Chemistry–Sustainability–Energy–Materials

Accepted Article

Title: Hydrogenation of Carbon Dioxide  to Methanol over  Non-Cu -

based Heterogeneous  Catalysts

Authors: Feng Sha, Zhe Han, Shan Tang, Jijie Wang, and Can Li

This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: ChemSusChem 10.1002/cssc.202002054

Link to VoR: https://doi.org/10.1002/cssc.202002054

01/2020
ChemSusChem 10.1002/cssc.202002054

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Hydrogenation of Carbon Dioxide to Methanol over Non-Cu-based
Heterogeneous Catalysts
Feng Sha,[a, b] Zhe Han,[a, b] Shan Tang,[b] Ji-Jie Wang,*[b] and Can Li*[b]
[a] F. Sha, Z. Han
School of Materials Science and Engineering & National Institute for Advanced Materials, Nankai University, Tianjin, 300350 (P.R. China)
[b] F. Sha, Z. Han, S. Tang, Dr. J.-J. Wang, Prof. C. Li
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023 (P.R. China)
E-mail: jjwang@dicp.ac.cn
canli@dicp.ac.cn

Accepted Manuscript

1
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ChemSusChem
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Abstract: The increasing atmospheric CO2 level makes CO2
reduction an urgent challenge facing the world. Catalytic
transformation of CO2 into chemicals and fuels utilizing renewable
energy is one of the promising approaches toward alleviating CO2
emissions. In particular, the selective hydrogenation of CO2 to
methanol utilizing renewable hydrogen potentially enables large
scale transformation of CO2. The Cu-based catalysts have been
extensively investigated in CO2 hydrogenation. However, it is not
only limited by long-term instability but also displays unsatisfactory
catalytic performance. The supported metal-based catalysts (Pd, Pt,
Au, and Ag) can achieve high methanol selectivity at low
temperatures. The mixed oxide catalysts represented by MaZrOx (Ma
= Zn, Ga, and Cd) solid solution catalysts present high methanol
selectivity and catalytic activity as well as excellent stability. This
review focuses on the recent advances in developing non-Cu-based
heterogeneous catalysts and current understandings of catalyst
design and catalytic performance. First, the thermodynamics of CO2
hydrogenation to methanol is discussed. Then, the progress in
supported metal-based catalysts, bimetallic alloys or intermetallic
compounds catalysts, and mixed oxide catalysts is discussed.
Finally, a summary and a perspective are presented.
1. Introduction
Carbon dioxide (CO2), a greenhouse gas, is closely
associated with the growing fossil energy consumption and the
consequent climate change. Although the advances in science
and technology have led to the increasing proportion of clean
energy, fossil resources such as coal and petroleum are still the
main source of energy supply, which are accompanied by an
enormous CO2 emission to the atmosphere. Continued
economic and population growth further drive the increase in
CO2 emissions. The atmospheric CO2 levels have increased
sharply from the pre-industrial level of 280 ppm to 412 ppm in
2020.[1] Therefore, there is a pressing need to efficiently reduce
both the dependence on fossil resources and CO2 emissions.
It has been proposed that the carbon capture and storage
(CCS) could reduce CO2 emissions via absorption and
adsorption trapping.[2] However, CCS is limited by high cost,
intensive energy requirements for CO2 separation, the
uncertainty of CO2 storage time in sites, and the impact of large
volumes of CO2 on natural systems.[3] Carbon capture, storage,
and utilization (CCSU), by contrast, is getting more and more
attention since it not only alleviates CO2 emissions, but also
utilizes CO2 as an environmentally friendly carbon-resource to
produce value-added chemicals, fuels, and even materials.
CCSU opens a new field in the conversion of “exhaust carbon”
into “working carbon” and has a great significance in sustainable
development.[4] But, a widely accepted opinion is that CO2 is so
thermodynamically stable that it is rarely used to its fullest
potential due to its low chemical potential. Therefore, CO2
conversion requires a high-energy input. To achieve energy-
demanding synthetic protocols using CO2 as the C1 building
block, the specific substrate with high-energy, such as H2, is
needed. More importantly, the hydrogenation reaction has been
considered as a feasible and powerful process among various
chemical conversions of CO2 since it offers a good opportunity
for sustainable development.[5] On the one hand, H2 could be
obtained from photocatalytic water splitting under direct
irradiation of sunlight and water electrolysis via electricity
generated from solar and photovoltaic cells as well as other
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10.1002/cssc.202002054
renewable energy with CO2-neutrality.[6] On the other hand, the
combination of CO2 and H2 can synthesize a variety of
chemicals such as oxygenates (alcohols, carboxylic acid, and
dimethyl ether) and hydrocarbons (olefins, liquid hydrocarbons,
and aromatics).[7]
This challenge still exists in the combined CO2 capture and
utilization. The gas effluents releasing from the most energy-
intensive industrial processes not only contains CO2, but also
accompanies with other components arising from combustion
such as H2O, N2, unreacted O2, dust, sulphur and nitrogen
oxides, which would result in the CO2 hydrogenation catalysts
deactivate rapidly. Thus, CO2 adsorption and purification for the
direct application of CO2 hydrogenation in those streams is
important. Amine scrubbers such as monoethanolamine,
Accepted Manuscript
diethanolamine and methyl diethanolamine as well as amine
blend solutions have been commonly employed industrially for
post-combustion CO2 capture, but the considerable energy
penalty for desorbing CO2 from liquids.[8] Solid sorbents such as
zeolites, carbon-based adsorbents, layered double hydroxides,
and metal-organic frameworks are considered to be good
candidates for CO2 capture owing to their promising adsorption
capacity, CO2 selectivity, stability and regenerability.[9] But these
solid absorbers are limited by the high synthesis cost and limited
adsorbent capacity. Ionic liquids present an advantages of high
CO2 solubility, good thermal stability and tuneable structures,
hence they have also been proposed as promising solvents to
replace the existing amine-based solvents.[10] The another
method of CO2 adsorption and purification is membrane
system.[11] The potential to perform separations at low energy
penalties makes membrane strategies attractive for practical
CO2 removal applications. On the other hand, Debecker et al
highlights the types of formulations of adsorbents, catalysts and
dual functional materials that have been proposed, some basic
process engineering aspects, and the reported performance for
the combined CO2 capture on solid adsorbents and CO2
methanation on metal-based catalysts.[12] Two solids in two
separate units is a first option that will mostly require process
optimization, which allows not only to treat complex gas effluents
but also to perform the methanation under clean conditions. One
unit with two solids constitutes a second option, in which the
catalysts have to exhibit high performance in its normal
operating conditions and withstand the operating conditions that
are applied during capture. One unit and one bifunctional solid is
the use of dual functional materials, bearing both a capture
function and a reduction function. Overall, the capture of CO2 by
adsorption and purification and its subsequent hydrogenation to
chemicals and fuels are promising line of research and
development.
It is worth noting that methanol is an important platform
chemical as well as an ideal liquid fuel. The direct synthesis of
methanol from the hydrogenation of CO2 has thus attracted
great interest. According to the idea of liquid sunshine proposed
by Shih and co-workers,[13] synthesis of methanol from CO2 and
hydrogen is the first target. The “methanol economy” proposed
by George Olah also positions CO2 hydrogenation to methanol
and derived products at its core.[14] Nowadays, methanol is one
of the top five commodity chemicals shipped around the world
each year. It is a primary raw material for the chemical industry,
increasingly used in the methanol-to-olefins and methanol-to-
aromatics processes.[15] Additionally, the market demand for
methanol-derived fuels has been dramatically increased from
6% in 2011 to 22% in 2016.[16] Thus, CO2 hydrogenation to
methanol is one of the attractive and potentially profitable routes
ChemSusChem
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in CCSU to mitigate CO2 emissions and reduce the dependence
on fossil resources.
The research progress on catalytic hydrogenation of CO2 into
fuels and chemicals through both homogeneous and
heterogeneous catalysis has been summarized in several
excellent reviews and perspectives.[3, 6d, 7h, 17] Although some
homogeneous catalysts show high activity and selectivity,[17a, 18]
they are confronted with difficulties in recovery and regeneration
of the catalysts. By contrast, heterogeneous catalysts are
preferable due to their advantages in stability, separation,
handling, and reuse, as well as reactor design which helps to
fulfill large-scale production with lower costs.[7h, 18] Besides,
these publications mainly focused on the general aspects of CO2
conversion and the discussion on Cu-based catalysts for CO2
hydrogenation to methanol. This review emphasizes on the
progress in developing non-Cu-based heterogeneous catalysts
for CO2-to-methanol conversion and tries to provide a current
understanding of catalysts design and catalysts advances. The
studies concerning the homogeneous catalysis, photocatalysis,
and electrocatalysis as well as the indirect hydrogenation of CO2
to methanol are beyond the scope of this review. In this paper,
we firstly discuss the chemical property and activation of CO2.
Then, the thermodynamic analysis of CO2 hydrogenation to
methanol is discussed. That is followed by discussions on the
progress in non-Cu-based heterogeneous catalysts, including
supported metal-based catalysts, bimetallic alloys or
intermetallic compounds catalysts, and mixed oxide catalysts
represented by MaZrOx (Ma = Zn, Ga, and Cd) solid solution
catalysts. Finally, a summary and a perspective are presented.
Feng Sha received his Master degree from Inner
Mongolia University of Technology in 2017. He is
currently a PhD candidate under the supervision
of Prof. Can Li in the School of Materials Science
and Engineering at Nankai University and the
State Key Laboratory of Catalysis at Dalian
Institute of Chemical Physics. His research
interests focus on the heterogeneous catalysts
for CO2 hydrogenation to methanol.
Ji-Jie Wang received his Ph.D. degree from
Xiamen University in 2013. He did
postdoctoral work at Dalian Institute of Chemical
Physics in 2013–2017. Currently, he is an
associate professor in the State Key Laboratory
of Catalysis at Dalian Institute of Chemical
Physics. His research interests include (1) CO2
hydrogenation to chemicals and fuels,
methanol steam reforming to hydrogenation, and
(3) liquid solar fuel synthesis.
Can Li received his Ph.D. degree in Physical
Chemistry from Dalian Institute of Chemical
Physics in 1989. He was promoted to full
professor in 1993 and has been a visiting
professor at the Université Pierre et Marie Curie
(Paris VI), the Lehigh University, the University of
Liverpool, and the Queensland University. He did
his postdoctoral work at Northwestern University
in 1994–1996. Currently, he is the head of Solar
Energy Research Division and the director of the
Dalian National Laboratory for Clean Energy. His research interests include (1)
environmental and green catalysis, (2) UV Raman spectroscopy and time-
resolved spectroscopy, (3) chiral catalysis and bio-catalysis, and (4) solar
energy utilization based on photo(electro)catalysis and photovoltaic cells.
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002054
2. The Properties and Activation of CO2
CO2 is a linear molecule. Despite overall a non-polar molecule,
CO2 has two polar bonds due to the electronegativity difference
between C and O atoms. The electronic structure of CO2 can be
marked as O−δ−C+2δ−O−δ, implying that CO2 can be treated as a
bi-functional molecule with two different reaction sites. The
carbon atom can be attacked by nucleophiles, while the oxygen
atoms can be attacked by electrophilic reagents. Meanwhile,
CO2 can react with base since it can form carbonic acid in water.
The physical state of CO2 changes with temperature and
pressure. CO2 becomes solid at low temperature and sublimes
on warming below 5.1 bar. When the temperature and pressure
exceed critical point (304 K, 73.9 bar), CO2 reaches the
Accepted Manuscript
supercritical state, where the density is close to liquid while the
viscosity is similar to gas. This state is often applied in the
pharmaceutical industry.
Although CO2 reacts readily with strong nucleophiles, it is
generally considered to be an “inert” molecule. This is caused by
the high kinetic energy barrier for the synthetic transformations
(C-H, C-C, and C-O bond formations) as well as the
thermodynamic constraints imposed by the extremely low
chemical potential of the CO2 molecule. On the one hand, CO2 is
thermodynamically stable (ΔGf0 = −394.4 kJ·mol−1). Thus the
conversion of CO2 requires huge amount of energy, which
depends upon the downward steps of the oxidation state of
carbon from +4 in CO2 to the value in the target chemicals. On
the other hand, the use of high-energy molecular reagents can
provide driving forces to make the transformations
thermodynamically feasible. Hence, CO2 chemical
transformation and utilization face huge scientific and technical
challenges.
CO2 is a green, abundant, and renewable carbon source.
However, it is not used widely as a raw material in current
industrial practices. The reason for this is that the carbon atom
in CO2 is in its highest oxidation state and is therefore relatively
inactive, which means a considerable energy input is required to
transform CO2 into useful chemicals. There are mainly four ways
to achieve CO2 transformation: (i) use high energy starting
materials such as hydrogen and chemically unsaturated
compounds, (ii) choose low energy synthetic targets, (iii) remove
his
by-products to drive the equilibrium shift to the products, and (iv)
supply other energy such as light or electricity. Selecting the
right conditions for the CO2 transformation is crucial in order to
achieve a negative Gibbs free energy change and low kinetic
energy barrier for the reaction.[19]
(2)
3. Thermodynamics of CO2 hydrogenation
It is well known that CO2 is a highly stable molecule with
almost the lowest Gibbs free energy. Therefore, it is more
energy-demanding if CO2 is used as the sole substrate.
However, it becomes thermodynamically easier if CO2 is used as
a co-reactant with another reactant with higher Gibbs free
energy, such as H2. The products of CO2 hydrogenation reaction
are closely related to the type of catalyst and reaction conditions.
Methane, the easiest C1 hydrocarbon of CO2 conversion,
mainly products from the CO2 methanation. CO2 methanation is
a highly favorable process with large negative values of enthalpy
and Gibbs free energy (eq. 1). Ni, Rh, and Ru with various
supports (such as SiO2, Al2O3, TiO2, CeO2, ZrO2) are the most
widely researched reported catalysts as their stronger
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ChemSusChem
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hydrogenation ability for reaction intermediate species to form
methane.[20] Fixed-bed reactors at atmospheric pressure, 320-
400 oC, and a 4:1 ratio of H2 to CO2 are generally employed for
the CO2 methanation. Compared to the methanol, methane is
much more stable and less reactive. As one of the most
important products of CO2 reduction, transition metal-based
systems like Cu, Pd, Pt, Au, and Ag have been proved to be
good catalysts for methanol synthesis, which are discussed in
the corresponding parts in the following. The hydrogenation
ability of these metals to the reaction intermediate species is
moderate, not enough for further hydrogenation to generate
hydrocarbons. It is worth noting that the catalytic behavior of
these metals is also depended on the type of support. Methanol
production is favored by a 3:1 ratio of H2 to CO2 and a
temperature around 200-300 oC with a pressure of 30-50 bar.
Thus, CO2 hydrogenation to methanol is more attractive and
profitable than CO2 methanation.
CO2 + 4H2 ⇆ CH4 + 2H2O (1) ΔH°298K = −252.9 kJ/mol
ΔG°298K = −130.8 kJ/mol
CO2 + 3H2 ⇆ CH3OH + H2O (2) ΔH°298K = −49.5 kJ/mol
ΔG°298K = −9.04 kJ/mol
CO2 + H2 ⇆ CO + H2O (3) ΔH°298K = +41.2 kJ/mol
ΔG°298K = −20.1 kJ/mol
CO + 2H2 ⇆ CH3OH (4) ΔH°298K = −90.6 kJ/mol
ΔG°298K = −29.1 kJ/mol
It could be seen that methanol formation and reverse water-
gas shift (RWGS) reaction compete with each other (eqs 2 and
3). Methanol also forms from the combination of the RWGS
reaction (eq 3) with the subsequent hydrogenation of CO (eq 4).
In view of thermodynamics, methanol formation (eqs 2 and 4)
is exothermic while RWGS reaction (eq 3) is endothermic.
According to Le Ch telier s principle, decreasing reaction
temperatures and increasing reaction pressures are more
favorable for methanol synthesis due to the exothermic nature
and the decrease in the number of molecules of the methanol
formation (eqs 2 and 4). Moreover, high molar ratio of H2/CO2
also favors methanol synthesis taking the two equilibria into
consideration.[21] Therefore, the overall process becomes
equilibrium limited, where thermodynamics and equilibrium shifts
interplay to determine the conversion and selectivity of the
products.
Thermodynamically, high pressure and low temperature are
favorable for methanol synthesis, as discussed above. Reaction
temperature higher than 513 K facilitates CO2 activation and
subsequent methanol formation.[17a, 22] Van Bennekom et al.
developed a model to simultaneously calculate the phase
equilibrium and chemical equilibrium for high-pressure methanol
synthesis (P = 20 MPa, 463-553 K) based on a modified Soave-
Redlich-Kwong equation of state.[23] The calculated gas
composition and equilibrium conversion, with and without the
formation of a liquid phase, are verified by the experimental
results obtained in a packed bed methanol synthesis reactor.
They found that the condensation of reaction products (mainly
methanol and water) drove the equilibrium reactions nearly to
completion.
As shown in Fig.1, equilibrium CO2 conversion notably
changes with pressure in a wide range of temperatures,
especially at 100-300 bar. This is caused by the formation of a
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10.1002/cssc.202002054
liquid phase and phase separation.[24] Equilibrium CO2
conversion increases with rising temperature at low pressure (<
100 bar), and decreases at high pressure. Methanol selectivity
decreases with rising temperature, which is caused by the
enhancement of endothermic RWGS reaction. It could be seen
that high reaction pressure is advantagous in CO2 hydrogenation
to methanol, which has been verified experimentally by Gaikwad
and co-workers.[25] The equilibrium CO2 conversion and
methanol selectivity are enhanced at higher H2/CO2 ratio (Fig. 1).
Bansode et al. found that the CO2 conversion was 37% with
methanol selectivity of 72% at the H2/CO2 molar ratio of 3, but
CO2 conversion rose drastically to 95% with methanol selectivity
of 98% when H2/CO2 molar ratio was increased to 10 while other
operating conditions remained unchanged.[25b] The
Accepted Manuscript
experimentally observed outstanding CO2 conversion and
methanol selectivity at high molar ratio of H2/CO2 mainly result
from the high H2 partial pressure that enhances the reaction rate.
Figure 1. Equilibrium CO2 conversion and methanol selectivity at different
temperatures with initial H2/CO2 mixtures of 3 (A) and 10 (B), and at (a) 10 bar,
(b) 30 bar, (c) 100 bar, (d) 200 bar, (e) 300 bar, (f) 400 bar, and (g) 500 bar.
Reproduced with permission from Ref. [17d]; copyright 2017, American
Chemical Society.
4. Supported Metal Catalysts for CO2
Hydrogenation to Methanol
Heterogeneous metal-based catalysts for methanol synthesis
from CO2 hydrogenation mainly use Cu and noble metals such
as Pd, Pt, Au, and Ag. Álvarez et al.[17d] analyzed the research
articles published in the past ten years on CO2 hydrogenation to
methanol. The results show that 79% of the reports are related
to Cu-based catalysts. It could be seen that Cu-based catalysts
are still the focus of current research. Although there still exist
debates in identifying the active sites and understanding the
mechanism, the structure-activity relationship of Cu-based
catalysts has been well established. However, Cu-based
catalysts present poor activity at low temperatures compared
with other catalysts,[26] where methanol synthesis is more
thermodynamically favorable. Moreover, Cu-based catalysts
also face severe deactivation over time. Due to these reasons,
noble metal catalysts are explored to improve the activity and
carried out for CO2 hydrogenation to methanol at low
temperatures, which is instrumental for the methanol synthesis
according to thermodynamics. The representative supported
metal-based catalysts are summarized in Table 1. The catalytic
ChemSusChem 10.1002/cssc.202002054

REVIEW
performances are discussed in the corresponding parts in the
following.

Accepted Manuscript

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ChemSusChem 10.1002/cssc.202002054

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Table 1 Catalytic performance of some non-Cu based catalysts for CO2 hydrogenation to methanol.

Catalyst H2/CO2 molar ratio TR (oC) PR (MPa) Space velocity[a] Conv. (%) Sel. (%) STY[b] Ref.

