C2, which they considered is respon-
that γ-Al2O3 performs best (followed by SiO2 and TiO2) be- sible for the formation of olefins and long-chain hydrocar-
cause of the strong metal–support interaction formed with bons. Beyond that, the investigation of the correlation be-
the active component, and it could avoid sintering of active tween the rate of FTS and the percentage of Fe carbide also
particles during reaction.75,76 However, others hold different indicates that iron carbide is the active phase for CO2-FTS.93
views; their studies revealed that ZrO2 provided the highest 3.1.2. Cobalt-based catalysts. Compared to the iron-based
selectivity and yielded lower olefins among a range of sup- catalysts, cobalt catalysts represent the optimal choice for the
ports (SiO2, Al2O3, TiO2, ZrO2, and CNT).79 In addition, a de- synthesis of heavier hydrocarbons from syngas and tend to
tailed study of supports revealed that promoted Fe supported have a much higher chain growth potential owing to their
on TiO2 tended to produce less undesired CH4 than Al2O3- ability to be substantially inactive in the water gas-shift
supported catalysts. Recently, some other supports have also
been introduced, Hu et al. reported that Fe-supported K-
OMS-2 nanocatalysts had the highest selectivity to light
olefins.90
Active sites. In spite of the progress in CO2-based FTS over
iron catalysts, the nature of the active sites of Fe-based cata-
lysts is still in dispute. Either the magnetite phase or the ox-
idic phase of iron is essential for the RWGS reaction, while
the carbide form of iron is responsible for chain propagation.
To assess the nature of iron phases, density functional theory
calculations were applied to Fe-based catalysts by Hakim and
co-workers, and their results have demonstrated that the
Fe3O4IJ111) surface was very capable of activating CO2.91 The
same results were obtained by Wei et al. They observed that
CO2 was initially reduced to CO by H2 via RWGS on Fe3O4
sites followed by a subsequent hydrogenation of CO to
α-olefins via FTS on Fe5C2 sites, as commented before.82
Since iron carbides are visualized as the “true Fischer– Fig. 12 Iron-phase composition as a function of time during
Tropsch catalyst”, much effort has been devoted to identify hydrocarbon synthesis on Fe/Al/Cu catalyst. Reaction conditions: 250
the iron carbides during CO2-FTS.76,79,92,93 By studying the °C, 1 MPa, 1800 ml(NTP) h−1 g(Fe)−1, H2/CO2 = 3.92

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(WGS) reaction. However, under a CO2/H2 regime, cobalt cata-
lysts, behaving like a methanation catalyst rather than
performing as a FT catalyst, do not follow the usual FT chain
growth mechanism at all, and the product distribution
changes significantly.67,94,95 As shown in Fig. 13, it clearly ap-
pears that the hydrogenation of CO2 over Co/Al2O3 catalysts
does not lead to a typical ASF distribution, differently from
what happens in the case of CO hydrogenation.96 Most at-
tempts yield CH4 as the main product.97,98 Akin et al. ob-
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served that products of CO2 hydrogenation contained 70
mol% CH4 over Co/Al2O3 catalyst,97 which is analogous to the
literature precedent.99
Therefore, tremendous attempts are employed to reduce
the production of CH4.95,98,99 Donner et al. found that the
shift from CH4 toward longer chain hydrocarbons can be
achieved by reducing the feed gas ratio of H2/CO2, as one can
see from Fig. 14.95 They regarded that the behavior was possi-
bly associated with the two different active sites (a distinct
break in the graph of Fig. 14 indicates two different growth
sites resulting in α1 and α2) for CH4 and C2–C4 products
presenting on the catalyst; the decreasing ratio of H2/CO2 led
to a lowering of the catalyst's methanation potential, con-
versely improving the length of hydrocarbons from (a) 0.41 to
(c) 0.54.