CuZn
3:1 240 3 - 16.1 36.5 44.5 [26d]
(Co-precipitation)

Cu/ZrO2(IV)
3:1 260 8 3600 (G) 8.6 92 154 [26e]
(Co-precipitation)

CuZnZr
3:1 240 5 - 22.4 64 453 [26f]
(Co-precipitation)

CuZnAl-400
3.03:1 240 3 - 59.5 73.4 131 [26g]

Accepted Manuscript
(Mechanical ball-milling)

Cu/Ga/Zn
3:1 270 2 18000 (W) 6 88 378 [26h]
(Co-impregnation)

Pd/Ga2O3
3:1 250 5 18000 (W) 19.6 51.5 649 [27a]
(Co-precipitation)

5Pd/rod Ga2O3
3:1 250 5 6000 (W) 11.0 41.3 - [27f]
(Impregnation)

5Pd/plate Ga2O3
3:1 250 5 6000 (W) 17.3 51.6 - [27f]
(Impregnation)

1%Pd/ZnO
3:1 250 2 3600 (W) 1.7 76 13.12 [28a]
(Sol-immobilisation)

1%Pd/ZnO
3:1 250 2 3600 (W) 3.2 22 8.64 [28a]
(Impregnation)

5%Pd/ZnO
3:1 250 2 3600 (W) 10.7 60 77.44 [28a]
(Sol-immobilisation)

5%Pd/ZnO
3:1 250 2 3600 (W) 8.7 1 1.76 [28a]
(Impregnation)

Ag@Pd-ZnO
3:1 270 4.5 9600 (G) 18 46 280 [28c]
(Impregnation)

5PdZn
3:1 250 2 3600 (W) 8.2 32 34.24 [28e]
(CVI)

5PdZn (1:5)/TiO2
3:1 250 2 3600 (W) 10.1 40 55.36 [28e]
(CVI)

1PdZn/CeO2
3:1 220 2 3600 (G) 14.1 97.2 165.85 [28f]
(Sol-gel)

5Pd5ZnCeO 2
3:1 220 3 2400 (W) 6.3 100 48.96 [28g]
(Chelating method)

0.5Ca5Pd5ZnCeO2
3:1 220 3 2400 (W) 7.7 100 61.76 [28g]
(Chelating method)

16Pd0.1Zn1/CNT(h-type)
3:1 250 3 1800 (W) 6.30 99.6 37.1 [28h]
(Impregnation)

22Pd0.1Zn1/CNT(p-type)
3:1 250 3 1800 (W) 6.22 95.2 35.0 [28h]
(Impregnation)

Pd/CeO2-500
3:1 230 3 - 3.1 91.7 - [29]
(Impregnation)

Pd-P/In2O3
4:1 300 5 21000 (W) 20 70 890 [30b]
(Impregnation)

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Pd-I/In2O3
4:1 300 5 21000 (W) 18 70 800 [30b]
(Impregnation)

Pd/In2O3/SBA-15
4:1 260 5 15000 (W) 12.6 83.9 352 [30d]
(Citric acid method)

Pd1Ga10-(Pd/CNT-h)
3:1 250 5 18000 (G) 6.5 95.7 555 [31a]
(Impregnation)

Pd1Ga10-CNT-h
3:1 250 5 18000 (G) 7.5 96.2 512 [31a]
(Impregnation)

Pd1Ga10-CNT-p
3:1 250 5 18000 (G) 6.2 96.6 428 [31a]
(Impregnation)

Pd/CNTs-in

Accepted Manuscript
3:1 250 2 1200 (W) 0.77 48.8 1.54 [31b]
(Impregnation)

Pd/CNTs-in
3:1 250 2 1200 (W) 0.61 13.4 0.35 [31b]
(Impregnation)

0.5Mg4Pd/SBA-15
3:1 250 4.1 - 3 40 0.31 [32b]
(Impregnation)

0.5Ca4Pd/SBA-15
3:1 250 4.1 - 7 39 0.46 [32b]
(Impregnation)

PtCr/SiO2
3:1 200 3 - 2.6 92.2 - [36]
(Impregnation)

PtW/SiO2
3:1 200 3 - 2.2 51.1 - [36]
(Impregnation)

Pt/film/In2O3
3:1 30 0.1 - 37 62.6 355 [40]
(Impregnation)

Au/TiO2
3:1 240 0.5 4800 (G) 13.1 0.6 - [41a]
(Deposition precipitation)

Au/ZrO2
3:1 240 0.5 4800 (G) 9.3 3.4 - [41a]
(Deposition precipitation)

Au/ZnO
3:1 240 0.5 4800 (G) 0.4 50.6 - [41a]
(Deposition precipitation)

Au/Al2O3
3:1 240 0.5 4800 (G) 3.7 0.4 - [41a]
(Deposition precipitation)

10Au/(3ZnO-ZrO2)
3:1 220 8 3300 (G) 2 100 19 [45]
(Co-precipitation)

10Ag/(3ZnO-ZrO2)
3:1 220 8 3300 (G) 1 95 8 [45]
(Co-precipitation)

PdMgGa
3:1 250 3 19200 (W) 1 47 - [51c]
(Co-precipitation)

1Pd/β-Ga2O3
3:1 250 3 80000 (G) <1 52 - [51d]
(Impregnation)

Ga3Ni5/SiO2
3:1 210 0.1 5310 (G) - - 240 [53b]
(Impregnation)

ZnO-ZrO2
3:1 320 5 24000 (W) 10 86 737 [7a]
(Co-precipitation)

CdZrOx
3:1 300 2 24000 (W) 5.5 80 - [7c]
(Co-precipitation)

GaZrOx 3:1 300 2 24000 (W) 2.4 75 - [7c]

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(Co-precipitation)

ZnO-ZrO2/UiO-66 3:1 320 3 18000 (W) 5.8 70 - [54]

ZnO/t-ZrO2
3:1 320 3 12000 (W) 9.2 93.1 350 [55]
(Microreaction synthesis)

ZnOx/ZrO2-600
3:1 300 2 7200 (W) 5.5 75.1 - [56]
(Impregnation)

In2O3/ZrO2
4:1 300 5 16000 (W) 5.2 99.8 295 [58a]
(Impregnation)

Inx/ZrO2
4:1 280 5 24000 (G) 2.5 60 87 [58c]
(Impregnation)

1.5YIn2O3/ZrO2

Accepted Manuscript
4:1 300 4 52000 (W) 7.6 69 420 [58d]
(Impregnation)

3La10In/ZrO2
4:1 300 4 52000 (W) 7.7 66 420 [58d]
(Impregnation)

20MnOx-Co3O4
3:1 250 1 88800 (G) 45.1 22.1 - [63]
(Sol-gel)

[a] (W) = WHSV = mass flow rate/catalyst mass (mL·gcat-1·h-1), (G) = GHSV = volume flow rate/bed volume (h-1). [b] Space time yield of methanol (gMeOH kgcat-1 h-1)

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4.1 Pd-based catalysts
Pd supported on different supports have been studied for
CO2 hydrogenation to methanol. At present, supports mainly
focus on Ga2O3,[27] ZnO,[28] CeO2,[28f, 28g, 29] In2O3,[30] carbon
materials,[28h, 31] and silica materials (SBA-15, MCM-41)[28b, 30c, 32]
to modify the electronic state of Pd for improving CO2
adsorption and activation.[33]
4.1.1 Pd supported on Ga2O3
Pd/Ga2O3 catalysts are active for the CO2 hydrogenation to
methanol, but not selective. The selectivity can be further
enhanced by tuning the interaction between Pd and Ga2O3 and
the shape of catalysts. The study by Fujitani et al. showed that
Pd/Ga2O3 was two times higher than Cu/ZnO in yield for
methanol synthesis from CO2 hydrogenation.[27a] The excellent
activity of Pd/Ga2O3 is attributed to the optimal amount of Pdn+
(0 < n < 2) stabilized by GaxOy. Subsequently, a sustained
research effort has been conducted to the Pd/Ga system for
CO2 hydrogenation to methanol.[27b-g] It is suggested that Pd/Ga
catalysts mainly transform CO2 into methanol via a bifunctional
pathway. The reaction intermediates chemisorbed on the
surface of Ga2O3 are hydrogenated from (bi)carbonates to
formate (mono and bidentate and bridged), methylenebisoxy,
and methoxy step by step to give methanol, while hydrogen
supply is accomplished via spillover from the palladium metal
particles.
Tsang et al. reported the shape effect of Pd-promoted Ga2O3
nano-catalysts by controlling the growth of nano-size Ga2O3
crystals with different shapes for methanol synthesis from CO2
hydrogenation.[27f, 27g] The authors prepared two types of Ga2O3
nanoparticles with different shapes, namely, the β-Ga2O3 rod
and β-Ga2O3 plate with the majority of their surfaces covered
with polar and non-polar facets, respectively. The same amount
of Pd was placed on the β-Ga2O3 rod and β-Ga2O3 plate. These
two catalysts were used as model catalysts to study the
morphology-performance relationship. By carefully testing these
model catalysts in combination with in-depth characterizations
including cyclic voltammetry, X-ray photoelectron spectroscopy
(XPS), and computing modeling, they found that the (002)
surface of the polar β-Ga2O3 plate could give oxygen defects
and mobile electrons in the conduction band more readily than
the non-polar (111) and (110) surfaces. The metal-support
interaction between Pd and the polar (002) surface of β-Ga2O3
plate is stronger than other non-polar surfaces. This stronger
metal-support interaction gives rise to higher metal dispersion
and facilitates electron transfer, leading to the formation of
PdGax and higher activity for methanol production from CO2
hydrogenation.
4.1.2 Pd supported on ZnO
Pd/ZnO catalysts are active in CO2 hydrogenation to
methanol. The product selectivity depends on support types,
preparation methods, and Pd precursors.[28a] Pd has a strong
inclination to form alloy species with ZnO when exposed to high
temperature under reducing environment,[34] which are
correlated with catalytic activity and methanol selectivity.[28b-h]
Iwasa et al. reported that Pd supported on ZnO showed the
highest activity and selectivity to methanol among the Pd
supported on Ga2O3, In2O3, SiO2, MgO, and ZrO2.[28b] This is
9
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10.1002/cssc.202002054
explained by the formation of PdZn alloys, which act as active
sites for the direct synthesis of methanol.
Hong et al. synthesized ZnO-supported Ag@Pd core@shell
structure and found that electron transfer from Ag to the Pd
shell significantly enhanced methanol selectivity.[28c] This offers
an alternative chance to enhance the catalytic performance and
reduce the Pd loading.
Díez-Ramírez et al. studied the catalytic performance of
Pd/ZnO catalyst in the hydrogenation of CO2 to methanol under
atmospheric pressure as PdZn alloys were well known to give
good performance in this reaction.[28d] The influence of
reduction temperature, calcination condition, metal loading, and
Pd precursor on the catalytic performance was studied. The
results show that higher reduction temperature and higher
Accepted Manuscript
metal loading are helpful to the formation of more PdZn alloy
particles, which lead to higher methanol production. In contrast,
fast calcination and insoluble metal precursor result in larger
metallic palladium particles, hindering PdZn alloy formation and
suppressing methanol production.
Bowker et al. investigated the formation of PdZn alloy
catalysts using chemical vapor impregnation to investigate their
activity in the CO2 hydrogenation reaction.[28e] PdZn supported
on TiO2 exhibits a high methanol yield of 1730 mmol·kgcat-1·h-1,
which is associated with the high dispersion of the supported
PdZn alloy nanoparticles with a narrow size distribution.
Detailed analysis reveals that the PdZn alloy phase stabilizes
the formate intermediate and hence gives high activity for
methanol formation from the CO2 hydrogenation.
Figure 2. (a) CO2 conversion, (b) methanol selectivity and (c) proposed
reaction mechanism over Ca-doped PdZn/CeO2 catalysts. Reaction
conditions: P=30 bar, H2/CO2=3/1, GHSV=2400 mL/(g h). Reproduced with
permission from Ref. [28g]; copyright 2018, Elsevier.
Zaman et al. developed highly selective PdZn/CeO2 and Ca-
doped PdZn/CeO2 catalysts for methanol synthesis from CO2
hydrogenation under mild reaction conditions.[28f, 28g] The
PdZn/CeO2 catalysts give maximum CO2 conversion of 14%,
which is close to thermodynamic equilibrium, and high
methanol selectivity of 95% (220 oC, 20 bar, 2400 h−1 GHSV).
The Ca-doped PdZn/CeO2 catalysts exhibit about 100%
selectivity to methanol with CO2 conversion of 7.7% (220 oC, 30
bar, 2400 h−1 GHSV) (Fig. 2a,b). The reason for the high
selectivity and activity lay in the excellent H2 dissociation ability
of PdZn alloy and the increased amount of oxygen-vacant sites
on CeO2, as illustrated in Fig. 2c. The amount of oxygen-vacant
sites on CeO2 could be modified by the surface morphology of
ChemSusChem 10.1002/cssc.202002054