Promoters. It has been shown that the addition of noble
metals to Co-based catalysts would be beneficial in view of re-
ducing the selectivity towards CH4.98,100 It was observed that
the CH4 selectivity decreased with C5+ hydrocarbons, dou-
bling upon the introduction of ruthenium. In the presence of
platinum, a large decrease in CH4 selectivity can be achieved,
as described by Willauer et al.95 Additionally, group VIII
metals have also been used as dopants. Copper present in co-
balt catalysts has been found to be very active in the WGS
without synthesizing significant quantities of CH4.99
In addition, literature data show that the incorporation of
alkali metals has a beneficial effect upon the catalysis; that
Fig. 13 Hydrocarbon experimental ASF plots reported in terms of
selectivity during CO and CO2 hydrogenation over Co/Al2O3 catalysts
under the same conditions.96
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Fig. 14 ASF distribution over the Co–Pt/Al2O3 catalyst at different H2/
CO2 ratios: (a) 3 : 1, (b) 2 : 1, and (c) 1 : 1. The dashed line is the fitted
plot, while the solid line is the actual data obtained from the catalyst,
with the data points highlighted by an ×.95
is, adding alkali metals on cobalt can increase the selectivity
to long-chain hydrocarbons and decrease selectivity to
CH4.73,98,99,101 The variation of alkali metal was investigated
by Owen and co-authors.98 They observed that the catalyst be-
ing promoted by sodium or potassium gives greater selectiv-
ity to C5+ hydrocarbons and lower selectivity to CH4 with no
significant decrease in CO2 conversion. They attributed the
improved C5+ hydrocarbon selectivity upon employing the al-
kali to an enhancement in surface-to-molecule charge trans-
fer, and the binding strength of CO increased while that of
H2 reduced, thus resulting in an increased chain growth
probability.83 As commented before, Gnanamani et al. pro-
posed that Na in association with cobalt carbide plays a piv-
otal role during the RWGS reaction, which is likely a prereq-
uisite for the conversion of CO2 to alcohols, and they
highlighted a role played by Na in stabilizing the carbide
phase.73 Similar phenomena can also be observed in the CO-
based FTS by Zhong et al.; they suggest that Na enhances the
formation of Co2C, which exhibits high selectivity towards
the formation of lower olefins whereas low selectivity towards
CH4 production.59
Supports. Supports have significant roles in the direct
conversion of CO2 into hydrocarbons over Co-based catalysts.
Most of the research in the field is focused on the use of SiO2
and Al2O3.73,95–98 However, some reports have shown that
other supports could outperform SiO2 and Al2O3.66 Owen
et al. investigated the effect of the supports (including SiO2,
CeO2, TiO2, ZrO2, Al2O3, ZSM-5, MgO) on Co–Na–Mo catalysts
for the conversion of CO2 to hydrocarbons, and the catalytic
performances of Co–Na–Mo deposited on different supports
are given in Table 1.66 It appears that catalysts supported on
SiO2 and ZSM-5 present the highest CO2 conversion values,
and catalysts utilizing ZrO2, Al2O3, TiO2, and CeO2 as support
obtained a similar CO2 conversion. However, the hydrocar-
bon selectivity differs, which decreases in the following order:
ZrO2, Al2O3, TiO2, CeO2. Introducing the MgO as support
yields a sole CO without hydrocarbons being formed. These
results demonstrate the importance of the support not only
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Table 1 Catalytic activity of Co–Na–Mo supported on a range of oxides66

CO2 CO HC Hydrocarbon distribution

Catalyst conversion selectivity selectivity
Entry support (%) (%) (%) C1 C2= C2 C3= C3 C4 C5 α
1 SiO2 30.0 21.5 78.5 57.1 0.0 9.3 0.1 11.8 9.3 12.3 0.48
2 SiO2a 15.6 59.0 41.0 42.1 0.0 10.7 1.7 14.1 12.7 18.7 0.52
3 CeO2 15.1 70.2 29.8 22.1 0.92 12.8 9.8 9.1 14.1 31.2 0.59
4 TiO2 13.5 66.7 33.3 23.1 0.77 9.9 9.2 7.0 13.7 24.2 0.60
5 Al2O3 15.4 57.3 42.7 29.3 0.0 12.3 4.1 14.1 13.9 27.1 0.57
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6 MgO 8.7 100 — 0.0 0.0 0.0 0.0 0.0 0.0 0.0 NA
7 ZrO2 14.4 16.7 83.3 26.8 0.0 14.8 12.9 8.2 14.9 22.4 0.52
8 ZSM-5 29.1 20.6 79.4 95.7 0.0 3.0 0.0 0.9 0.2 0.2 0.17

Reaction conditions: 200 °C, 0.1 MPa, H2/CO2 = 3 : 1 and 8 SCCM total flow, WHSV: 0.35 h−1. a WHSV: 1.73 h−1.

on the cobalt crystallite size but also the critical effect of the
metal–support interaction on the product distribution.
Active sites. In spite of the progress in the selectivity to
heavier hydrocarbons (especially C5+ hydrocarbons) by the
promotion of alkali promoters like Na and K, reports on the
state and nature of the active phase of cobalt that is
responsible for the observed increase in C5+ hydrocarbons
are scarce. In order to shed further light on the nature of the
active phase of cobalt during catalysis, Gnanamani et al.
investigated the influence of pretreatment conditions of
cobalt on the performance of CO2 hydrogenation over 1% Na/
20% Co–SiO2 catalyst.73 Three different activation conditions,
such as H2, CO/H2 and CO, were employed to control the
chemical nature of cobalt phases. Fig. 15 shows the product
selectivity described versus the method of activation. As one
can see, the metallic form of cobalt is obtained and the
products are primarily CH4 and lower hydrocarbons (C2–C4)
in the case of H2 pretreated catalysts, while pretreating with
pure H2 or CO/H2 at 250 °C yields a fraction of CoO, which
suppresses the hydrogenation activity of cobalt to some
degree; as a result, selectivity to CH4 declines. Moreover, after
CO activation, CoO and cobalt carbide phases form and
produce significantly less CH4, and the selectivity for
alcohols increases to 73.2%. Their studies reveal that the
partially carburized form of cobalt is responsible for the high
alcohol selectivity (73.2%) observed.
However, the above-mentioned Co-based catalysts are pri-
marily prepared by traditional coprecipitation, impregnation,
or physical mixing methods and contain multiple compo-
nents including various promoters as well as supports. Thus,
they exhibit large uncertainties on the spatial arrangements
of active sites. More recently, Xie et al. prepared a well-
defined CeO2–Pt@mSiO2–Co core–shell catalyst (a schematic
of the synthetic process and TEM images of each step are
presented in Fig. 16) for the targeted synthesis of C2–C4 hydro-
carbons from CO2 hydrogenation via a two-step tandem reac-
tion; that is, the RWGS reaction is conducted over a CeO2/Pt
interface and the formed CO subsequently reacts with H2
through the FTS process on the Co/mSiO2 interface.102 A selec-
tivity of 60% toward C2–C4 hydrocarbons was obtained, which
gives impetus to the rational design multifunctional catalysts
with high performance for tandem conversions.
3.1.3. Mixed Fe–Co catalysts. Mixed Fe–Co catalysts are
also active for CO2 hydrogenation.80,103,104 Satthawong et al.
claimed that the addition of a small amount of Co with Fe
led to a dramatic improvement in selectivity to C2+ hydrocar-
bons.103 Gnanamani et al. has also shown that Fe–Co bime-
tallic catalysts outperform monometallic catalysts (Fe or Co)
for CO2 hydrogenation for the production of higher C2+ hy-
drocarbons,80 and the catalyst containing a 50 : 50 Co : Fe
composition was found to be the optimum for the production
of higher hydrocarbons. Although K-promoted or Na-
promoted Fe–Co catalysts exhibit an increased selectivity to
higher hydrocarbons, the selectivity to CH4 is still too high.