REVIEW
CeO2 with the incorporation of Pd, Zn, and Ca. As a promoter, scale and holds a potential for tailoring new or existing
the addition of Ca to the CeO2-supported PdZn catalysts promoted systems in current and emerging applications of
slightly improves the selective conversion of CO2 to methanol heterogeneous catalysis.
by raising the amount of oxygen-vacant sites. In-situ DRIFTS
studies suggest that the reaction mechanism is the formate
pathway for selective formation of methanol.

4.1.3 Pd supported on CeO2 and In2O3

Pd/CeO2 and Pd/In2O3 catalysts have recently shown great

potential for methanol synthesis from CO2 as both CeO2 and
In2O3 their ability to provide surface and bulk oxygen vacancies,
which facilitates the CO2 adsorption and activation.[28f, 28g, 29, 30]
Li et al. found that Pd/CeO2 catalyst reduced with hydrogen
Figure 3. Schematic representation of the distinct role of palladium in
equilibrated CP and DI systems with In2O3 as references. Adapted with
permission from Ref. [30c]; copyright 2019, Springer Nature.

Accepted Manuscript
at 500 oC exhibited high activity and long lifetime for methanol
synthesis, which might be attributed to the strong metal-support
interaction (SMSI) between Pd and CeO2.[31] This SMSI
Zhang et al. reported that highly dispersed Pd and In2O3 NPs
promotes the formation of Ce2O3 from the partial reduction of
on the SBA-15 exhibited superior catalytic activity with 83.9%
CeO2 at 500 oC and maintains this active Ce2O3 during the
methanol selectivity, 12.6% CO2 conversion, and no apparent
reaction process. When Pd/CeO2 was reduced at temperature
deactivation during 120 h on stream under reaction conditions
ranging from 200 to 400 oC, the catalyst activity dropped as
of 260 oC, 5 MPa and 15,000 mL·h-1·gcat-1, which was attributed
Ce2O3 re-oxidizes to restore the original CeO2 state. The Ce2O3
to the synergetic effect of H2 dissociation on Pd species and
had a stronger combination with adsorbed CO which prevented
CO2 activation on In2O3.[30d] Doping of Pd not only facilitates the
it from re-oxidation by adsorbed oxygen atoms. CO2 was
creation of more oxygen vacancies on the surface of In2O3, but
adsorbed disassociatively on the reduced ceria surface, with
also significantly improves the ability to adsorb and dissociate
the aid of hydrogen spilled over from Pd, to form adsorbed CO
H2, providing the needed H atoms for hydrogenation of CO2.
and surface oxygen atoms. When the surface oxygen atom
Moreover, the highly ordered mesostructure of SBA-15
from the decomposition of CO2 reacted with hydrogen from Pd
provides a large surface to disperse the active components for
to form water, the active site Ce3+ might continue to play an
improving the catalytic activity.
important role producing adsorbed CO and then successively
Jaramillo et al. found that the coexistence of In2O3 and Pd-In
hydrogenate it to methanol, as occurred with Pd/CeO2 reduced
alloy phases resulted in the promotion of the catalytic activity
at 500 oC.
and selectivity toward methanol in CO2 hydrogenation based on
Liu et al. predicted that the Pd/In2O3 catalyst would be an
characterization results and density functional theory.[30e]
excellent catalyst for methanol production from CO2
Although all InPd/SiO2 bimetallic catalysts have enhanced
hydrogenation based on density functional theory and
catalytic performance than In/SiO2 or Pd/SiO2 catalysts, the
microkinetic studies.[30a] Subsequent experimental studies
methanol synthesis is maximized when the catalyst contained
showed that In2O3 supported highly-dispersed Pd nanoparticles
both In-Pd intermetallic compounds and an indium oxide phase.
significantly improved hydrogen dissociative adsorption ability,
Similar promotional effects are observed in a non-precious
supplied hydrogen for the hydrogenation steps, and facilitated
metal containing In-Ni/SiO2 system, which suggests that the
oxygen vacancy creation, which contributed to the superior
promotion effect could be translatable to other alloy/oxide
performance for CO2 hydrogenation to methanol with CO2
systems.
conversion > 20% and methanol selectivity > 70% at 300 oC
and 5 MPa.[30b]
4.1.4 Pd supported on carbon materials
Pérez-Ramírez et al prepared Pd-promoted In2O3 using co-
precipitation (CP) and dry impregnation (DI) and compared their
Pd-based catalysts supported on carbon nanotubes (CNTs)
catalytic performance in CO2 hydrogenation to methanol at 553
have been reported to exhibit excellent performance in CO2
K and 5 MPa.[30c] The incorporation of palladium increases the
methanol space time yield higher than that of pure In2O3. hydrogenation to methanol.[28h, 31] The CNTs or the Pd-
decorated CNTs can serves as catalyst supporter and promoter
Comparing the methanol selectivity over Pd/In2O3 (CP),
for the Pd/ZnO or Pd/Ga2O3 catalysts in CO2 hydrogenation to
Pd/In2O3 (DI) and In2O3 at a CO2 conversion of 3% reveals that
methanol.[28h, 31a] Using the CNTs as the catalyst support leads
palladium has a beneficial effect on the product distribution
when added through CP but not via DI. In the Pd/In2O3 (CP) to an increase of the relative content, at surface of the
functioning catalyst, of the catalytically active Pd0-species
catalyst, palladium atoms replace indium atoms in the active
closely associated with the methanol generation. The Pd-
In3O5, which results in additional palladium atoms deposits onto
decorated CNTs not only increases the surface concentration of
the surface forming low-nuclearity clusters anchored to the
active site. The small size of the palladium cluster fosters H2 the active Pd0-species, but also improves the capability of
adsorbing and activating H2. As demonstrated by the H2-TPD
activation to improve the production of methanol and remains
experiment, the sequence of increasing concentration of H-
unaltered within 500 h (Fig. 3b). In the Pd/In2O3 (DI) catalyst,
adspecies at the surface of the functioning catalysts was
palladium steadily agglomerates with time on stream forming
nanoparticles. The palladium nanoparticles mediates the Pd1Ga10-12.6%(3%Pd/h-CNTs) > Pd1Ga10-12.6% h-CNTs >
Pd1Ga10-12.6% p-CNTs > Pd1Ga10, in line with the observed
parasitic RWGS reaction, further reducing the selectivity of
sequence of reaction activity over these catalysts for the CO2
methanol (Fig. 3c). This work marks a step ahead toward green
hydrogenation to methanol.
methanol production via engineering promotion at the atomic