3.1.4. Reaction mechanisms (CO-FT vs. CO2-FT). A great
deal of studies have been conducted on catalytic hydrogena-
tion of CO2, for cobalt and iron catalysts; a significant in-
crease in formation of CH4 (the most thermodynamically fa-
vored hydrocarbon product) was noted upon switching the
reactants from syngas to CO2/H2. A comparative study of FTS
with CO/H2 and CO2/H2 over Co-based catalysts has been car-
ried out by many researchers.75,94,96,105 With respect to CO or
CO2 hydrogenation, Zhang et al. found that the catalytic ac-
tivities obtained were similar while the selectivities of the two
processes were extremely different.94 For CO hydrogenation,
normal FTS product distributions were observed with an α of
Fig. 15 Effect of catalyst activation conditions of 1% Na–20% Co/SiO2
on CO2 hydrogenation selectivity (reaction conditions: 220 °C, 18.9
bar, 3000 ml h−1 gcat−1, H2/CO2 = 3 : 1).73

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Fig. 16 Synthesis and characterization of the CeO2–Pt@mSiO2–Co tandem catalyst. (a) Schematic of the synthetic process. TEM images of each
step: (b and c) CeO2 nanoparticles, (d and e) overgrowth of Pt nanoparticles on CeO2, (f and g) silica shell coating on CeO2–Pt composite
nanoparticles, (h and i) deposition of Co nanoparticles on CeO2–Pt@mSiO2, and (j) scaled up preparation of CeO2–Pt@mSiO2–Co nanoparticles.
One-pot synthesis can yield 300 mg of catalyst.102
about 0.80; when it comes to the hydrogenation of CO2, with
CH4 largely dominating the product distribution, similar re-
sults were reported by Riedel et al.75 As a consequence, it is
obvious that hydrogenation of CO2 does not lead to a typical
ASF distribution, which differs from what takes place for CO
hydrogenation. Visconti et al. ascribed the change in the yield
products to two main reasons.96,105 On the one hand, the dif-
ferent adsorption strengths of CO2 and CO on the catalyst
surface, that is, the different H/C ratios on the surface of the
catalyst within the two processes, cause the decrease in chain
propagation ability. They consider that during the hydrogena-
tion of CO2, a higher H/C ratio is obtained due to the weak
CO2 adsorption on the surface. This favors the hydrogenation
of surface-adsorbed intermediates, leading to the formation
of CH4 and a decrease of chain growth ability. On the other
hand, the lower CO partial pressure may motivate the second-
ary reactions of olefin in CO2 hydrogenation, thus yielding
more saturated hydrocarbons.
To throw light upon the process of CO2 hydrogenation,
previous work has been reported in the mechanism of cata-
lytic hydrogenation of CO2 to hydrocarbons.94 Saeidi et al.
presented a reaction mechanism for hydrogenation of CO2 to
hydrocarbon over iron catalysts as shown in Fig. 17.106 It can
be seen from Fig. 17 that CO2 is initially reduced by ironIJII)
followed by H radical absorption on the catalyst surface. OH,
formic acid and CO are formed when the residual H attacked
carbonyl C. The Fe–CH2 radical, considered as a C–C propa-
gation species, is then formed in the same way.106
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3.2. Bifunctional catalysis via methanol intermediates
Direct conversion of CO2 into hydrocarbons can also be
achieved via methanol-mediated reactions. In the methanol-
mediated approach, hydrocarbon synthesis was conducted
over a hybrid catalyst composed of a methanol synthesis cata-
lyst and a zeolite catalyst (MTH) from CO2 hydrogenation,
which is advantageous to produce desirable hydrocarbons. In
general, CO2 and H2 react over the Cu-based catalysts to syn-
thesize methanol, which is subsequently transformed into hy-
drocarbons over a zeolite catalyst. The distribution of hydro-
carbons over hybrid catalysts greatly depended on the zeolite,
which affected both the CO2 hydrogenation rate and the de-
sired hydrocarbon yields. Up to now, considerable efforts have
been made to explore effective ways of the direct synthesis of
hydrocarbons from CO2 and H2 via methanol intermediates.