10
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ChemSusChem
REVIEW
Wang et al. incorporated Pd nanoparticles inside and outside
the CNTs, as shown in Fig. 4, and carefully examined these
catalysts in the reaction of CO2 hydrogenation to methanol.[31b]
The CO2 conversion of the Pd/CNTs-in catalyst is 1.3 times
than that of the Pd/CNTs-out catalyst, and the methanol
selectivity of the Pd/CNTs-in catalyst is 3.6 times than that of
the Pd/CNTs-out catalyst (Fig. 4c). These difference are
caused by the channel structure and electronic density
differences between the inside and outside of CNTs, which
result in slightly smaller Pd nanoparticles size, more Pdδ+
species, and higher H2 pressure inside the CNTs than outside.
This work shows that the Pd0-Pdδ+ sites are responsible for CO2
hydrogenation to methanol, in which Pd0 activates H2 and Pdδ+
species activated CO2. At the same time, the locally higher H2
pressure inside CNTs increases the hydrogenation rate.
Figure 4. TEM images and particle size distribution of catalysts: (a) Reduced
Pd/CNTs-in catalyst, (b) Reduced Pd/CNTs-out catalyst; (c) Space time yield
and selectivity of methanol at varied temperatures on Pd/CNTs-in and
Pd/CNTs-out catalysts, reaction conditions: 2.0 MPa, H2/CO2/Ar = 72/24/4,
GHSV = 1200 mL·h-1·g-1. Reproduced with permission from Ref. [31b];
copyright 2015, Royal Society of Chemistry.
4.1.5 Pd supported on silica materials
Supporting Pd-based catalysts on mesoporous silica
materials is expected to improve methanol synthesis activity
since the uniform pore structures of mesoporous materials can
provide nano-sized and uniform reaction environments, which
can stabilize small Pd and metal oxide nanoparticles inside
mesopores.
Previous studies showed that Pd/SiO2 had no activity for
methanol synthesis from CO2 and H2.[28b, 35] Alkali and alkaline
earth metals are known as effective promoters for enhancing
the methanol synthesis activity of Pd/SiO2 catalyst.[32a] Song et
al. studied the cooperative effects of nano-structured
mesoporous supports and alkali/alkaline earth metal additives
on methanol synthesis.[32b] Small mesopores in MCM-41 and
SBA-15 work as templates for the formation of small Pd0
nanoparticles and lead to the higher activities for CH3OH
formation than the conventional amorphous silica. Pd supported
on MCM-41and SBA-15 without any promoters exhibit weak
activities for methanol formation, while the addition of K, Mg,
and Ca enhances activities significantly.
4.2 Pt-based catalysts
Pt is active in hydrogenation reactions and has also been
studied for methanol synthesis from CO2 and H2. The catalytic
performance can be improved by incorporating the additives
and increasing the Pt dispersion. Fujimoto et al. reported that
11
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10.1002/cssc.202002054
the SiO2-supported PtW and PtCr bimetallic catalysts prepared
by using bimetal carbonyl hydride complexes exhibited very
high selectivity and long lifetime for methanol synthesis.[36] In
contrast, the conventionally impregnated monometallic and
bimetallic catalysts are almost inert or produced mainly CO. W
and Cr, as additives, can interact with Pt to suppress the
sintering of Pt and provide active bimetallic ensemble sites,
which are responsible for the high activity and methanol
selectivity.
Jeong et al. examined the impact of acidity on the
hydrogenation of CO2 to methanol and dimethyl ether using Pt
supported on Nb2O5.[37] The increase of support acidity
enhances the metal-support interaction and metal dispersion,
improves the CO2 conversion, while it is detrimental for the
Accepted Manuscript
production of methanol due to unfavorable adsorption of CO2
molecules and the formation of carbon-containing species on
the surface of the support with high acidity.
Li et al. investigated the influence of Pt content on the
performance in CO2 hydrogenation using the Pt/In2O3
catalysts[38]. The Pt species was introduced into In2O3 by co-
precipitation. They found that the methanol selectivity increased
with the addition of a small amount of Pt into In2O3 when the Pt
content was lower than 0.34 wt.%. However, further increasing
the Pt content to 0.34 wt.% and 0.58 wt.% lead to a slight
decrease in the methanol selectivity. Stability tests of Pt/In2O3
and In2O3 show that the introduction of Pt does not have a
significant impact on the change of methanol selectivity during
the long time reaction. At the same time, the drop of CO2
conversion is mitigated, indicating that the introduction of Pt
could increase the stability of the catalysts.
Figure 5. (a, d) HRTEM and (b, e) STEM images of (a, b) as-prepared 0.58
wt.% Pt/In2O3 and (d, e) used 0.58 wt.% Pt/In2O3 after reaction. The
atomically dispersed Pt species and Pt nanoparticles are marked with arrows
and circles, respectively, in the STEM images. (c) XPS Pt 4d spectra of the
as-prepared and used 0.58 wt.% Pt/In2O3. Reproduced with permission from
Ref. [38]; copyright 2020, Elsevier.
The Pt species in the 0.58 wt.% Pt/In2O3 before and after
used in CO2 hydrogenation were studied by atomic-resolution
TEM and XPS (Fig. 5). Atomic-resolution TEM images proves
that the Pt species in the as-prepared 0.58 wt.% Pt/In2O3 is in
the atomically dispersed state. After used in CO2 hydrogenation,
a small amount of Pt nanoparticles form from the sintering of
the atomically dispersed Pt species, while there is still a
significant amount of atomically dispersed Pt species. XPS
results show that the atomically dispersed Pt species in the as-
prepared 0.58 wt.% Pt/In2O3 are in the cationic state, while the
Pt species in the used catalysts are in the mixed metallic state
and cationic state, in agreement with TEM results. Combined
with the reaction results, they propose that the atomically
dispersed Ptn+ species are responsible for the increased
ChemSusChem
REVIEW
methanol selectivity while the Pt nanoparticles forming during
CO2 hydrogenation mainly promote the RWGS reaction.
The role of Pt in the Pt/In2O3 catalysts during CO2
hydrogenation was further studied by H2-TPD and H2-D2
isotopic exchange reaction. H2-TPD results show that the
introduction of Pt into In2O3 changes the adsorption strength of
H2 on the catalysts. New adsorption sites are also created after
the introduction of Pt. The results of the H2-D2 isotopic
exchange reaction prove that the Ptn+ species are active in the
activation of H2. They propose that the oxidation effect of the
CO2 and the product H2O, as well as the interaction between Pt
and In2O3 lattice, could help in the stabilization of Pt in the
cationic state against reduction during CO2 hydrogenation.
Therefore, a significant amount of atomically dispersed Ptn+
species are preserved after CO2 hydrogenation.
Liu et al. prepared Pt/In2O3 catalyst by the deposition-
precipitation method and tested the catalytic performance for
CO2 hydrogenation to methanol over the Pt/In2O3 catalyst and
the pure In2O3 catalyst.[39] When the reaction temperature
increases from 200 to 300 oC, the selectivity towards methanol
maintains ca. 100% at temperatures below 225 °C, 74% at
275 °C and 54% at 300 °C, respectively. Compared with pure
In2O3 catalyst, the activity and the stability of the Pt/In2O3
catalyst are highly improved. The BET, XRD, and TEM results
of the catalysts indicates that the Pt nanoparticles are well-
dispersed with an average particle size of 1.47 nm. More
importantly, TEM and H2-TPR results show that there are SMSI
between Pt and In2O3. The SMSI inhibits the over-reduction of
In2O3, resulting in the improved stability of the catalyst. The
synergy between the supported Pt nanoparticles and In2O3 also
balances the hydrogen activation and the density of the surface
oxygen vacancies in In2O3, which lead to the high activity for
CO2 hydrogenation and enhanced stability of the Pt/In2O3
catalyst.
Pan et al. prepared a Pt/film/In2O3 catalyst with highly
dispersed Pt nanoparticles, which achieved CO2 conversion of
37.0% and methanol selectivity of 62.6% at 1 atm and 30 oC by
using a dielectric barrier discharge plasma reactor.[40] The high
dispersion of Pt nanoparticles and the film, which suppresses
the aggregation of Pt nanoparticles and transfers the electrons
from the catalyst to CO2, promotes the adsorption of CO2 and
enhances the hydrogenation of CO2 to methanol. As described
by the FTIR spectra, Pt/film/In2O3 has a higher ability in
producing methoxy species from CO2 hydrogenation, which
could also be an origin for the enhanced methanol production of
Pt/film/In2O3. This would be helpful for efficient methanol
production from CO2 hydrogenation under atmospheric
pressure and room temperature.
4.3 Au/Ag-based catalysts
Au is also beneficial for methanol synthesis. Au supported on
various metal oxide such as ZnO,[41] ZrO2,[41a, 42] CeO2,[41b]
TiC,[43] ZnO-TiO2,[44] ZnO/ZrO2,[45] CeOx/TiO2[46] are active for
methanol formation. Smaller Au particles are shown to give
higher methanol productivity.[42, 44] Besides the Au nanoparticle
size, the activity of Au catalysts also strongly depends on the
support.
Behm et al. investigated the activity and selectivity of different
Au catalysts with an almost identical Au particle size (Au/TiO2,
Au/ZrO2, Au/ZnO, and Au/Al2O3) for methanol formation at 5 bar
and temperatures between 220oC and 240oC.[41a] The results
show that the activity decreases in the order of Au/ZrO2 >
12
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10.1002/cssc.202002054
Au/ZnO > Au/TiO2 > Au/Al2O3. The Au/ZnO catalyst exhibits
high selectivity (> 50%). The difference in activity and selectivity
for various catalysts is attributed to the nature of the support.
Konsolakis et al. reported that Au nanoparticles supported on
ZnO and CeO2 were highly selective towards methanol. TiO2-
and Fe2O3-based catalysts almost catalyze exclusively the
production of CO and/or CH4 with high CO2 conversion, while
Au/Al2O3 is practically inactive in the investigated temperature
range (200 oC - 350oC).[41b] It is obvious that Au NPs must be
combined with particular reducible metal oxides (such as CeO2
or ZnO) to obtain high methanol formation rates. These results
imply the existence of SMSI (either geometric or electronic)
under working conditions, which are able to tune the local
surface chemistry of active sites finely. The synergistic
Accepted Manuscript
interaction between oxygen vacancies on the Au-CeO2 (Au-
ZnO) interface and SMSI are accounted for the enhanced
performance.
Chen et al. found that the electronic polarization at the metal-
oxide interface of Au nanoparticles, which were anchored and
stabilized on CeOx/TiO2 substrate, promoted CO2 adsorption
and activation, and further improved the selectivity toward
methanol.[46] This illustrates the importance of localized
electronic properties and structure in catalysis for CO2
hydrogenation.
The research of Ag catalysts in methanol synthesis from CO2
hydrogenation is relatively less. In general, Ag is used as a
promoter in catalysts to play a key role for CO2 hydrogenation
to methanol.[45, 47] Grabowski et al. investigated the polymorphic
ZrO2 phases and the Ag electronic state in Ag/ZrO2 and
Ag/ZrO2/ZnO catalysts.[48] The oxygen vacancies existing in the
ZrO2 sublayer stabilize the thermodynamically unstable t-ZrO2
phase and the Ag+ cations, which act as the active phase for
methanol synthesis. The methanol formation rate increases
with increasing t-ZrO2 phase and Ag+ content.
5. Bimetallic Catalysts for CO2 Hydrogenation
to Methanol
Bimetallic catalysts such as alloys and intermetallic
compounds (IMCs) have emerged as an important kind of
catalysts for CO2 hydrogenation to methanol, due to the tunable
electronic, geometric, and chemical properties caused by
strong synergies.[9] Precious metal-based alloy catalysts hold
the potential of low-temperature hydrogenation capacity owning
to the alloy active sites. But the atomic ratios of alloys are easily
affected by the reduction conditions and metal composition so
that it is difficult to obtain an ideal alloy structure with uniform
atomic ratios. The IMCs provide a potential solution to this
issue and can form a stable bimetallic catalysts with
controllable and homogeneous atomic ratios.[49] IMCs have
unique advantages: (i) uniform, stable geometric and electronic
structures; (ii) electronic structure of active metals can be
modified by neighboring atoms.[50] Therefore, IMCs have
attracted extensive attention for methanol synthesis. Notably,
PdGa,[51] PdIn,[30d, 52] and NiGa[53] IMCs have been reported as
highly active and selective catalysts for CO2 hydrogenation to
methanol.
Manrique et al studied that the promotion of Pd with Ga and
Zn in the hydrogenation of CO2 to methanol.[51a, 51b] Mono and
intermetallic catalysts (Pd/SiO2, PdeGa/SiO2 and PdeZn/SiO2)
with similar average metal particle sizes (between 9 and 12 nm)
were synthesized via incipient wetness impregnation to
ChemSusChem
REVIEW
eliminate the cluster size effects of Pd. The catalytic results
shows the selectivity to methanol increases from 3% for
Pd/SiO2 to 12% for Pd-Ga/SiO2 and 30% for Pd-Zn/SiO2. The
activity increase towards the methanol synthesis probably
results from the formation of intermetallic compounds Pd2Ga
and PdZn, as evidenced by a combination of XRD, XPS and
CO-IR adsorption experiments. Recent work further reveals that
the existence of bimetallic Pd-Ga sites is responsible for the
increase in activity towards methanol synthesis.[51b] The
separate phases of Pd and Ga (Pd and Ga2O3) are not as
active for methanol formation. A significant increase in the
methanol formation rate and selectivity is observed after
promotion of Pd with Ga comparing to those of the unpromoted
SiO2-supported Pd catalyst. Characterization by quasi in situ
XPS, XRD, CO adsorption DRIFTS and TEM-EDS
demonstrates that the primary cause for the increase in activity
towards methanol synthesis is the formation of intermetallic
compounds of Pd2Ga, rather than a cooperative mechanism
between Pd and Ga2O3. The variation of the Pd/Ga ratio
defines the surface concentration of Ga2O3, where the
deposition of excess Ga in its oxidized form on the mono or
bimetallic phases of the catalysts inhibits their catalytic
performance. Operando DRIFTS characterization shows the
formation of bidentate formate species on the metallic Pd or Pd-
Ga sites acting as intermediates in the hydrogenation of CO2 to
methanol.
Behrens et al. synthesized supported PdZn, Pd2Ga, and Pd
catalysts via reductive decomposition of ternary hydrotalcite-like
compounds.[51c] They observe that the PdZn and Pd2Ga IMCs
are present in the form of nanoparticles with an average
diameter of 6 nm or less after reducing the PdZnAl and
PdMgGa precursors. The monometallic Pd nanoparticles is
obtained by reducing the analogous PdMgAl precursors without
second reducible species. The catalytic properties of Pd are
positively affected by PdZn and Pd2Ga IMCs formation for
methanol synthesis. The PdZnAl and PdMgGa show similar
steady-state activities for methanol synthesis of 17.6 and 18.7
μmol/(gcat·min), respectively. These activities amounted to
nearly 30 times the methanol synthesis activity of 0.65
μmol/(gcat·min) for PdMgAl. The presence of Zn and Ga also
improves the selectivity to methanol.
Figure 6. HRTEM image of the postreaction Pd/β-Ga2O3 catalyst (inset: [101]
zone axis simulation image of a β-Ga2O3 crystal). Reproduced with
permission from Ref. [51d]; copyright 2012, Elsevier.
13
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10.1002/cssc.202002054
Collins et al. found that Ga-Pd bimetallic particles formed
under reductive atmosphere above 523 K using quasi in-situ
high resolution transmission electron microscopy, as shown in
Fig. 6.[51d] But the Ga-Pd bimetallic particles were unstable and
suffered from dramatic and extensive encapsulation by Ga2O3
upon air exposure. The Ga-Pd bimetallic particles mainly
dissociate and spill over H to the gallium sites, where the
stepwise hydrogenation of reaction intermediates takes place
from (bi)carbonate, formate, methoxy to methanol. The
bimetallic sites also hamper methanol decomposition and CO
production. Similarly, Cardona-Martinez et al. reported that the
catalytic activity of methanol synthesis improved with the
increasing amount of Pd2Ga intermetallic compound using Pd
catalysts supported on Ga2O3 with various crystalline
Accepted Manuscript
phases.[49e] The Pd2Ga content varies depending on the Ga2O3
polymorphs. The catalytic activity is also influenced by the CO2
adsorption properties on the different Ga2O3 polymorphs.
Yang et al. studied the reaction mechanism of methanol
synthesis over the intermetallic PdIn catalyst through DFT
calculations and microkinetic analysis.[52] They found that
methanol formation occurs via HCOO → HCOOH → H2COOH
→ CH2O + OH → CH3O + OH → CH3OH(g) + H2O(g) on both
surfaces. The dominant surface species is HCOO. The rate-
controlling transition state for methanol formation is HCOOH
hydrogenation on PdIn(110), while on PdIn(211) it changes
from H2COOH dissociation to HCOOH hydrogenation with
increase in temperature.
Ni-Ga IMCs have been identified as catalysts with interesting
activity, selectivity, and stability for ambient pressure CO2
hydrogenation to methanol. As shown in Fig. 7a, Nørskov et al.
first predicted the catalytic activity of Ni-Ga IMCs by
computational methods and the descriptor-based analysis of
the process, and further compared with Cu-Zn, Cu, Ni, and Pd
as benchmark catalysts.[53a] Then, they synthesized and tested
a series of Ni-Ga catalysts with different Ni:Ga ratios supported
on silica. The results show that Ni5Ga3/SiO2 expresses
particularly activity and selectivity. The Ni5Ga3/SiO2 displays
same or better methanol synthesis activity, as well as
considerably lower production of CO compared with
conventional Cu/ZnO/Al2O3 catalysts (Fig. 7b,c). The difference
can be understood considering that the gallium-rich sites
facilitate methanol synthesis while the nickel-rich sites promote
RWGS reaction (and methanation) until they become self-
poisoned by CO and carbon, respectively. As the Ni5Ga3 IMCs
have the most active and selective composition, subsequent
work mainly focuses on the synthesis and characterization of
this active phase.[53b] The study demonstrates that the desired
phase and composition of Ni-Ga IMCs are formed via direct
reduction of the corresponding nitrates under dynamic
hydrogen atmosphere. Upon decomposition of nitrates, highly
dispersed Ni(II) nanocrystallites serve as centers for the further
reduction of the nickel and gallium oxides. Metallic gallium is
incorporated into the nickel lattice to form an intermetallic phase.
A recent work reveals that the Ga-oxide shell surrounding the
metallic core is formed via Ga migrating from the subsurface
region to the surface of the nanoparticles when exposed to
air.[53c] The surface oxidized Ni5Ga3 is more active than fully
reduced Ni5Ga3 for methanol synthesis. The resultant Ga-rich
surface and the synergy between remaining Ga2O3 and Ni-Ga
IMCs make surface oxidized Ni5Ga3 more active than fully
reduced Ni5Ga3 for methanol synthesis.
ChemSusChem
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Figure 7. (a) Theoretical activity volcano for CO2 hydrogenation to methanol.
Turnover frequency (TOF) is plotted as a function of ΔE0, relative to Cu(211).
ΔE0 for the stepped 211 surfaces of copper, nickel and palladium is depicted
as open black circles, and CutZn is depicted in orange. ΔE0 for Ni-Ga
intermetallic compounds is depicted in red. Closed circles indicate nickel-rich
sites, open circles gallium-rich sites and half-open circles mixed sites.
Reaction conditions are 500 K, 1 bar, and a CO2:H2 ratio of 1:3. (b) Yield of
methanol of a series of NixGay catalysts compared with Cu/ZnO/Al2O3 as a
function of temperature at atmospheric pressure. (c) Comparison of the CO
to methanol ratio of Cu/ZnO/Al2O3 with Ni5Ga3. Reaction conditions: Gas
composition: H2/CO2 = 3:1, GHSV = 6000 h-1. Reproduced with permission
from Ref. [53a]; copyright 2014, Springer Nature.
Shen et al. investigated the reaction mechanisms of CO2
hydrogenation to methanol over Ni-Ga IMCs using DFT
calculations.[53d, 53e] The study shows that all the intermediates
involved in the hydrogenation process, except for the O atom,
prefer to bond with surface Ni sites along the step edge. The
dissociative adsorption of H2 on the Ga3Ni5(221) surface is
spontaneous and highly exothermic. Moreover, the introduction
of Ga indeed promotes H2 dissociative adsorption on the
surface, which is verified by the projected density of states
analysis.[53d] In recent work, they studied the impacts of the size
and support of Ga-Ni clusters, including Ga3Ni5, Ga6Ni10,
Ga12Ni20, Ga15Ni25, Ga24Ni40 nanoclusters, and γ-Al2O3/SiO2
supported Ga6Ni10, on CO2 hydrogenation to methanol at
electronic and molecular levels using DFT calculations.[53e] The
results indicate that cluster size has a significant impact on the
activation barrier of the rate-limiting step of hydrogenation
process. Among the studied Ga-Ni clusters, the Ga6Ni10 cluster
has the lowest activation barrier resulted from the d-band
center location and the exposed active sites. Meanwhile, the
support with increasing electron transfer abilities is preferable
for decreasing activation barriers.
6. Mixed Oxide Catalysts for CO2
Hydrogenation to Methanol
In recent years, mixed oxide catalysts represented by solid
solutions and In2O3-based oxides are emerging as active and
cost-effective catalysts and developing rapidly for CO2
hydrogenation to methanol. The MaZrOx (Ma = Zn, Ga, Cd) solid
solution catalysts and indium-based oxide catalysts as well as
Co-based oxide catalysts have been investigated in the thermal
hydrogenation of CO2 to methanol.
6.1 Solid Solution Catalysts
Wang et al. reported that the binary metal oxide ZnO-ZrO2 in
the solid solution state was an active catalyst for CO2
hydrogenation to methanol with high selectivity and stability.[7a]
As shown in Fig. 8a, the CO2 conversion of 13% ZnO-ZrO2 is
14
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10.1002/cssc.202002054
about 1.3 and 14 times higher than those of ZnO and ZrO2,
respectively. The methanol selectivity increases from no more
than 30% for ZnO or ZrO2 to more than 80% for 13% ZnO-ZrO2.
The catalytic activity of 13% ZnO-ZrO2 prepared by co-
precipitation is also about six times higher than that of the
mechanically mixed ZnO and ZrO2 (Zn/(Zn+Zr)=13%), which
indicates that there is a strong synergetic effect between these
two components in the CO2 hydrogenation.
Accepted Manuscript
Figure 8. Catalytic performance of the ZnO-ZrO2 catalyst. (a) Dependence of
catalytic performance at 320°C on the Zn/(Zn + Zr) molar ratio. Inset: purple,
normalized activities for ZnO, 13% ZnO-ZrO2, and ZrO2 by specific surface
area; dark yellow, normalized activities for mechanically mixed ZnO and ZrO2
in the same composition. (b) Catalytic performance at the reaction
temperatures from 200° to 380°C with H2/CO2 = 3:1 and 4:1. (c) Catalyst
stability test in 550 hours. (d) Catalyst stability toward the S-containing
molecules (50 ppm H2S or SO2 in Ar) and annealing. Reaction conditions: 5.0
MPa, H2/CO2 = 3:1, 320°C, GHSV = 24000 ml/(g hour), using a tubular fixed-
bed reactor with the 13% ZnO-ZrO2 catalyst. Reproduced with permission
from Ref. [7a]; copyright 2017, Science.
As shown in Fig. 8b, CO2 conversion increases while
methanol selectivity decreases with rising reaction
temperatures. Methanol selectivity can still be kept at 86% with
excellent CO2 single-pass conversion of 10% even though the
temperature is increased to 320oC. Higher pressure, space
velocity, and H2/CO2 ratio are beneficial to the methanol
selectivity. More importantly, this catalyst presents high stability
for at least 500 hours on stream, resistant to sintering at high
temperature, and no apparent deactivation in the presence of
sulfur-containing species (SO2 or H2S) (Fig. 8c,d), which makes
the catalyst viable in industrial processes.
XRD patterns show that there is no ZnO phase. At the same
time, the phase of ZrO2 changes from monoclinic to tetragonal
when ZnO (5 to 33%) is incorporated, indicating that the ZnO-
ZrO2 solid solution might form (Fig. 9a). From Fig. 9b, the
interplanar spacing of 13% ZnO-ZrO2 is ca. 0.294 nm, which is
attributed to the (011) surface of tetragonal ZrO2. As the ionic
radius of Zn2+ (0.74 Å) is smaller than that of Zr4+ (0.82 Å), the
interplanar spacing would decrease when Zn2+ is incorporated
into the lattice of ZrO2. This is confirmed by XRD as the
diffraction peak corresponding to the (011) plans of ZrO2 shifts
towards high angle with the increasing amount of Zn added
from 5 to 33%. The element distribution analysis proves that Zn
is highly dispersed in ZrO2 (Fig. 9c). XPS results also show that
the Zn is relatively rich on the surface since Zn concentration in
the surface region is higher than the theoretical value (Fig. 9d).
These characterization results further affirms that ZnO-ZrO2 is
in a solid solution state with Zn incorporating into the ZrO2
ChemSusChem
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lattice, as schematically depicted in Fig. 9e. Combining detailed
characterization with CO2-TPD and H2-D2 exchange reaction, it
could be concluded that the satisfactory catalytic performance
results from the synergetic effect between the Zn and Zr sites
and the simultaneous activation of H2 and CO2 on the
neighboring Zn and Zr sites.
Figure 9. Structural characterization of the ZnO-ZrO2 catalyst. (a) XRD
patterns of ZnO-ZrO 2. (b) High-resolution transmission electron-microscopy.
(c) aberration-corrected scanning TEM-high-angle annular dark-field images
and element distribution of 13% ZnO-ZrO2. (d) Zn concentration in the
surface region of ZnO-ZrO2 measured by XPS. (e) Schematic description of
the ZnO-ZrO2 solid solution catalyst model. Reproduced with permission from
Ref. [7a]; copyright 2017, Science.
In situ DRIFTS and DFT calculations were performed to
understand the reaction mechanisms. In situ DRIFTS results
indicate that the surface HCOO* and H3CO* species on the
13% ZnO-ZrO2 solid solution catalyst can be hydrogenated to
methanol. DFT calculations show that CO2 hydrogenation to
methanol on the surface of ZnO-ZrO2 is through the formate
pathway rather than the CO pathway, as illustrated in Fig. 10.
H2 is adsorbed and dissociated on the Zn site, and CO2 is
adsorbed on the coordination unsaturated Zr site. The CO2*
transforms into HCOO* species via hydrogenation. The HCOO*
species is further hydrogenated to the H2COO* species. The
H2COO* species is protonated by an OH* group and forms
H2COOH* species, in which the C-O bond is cleaved and
thereby generating H2CO* and OH* bound on Zr and Zn sites,
respectively. The generated H2CO* is hydrogenated to H3CO*
and methanol forms from the H3CO* protonation.
15
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10.1002/cssc.202002054
Figure 10. DFT calculations. Reaction diagram [energy (E) and Gibbs free
energy (G) at a typical reaction temperature of 593 K] of CO2 hydrogenation
to methanol on the (101) surface of the tetragonal ZnO-ZrO2 model. Adapted
with permission from Ref. [7a]; copyright 2017, Science.
To investigate the general feature of solid solution catalysts
for CO2 hydrogenation, the authors investigated the ZnO-based
and ZrO2-based composite oxide catalysts and found that there
was a class of mixed-metal oxides, besides ZnZrOx, showing
good performance.[7c]
Accepted Manuscript
Figure 11. The methanol selectivities and CO2 conversions for (a)
11.5%ZnMbOx (Mb=Mg, Ca, Sc, Ti, V, Cr, Mn, Ga, Y, Zr, Cd, In, Sn, La, Ta,
Pb) and (b) 11.5%MaZrOx (Ma=Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Zn, Ga, Y, Mo,
Cd, In, La, Ce) catalysts. The reaction conditions: H2/CO2 = 3/1, 24000h−1, 2
MPa, 300 °C. Reproduced with permission from Ref. [7c]; copyright 2019,
American Chemical Society.
As shown in Fig. 11, most of ZnMbOx (Mb = Mg, Ca, Sc, Ti, V,
Cr, Mn, Ga, Y, Zr, Cd, In, Sn, La, Ta, Pb) catalysts show higher
methanol selectivity than ZnO (29%), except ZnCrOx and
ZnTaOx. The CO2 conversion of ZnMbOx strongly depends on
the type of Mb, only ZnTiOx, ZnCrOx, ZnGaOx, ZnZrOx, and
ZnInOx display higher CO2 conversion than ZnO (1.1%). For
MaZrOx (Ma = Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Zn, Ga, Y, Mo, Cd,
In, La, Ce) catalysts, most of them represent similar CO2
conversion and methanol selectivity to ZrO2 (X(CO2) = 0.14%,
S(CH3OH) = 26%). However, the CdZrOx and GaZrOx catalysts,
besides ZnZrOx catalyst, also exhibit good catalytic
performances, which indicates that there is a versatile feature
of solid solution catalysts for CO2 hydrogenation to methanol.
ChemSusChem
REVIEW
Figure 12. The CO2 conversions and methanol selectivities on (A) CdO,
11.5%CdZrOx, and ZrO2, (B) Ga2O3, 11.5%GaZrOx, and ZrO2. The effect of
reaction temperature and pressure on the CO2 conversions (C) and methanol
selectivities (D) for 11.5%CdZrOx and 11.5%GaZrOx catalysts. The standard
reaction conditions: H2/CO2 = 3/1, 24000h–1, 2 MPa, 300 oC. Reproduced
with permission from Ref. [7c]; copyright 2019, American Chemical Society.
There is no doubt that MaZrOx (Ma = Cd, Ga) catalysts show
an obvious enhancement in catalytic activity and methanol
selectivity, compared with the individual oxides (Fig. 12). When
the temperature increases from 280oC to 360oC, the CO2
conversion increases, while the methanol selectivity decreases
possibly resulting from the intensification of the RWGS reaction.
Both the CO2 conversion and methanol selectivity increase with
the reaction pressure.
XRD, high-resolution transmission electron microscopy, high-
angle annular dark-field scanning transmission electron
microscopy, and low-energy ion scattering spectrum prove that
MaZrOx (Ma = Cd, Ga) forms solid solution structure with the
incorporation of Ma (Ma = Cd, Ga) into the ZrO2 lattice and
affords two sites (Ma and Zr) on the surface. CO2-TPD results
deduce that the Zr site is mainly responsible for CO2 adsorption
and activation. H2-D2 exchange reaction concludes that there is
a strong synergetic effect in the H2 activation between the two
sites, (Ma = Cd, Ga) and Zr in MaZrOx catalysts. XPS results
show that the oxygen vacancy contents of MaZrOx (Ma = Cd, Ga)
are much more than that of individual ZrO2 (31.6%(31.2%) vs
12.4%), which is attributed to the additional oxygen vacancies
created by the introduction of Ma2+/3+ (Ma = Cd, Ga) cations into
the matrix of ZrO2. Based on the results of CO2-TPD, XPS and
H2-D2 exchange reaction, the electronic property of Ma (Cd, Ga)
is modified via the interaction between Ma and Zr in the solid
solution structure, which enhances the ability for activation of
H2 and further improves the selectivity and activity for CO2
hydrogenation to methanol. DFT calculations also suggest that
two different surface sites of the MaZrOx (Ma = Cd, Ga) are
responsible for CO2 and H2 activation, respectively, which is in
good agreement with the CO2-TPD, XPS, and H2-D2 exchange
results. In summary, solid solution catalysts offer alternatives to
metal-based catalysts and opportunities in developing active,
selective, and cost-effective catalysts.
Recently, Zhan et al. prepared MxOy-ZrO2 (M = Zn, Co, or Cu)
solid solutions by using Schiff base to bridge Zn2+, Co2+, and
Cu2+ into the robust UiO-66 frameworks and control the amount
of doping metal ions.[54] The CO2 hydrogenation reaction results
show that Co3O4-ZrO2, CuO-ZrO2, and ZnO-ZrO2 give products
towards CH4, CO, and methanol, respectively. Cao et al. found
that the ZnO/t-ZrO2 catalyst obtained from the micro-reaction
synthesis method provides more uniform solid solution structure
and abundant oxygen vacancy defects. This catalyst exhibits
excellent activity and thermal stability as well as regeneration
performance.[55] Witoon et al. reported that the calcination
temperatures of dried ZrO2 support influenced the phase,
crystallinity, and adsorptive properties of ZnOx/ZrO2 solid
solution catalysts prepared by impregnation method.[56] It could
16
This article is protected by copyright. All rights reserved.
10.1002/cssc.202002054
be seen that the catalytic properties of solid solutions are
strongly affected by the surface properties and the crystal
structures, which highly depends on the preparation methods.
6.2 In2O3-based Oxide Catalysts
Recently, In2O3 and In2O3-based oxide catalysts have
emerged as an active and selective catalyst for CO2
hydrogenation to methanol, with prospects for industrial
deployment.[57-61]
Ge et al demonstrated that the oxygen vacancy on the In2O3
(110) surface assisted CO2 activation and hydrogenation and
stabilized the key intermediates involving in methanol formation
by periodic DFT calculations.[57a] Liu et al confirmed that In2O3
Accepted Manuscript
alone was an active and selective catalyst for CO2
hydrogenation to methanol.[57b] Pérez-Ramírez et al found that
the apparent activation energy determined experimentally for
CO2 hydrogenation to methanol over bulk In2O3 was lower than
the one for the RWGS reaction by elucidating the mechanistic
and kinetic fingerprints in detail, which is in line with the high
methanol selectivity observe.[57c] M5ller and coworkers probed
the structural evolution of In2O3 nanoparticles with time on
stream by operando XAS-XRD, and the results showed that
In2O3-x was the active phase while the catalyst deactivation was
due to the formation of In0.[57d] More recently, Sun and Gao et al
successfully designed a much higher performance In2O3
nanocatalyst for CO2 hydrogenation to methanol under the
guide of computational study.[57e] The authors first performs
extensive DFT calculations to establish the catalytic
mechanisms of the In2O3 catalyst during CO2 hydrogenation to
methanol and to CO by identifying the preferred pathways and
rate-determining steps. The computational results show that the
hexagonal-phase In2O3(104) surface has the best catalytic
performance in terms of reactivity and selectivity. According to
the computational results, authors prepare pure cubic-phase
In2O3 and hexagonal-phase In2O3 nanoparticles with different
morphologies and evaluate their performance for CO2
hydrogenation to methanol. The experimental results
demonstrate that the catalytic performance is related to the
shape of In2O3 nanoparticles due to their different phases and
exposed facets. As shown in Fig.13, the hexagonal-phase In2O3
nanomaterial with high proportion of the exposed (104) surface
displays the highest activity and methanol selectivity with high
catalytic stability, confirming the theoretical prediction. Under
the reaction conditions of 300 oC, 5.0 MPa, 9000 mL/(gcat−1·h−1),
and H2/CO2 = 6, methanol selectivity achieves 92.4% with a
single-pass CO2 conversion of more than 17%. This work may
open new avenues toward computer-aided rational design of
efficient catalysts for methanol synthesis.
Figure 13. Catalytic performance of various In2O3 for CO2 hydrogenation. (A)
CO2 conversion and methanol selectivity over In2O3 with different crystal
phases and morphologies. Insert: Normalized activities for cubic-phase In2O3-
S, cubic-phase In2O3-P, hexagonal-phase In2O3-L, and hexagonal-phase
In2O3-R by specific surface area after pretreatment in pure Ar at 300°C for 44
ChemSusChem 10.1002/cssc.202002054