3.2.1. Synthesis of olefins. Lower olefins are basic carbon-
based building blocks that are widely used in the chemical in-
dustry and are traditionally produced through thermal or cata-
lytic cracking of a range of hydrocarbon feed stocks, such as
naphtha, gas oil, condensates and light alkanes.57,58,107 Selec-
tive synthesis of lower olefins from a CO2 + H2 mixture by one-
pass conversion via methanol synthesis was investigated by
Inui et al.108 The authors considered that for the selective syn-
thesis of olefin, a weakly acidic and narrow pore microporous
crystalline catalyst such as SAPO-34 was required. A bifunc-
tional catalyst containing In2O3 and SAPO-34 could realize the
direct production of lower olefins from CO2 hydrogenation
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Fig. 17 Reaction mechanisms of CO2 to hydrocarbons.106
with excellent selectivity and high activity. The selectivity of C2–
C4 olefin reached up to around 76.9% with a much lower CH4
selectivity of 4.4% and CO2 conversion was above 34%.109
3.2.2. Synthesis of LPG. LPG is a good substitute for fuel
in spark ignition engines and is used as a replacement for
aerosol propellants and refrigerants. Therefore, direct synthe-
sis of LPG from CO2 hydrogenation is a desirable route for
converting the most abundant carbon resource to highly valu-
able products.110,111 Jeon et al. investigated the catalytic per-
formance of a range of hybrid catalysts consisting of metha-
nol synthesis catalysts (for example, Cu/ZnO/ZrO2 and Cu/
ZnO/Al2O3) and zeolites (for example, SAPO-5, SAPO-44 and
HZSM-5) for the direct synthesis of hydrocarbons from CO2
hydrogenation via methanol.110 They concluded that propane
was the main product on the hybrid catalysts with SAPO-44,
while on the hybrid catalysts with SAPO-5 isobutene was the
predominant product due to the different acidity and pore
size between those zeolites. The selective synthesis of LPG
over the hybrid catalysts composed of a Zr-modified Cu–Zn–
Al methanol catalyst with a Pd-modified zeolite (Pd-β) was
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also studied by Li et al.111 Their results revealed that the hy-
brid catalyst was active and stable for LPG synthesis even at
low temperature (260 °C), and the conversion of CO2 and the
yield of hydrocarbons can reach up to 25.2% and 13.3%, re-
spectively, while the selectivity of LPG was as high as 75%
with limited CH4 formed (only 1%), indicating that the
proper use of a methanol catalyst with zeolite made it a pos-
sibility to obtain the specified hydrocarbons from CO2. Park
et al. proposed that the yield of hydrocarbons was mainly de-
termined by the amount of acid sites of zeolite according to
their studies.112 Furthermore, they found that the main prod-
uct was C3 or C4 hydrocarbons in the case of the hybrid cata-
lyst consisting of Cu/ZnO/ZrO2 and SAPO zeolite, and they
suggested that the mechanism operating for SAPO was the
carbon pool mechanism.
3.2.3. Synthesis of gasoline. Gasoline is a very important
transportation fuel widely used around the world. Systems
which combine methanol synthesis catalysts and zeolites
which can produce enhanced yields of C2+ hydrocarbons by
combining methanol synthesis and the MTG reaction. Aimed
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Fig. 18 Molecular level mechanism for CO2 hydrogenation into hydrocarbons over an In2O3/HZSM-5 bifunctional catalyst.109

at obtaining a gaseous fuel from CO2 hydrogenation, a cata- two components (mortar mixing) was further shortened,
lyst system involving a methanol synthesis catalyst (Pd–Na- which leads to a severe deactivation with very low C5+ hydro-
modified Cu–Cr–Zn oxides) and a typical MTG catalyst (H- carbon selectivity. Moreover, the catalytic performance for
ZSM-5) was adopted, and the selectivity of C2+ hydrocarbons CO2 hydrogenation was also evaluated using pellet catalysts
among the yielded hydrocarbons was up to 71.8% over the with a cylindrical shape (Φ3.0 mm × 3.5 mm) under industri-
above composite catalysts.113 Fujiwara et al. studied the hy- ally relevant conditions. Tail gas recycling, which was com-
drogenation of CO2 over a Cu–Zn–Cr-oxide/zeolite composite monly used in industry for more efficient utilization of the
catalyst system.114 They found that Cu–Zn–Cr/HY exhibited feed, could improve the catalytic performance for CO2 hydro-
the best performance for CO2 hydrogenation with a CO2 con- genation to C5+ hydrocarbons significantly, suggesting a
version and hydrocarbon selectivity of 39.9% and 12%, re- promising prospect for industrial application.
spectively, and the selectivity of C2+ hydrocarbons was as high To selectively synthesize isoalkane, which is considered as
as 95.8% under reaction conditions of 400 °C, 0.5 MPa, H2/ a fuel additive both for improving the octane value of gasoline
CO2 = 3, and 3000 ml h−1 gcat−1. Moreover, it was also con- and for enhancing automobile exhaust, some authors took
firmed that the MTG reaction and the decomposition of meth- the hybrid catalyst composed of Fe–Zn–Zr and HY zeolite as
anol into CO controlled the production of C2+ hydrocarbons.