REVIEW
hours. (B) Stability test of hexagonal-phase In2O3-R. Standard reaction suppresses CO2 dissociation and stabilizes H2COO species on
conditions: 300°C, 5.0 MPa, 9000 ml/(gcat−1·h−1), H2/CO2/N2 = 73/24/3.
the surface of In2O3 catalyst.
Reproduced with permission from Ref. [57e]; copyright 2020, Science.
Witoon et al. found that the phase, crystallinity, pore structure,
morphology, electronic properties as well as adsorptive
properties of GaxIn2−xO3 catalysts could be modified by tuning
Pérez-Ramírez et al. developed a highly efficient In2O3/ZrO2
the Ga/In ratio.[60] Incorporation of Ga into the In2O3 lattices at x
catalyst for the hydrogenation of CO2 to methanol with very
= 0.4 (Ga0.4In1.6O3) maximizes the methanol yield between
high selectivity to methanol, outstanding activity, and
340oC and 360oC, which is attributed to the increased binding
remarkable stability during 1000 h on stream under industrially
energy of CO2 and H2 on the catalyst surface. Gascon et al.
relevant conditions, as shown in Fig. 14.[58a] In-depth
reported Co-supported In2O3−x films preferentially yielded
characterization confirms that the oxygen vacancies act as
methanol with high selectivity (> 80%) at conversion levels
active sites. The creation and annihilation of oxygen vacancies
close to thermodynamic equilibrium, rather than CO and
are the key steps in the catalytic cycle. The number of active
methane.[61]
oxygen vacancies can be increased by adding CO to the feed
gas or using the electronically interacting ZrO2 support, which