However, only low yields of hydrocarbons are obtained,
with CO and CH4 being the predominant products over the
above-mentioned catalysts. Ereña et al. found that the syn-
thetic gasoline fraction was higher over the bifunctional cata-
lysts composed of Cr2O3–ZnO and ZSM-5 than other catalysts,
with a selectivity of 36.1 wt% for total hydrocarbons and C5+
selectivity of 53.9%.115 Very recently, an In2O3/HZSM-5 bifunc-
tional catalyst reported by Gao et al. has exhibited excellent
performance for the direct production of gasoline-range hy-
drocarbons from CO2 hydrogenation with high selectivity and
a remarkable stability.109 The C5–C11 selectivity in hydrocar-
bon distribution reached up to 80% with only 1% CH4 under
reaction conditions of 340 °C, 3 MPa, H2/CO2 = 3, and 9000
ml h−1 gcat−1. The oxygen vacancies on In2O3 surfaces activate
CO2 and H2 to form methanol, and C–C coupling subse-
quently occurs inside zeolite pores to produce gasoline-range
hydrocarbons (Fig. 18). The key intermediates involved in
methanol synthesis are more stable on the defective In2O3
surface than those on the Cu surface, which strongly sup-
presses the formation of CO. Consequently, CO selectivity
over In2O3 integrated with the zeolite (<45%) is much lower Fig. 19 Influence of the integration manner of the active components
than that over traditional Cu-based catalysts (>90%) at 340 (In2O3/HZSM-5 mass ratio = 2 : 1) on catalytic behaviours under the
°C. In addition, by moving the two components into a closer same conditions. (a) Dual-bed configuration with In2O3 packed below
HZSM-5 and separated by a layer of quartz sand. (b) HZSM-5 packed
proximity (from Fig. 19a–d), CO selectivity decreased and the
below In2O3 and separated by quartz sand. (c) Stacking of granules
C5+ selectivity was enhanced. However, the number of with In2O3, HZSM-5 and quartz sand particle sizes of 250–380 μm. (d)
strongly acidic sites of the spent catalyst presented in In2O3 and HZSM-5 particles well mixed without quartz sand. (e) In2O3
Fig. 19e decreased markedly when the distance between the and HZSM-5 mixed with an agate mortar.109

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Catalysis Science & Technology
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Scheme 1 Proposed reaction path of isoalkane formation from CO2 +
H2 over Fe–Zn–Zr/HY hybrid catalyst.116
the catalyst for isoalkane synthesis from CO2 hydrogena-
tion.116,117 Ni et al. confirmed that the Fe–Zn–Zr not only acts
as a methanol synthesis catalyst but also benefits isoalkane
formation.116 A reasonable intact route to isoalkanes is pro-
posed according to their results, as shown in Scheme 1. First,
the methanol is formed over the Fe–Zn–Zr catalyst and then
converted to C1 and C4 and further into hydrocarbons includ-
ing i-C4 and i-C5 over HY zeolite. Moreover, the formed C3 can
further react with methanol to obtain i-C4, while i-C5 can be
synthesized from C2 and C3. However, the synergistic effect of
metal oxide and zeolite in the mechanical mixture is very
poor, and the selectivity to isoalkanes is still unsatisfied. To
overcome the above problems, a core–shell catalyst with Fe–
Zn–Zr as the core and a zeolite (HZSM-5, Hbeta and HY) as
the shell was prepared using a simple cladding method devel-
oped by Wang et al. (Fig. 20).118 Compared with the conven-
tional Fe–Zn–Zr/zeolite prepared by mechanical mixing, the
Fe–Zn–Zr@zeolite core–shell catalyst exhibited a significantly
improved confinement effect on the promotion of the direct
synthesis of isoalkanes from CO2, and the selectivity to iso-
alkanes in the yielded hydrocarbons reached up to 81.3%.
4. Conclusions and future
perspectives
The utilization of CO2 as the carbon source for the produc-
tion of hydrocarbons is an effective way to introduce renew-
Fig. 20 Illustration of the Fe–Zn–Zr@zeolite core–shell catalyst preparation by a simple cladding method.118
This journal is © The Royal Society of Chemistry 2017
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able energy in the chemical industry value chain while im-
proving resource efficiency and limiting greenhouse gas
emissions. CO2 can be hydrogenated to hydrocarbons by ei-
ther indirect or direct routes, but in all cases there are nu-
merous technical and economic barriers to overcome, which
will further drive the research and development in the pro-
duction processes including the development of catalysts, re-
actors and related process technology from non-petroleum
feedstocks.
We have analyzed here the status of research in the indi-
rect routes. The catalytic chemistry of the CO2 hydrogenation
to methanol reaction and the subsequent production of ole-
fins, LPG, gasoline and aromatics via MTH as well as RWGS
reaction and value-added hydrogenation are then synthesized
via FTS, or cracking of heavy hydrocarbons produced in the
FT process is well established, even if there is still the need
for development. Also in terms of process development most
of the knowledge necessary is available. Minor technological
barriers to develop these routes are thus present.
As compared with the indirect route, the direct conversion
of CO2 into hydrocarbons would be more economical and en-
ergy-efficient. Various attempts have been made to transform
carbon dioxide into hydrocarbons directly on FT-based cata-
lysts. The use of CO2 via FT reactions should be focused ei-
ther on the selective synthesis of short-chain olefins or on
the synthesis of hydrocarbons to be used as fuels. It is appar-
ent that catalysts play a key role in driving success. Neverthe-
less, the nature of the active sites and interactions among ac-
tive components, promoter and support as well as reaction
mechanisms are still in dispute. There is a need for an im-
proved catalyst incorporating both RWGS activity and chain
growth. Nano-structured, porous, and functional materials
are of paramount importance to these catalytic conversion
processes. With a better understanding of the fundamental
structure–composition–activity relationships of these catalytic
systems, the catalysts can be tuned for better catalytic
performance.
The CO2-FT reaction is essentially a modification of the
FTS, where CO2 is used instead of CO, and thus the distribu-
tion of hydrocarbons is limited by an ASF model. The meth-
odology of reaction coupling has resulted in a significant
breakthrough in the direct synthesis of olefin, LPG and gaso-
line from CO2 hydrogenation using bifunctional catalysts,
which provide an important platform for CO2 conversion into
Catal. Sci. Technol., 2017, 7, 4580–4598 | 4595

Minireview
chemicals and fuels. As stated above, the bifunctional catalyst
separates CO2 activation and C–C coupling onto two types of
active sites with complementary and compatible properties.
During CO2 hydrogenation, CO2 is activated on Cu-based cat-
alysts or an oxide surface with oxygen vacancies and hydroge-
nated to methanol intermediate species, while C–C coupling
is controlled within the pores of zeolite. The activation mech-
anism of CO2, the rule of the formation of reaction interme-
Published on 06 September 2017. Downloaded by University of Winnipeg on 1/23/2019 4:28:10 AM.
diates and C–C precise coupling, the synergy mechanism of
two active sites, as well as the deactivation behavior need to
be further clarified, even if relevant research has been made
recently. With the assistance of numerous in situ characteri-
zation techniques and theories, the design of cost-effective
catalysts will be promoted a great deal. Last but not least, fu-
ture research should certainly emphasize the rational design
of highly active catalysts for direct conversion of CO2 into
value-added hydrocarbons.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (21503260, 21773286), the Minis-
try of Science and Technology of China (2017YFB0602202,
2017YFB0602205), Shanghai Municipal Science and Technol-
ogy Commission, China (15ZR1444500, 16DZ1206900), the
“Frontier Science” program of Shell Global Solutions Interna-
tional B. V. (PT65197), and Science and Technology Innovation
Fund of Shanghai Advanced Research Institute, CAS (172001).
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