Accepted Manuscript
6.3 Co-based Oxide Catalysts
also prevents the sintering of the In2O3 phase to maintain
excellent stability. Recent work revealed that the monoclinic
Co-based oxide catalysts are discovered as a highly selective
ZrO2 presented two distinctive promotional effects as the
and stable catalyst for green methanol production from CO2.
support for In2O3 in the hydrogenation of CO2 to methanol,
Somorjai et al. reported a highly active and selective MnOx/m-
which was identified by detailed characterization via thermal,
Co3O4 catalyst for methanol synthesis from CO2
sorption, microscopy, and spectroscopy techniques and kinetic
hydrogenation.[62] The MnOx/m-Co3O4 catalyst is composed of
analysis.[58b] On the one hand, the epitaxial alignment of In2O3
manganese oxide nanoparticles supported on mesoporous
occurs on the monoclinic ZrO2 support, which ensures high
spinel cobalt oxide. This catalyst exhibits higher methanol yield
dispersion of the active oxide. On the other hand, less favorable
than the individual catalyst components. Catalyst
lattice matching between In2O3 and monoclinic ZrO2 generates
characterization results show that the active phase of the
tensile strain, which favors the formation of more and possibly
catalyst is MnO NPs, which uniformly disperses over grains of
diverse oxygen vacancies on In2O3. Han et al. demonstrated
metallic cobalt cores with thin cobalt oxide shells. The
highly tunable selectivity in CO2 hydrogenation under
MnOx/CoO interface facilitates activity enhancement towards
industrially relevant conditions using Inx/ZrO2 catalysts by
methanol, which is verified by an inverted hybrid catalyst of
varying the indium loading in a broad range, which was related
CoOx NPs supported on mesoporous MnO2. Subsequently, Yu
to different indium species on the surface.[58c] Lobo et al.
et al. found that manganese incorporated into the lattice of
reported that the Y or La-promoted In2O3/ZrO2 catalysts had
Co3O4 spinel could markedly increase the methanol selectivity
about 20% higher methanol selectivity than the non-promoted
due to the synergistic effect between manganese and cobalt
catalyst.[58d]
surface species.[63] The enhanced methanol selectivity is
attributed to the higher surface concentration of manganese,
increased total basicity, and higher surface area. Recently,
Wang and Xiao et al investigated that how cobalt could be
optimized to give efficient catalysts for methanol production by
choice of a silica support.[64] The authors find that the superior
catalysts for CO2 hydrogenation to methanol are obtained by
optimizing the cobalt-to-silica ratio. The amorphous silica acts
as support and ligand to modify the cobalt species by
constructing abundant Co-O-SiOn interfaces. The Co-O-SiOn
Figure 14. (a) Methanol STY for different supported catalysts after 4 h on
stream. (b) Evolution of the methanol STY with time on stream (TOS) over interfaces stabilize spectroscopically identified *CH3O
In2O3/ZrO2 and Cu-ZnO-Al2O3. c) HRTEM micrograph of the In2O3/ZrO2 intermediates and favor the reactivity of *CH3O intermediates
catalyst obtained after 4 h on stream. Reaction conditions: T=573 K, P=5.0 undergoing hydrogenation to methanol rather than the C-O
MPa, H2/CO2=4:1, and GHSV=16000 h-1. Reproduced with permission from
dissociation associated with hydrocarbon formation (Fig. 15).
Ref. [58a]; copyright 2016, John Wiley and Sons.
This work indicates that the reaction pathways of CO2
hydrogenation to methanol on the supported cobalt catalysts
can be tuned by optimizing the catalyst structures, which may
Yu et al. carried out the density functional theory study to
open the way to new control of catalysts by supports and help
investigate the mechanism of methanol synthesis from CO2 and
guide the design of improved catalysts for CO2 selective
CO hydrogenation on the defective ZrO2 supported In2O3 (110)
hydrogenation to methanol.
surface.[59] The calculation results demonstrate that methanol
synthesis from CO2 hydrogenation mainly proceeds via the
HCOO route. The hydrogenation of HCOO to H2COO species
is the rate-determining step for the HCOO route, while the
direct dissociation of CO2 to CO is kinetically and energetically
prohibited. In contrast, CO hydrogenation to methanol is much
facile. The rate-determining step is the formation of H3CO
species on the vacancy site. This explains the promotional
effect of CO co-feeding on the activity of CO2 hydrogenation to
methanol on In2O3 catalyst. Besides, the ZrO2 support

17
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ChemSusChem
REVIEW
Figure 15. Synthesis and catalysis strategies of Co@Six catalysts. The
procedures with cobalt phyllosilicates as intermediates for synthesizing
Co@Six. Within the highlighted square, the CO2-to-methanol transformation
on Co@Six catalysts. Adapted with permission from Ref. [64]; copyright 2020,
Springer Nature.
7. Summary and Perspectives
Combining the captured CO2 and hydrogen produced from
renewable energy to synthesize green methanol, as highlighted
as “methanol economy”[14] and named as “liquid sunshine”[13],
has great potential for mitigating energy crises and climate
change. In the past decades, there has been considerable
progress in developing various heterogeneous catalysts for
CO2 hydrogenation to methanol. Among metals, alloys or
intermetallic compounds, and metal oxide heterogeneous
catalysts, the non-Cu based catalysts with good performance
and high stability are developing rapidly. The supported metal
catalysts (Pd, Pt, Au, Ag) can achieve higher methanol
selectivity at low temperatures, depending on the support types
and preparation methods as well as metal precursors, but face
the problems of low activity and high cost. Although alloys or
IMCs catalysts have some advantages in tunable electronic,
geometric, and chemical properties, alloys or IMCs catalysts
with ideal and uniform atomic ratios are difficult to obtain since
the atomic ratios are easily affected by the reduction conditions
and metal composition of the catalyst. The newly emerging
mixed oxide catalysts represented by MaZrOx (Ma = Zn, Ga, Cd)
solid solution catalysts and indium-based hybrid oxide catalysts
as well as Co-based hybrid oxide catalysts present higher
methanol selectivity and catalytic activity as well as good
stability, which are promising for the conversion of CO2 to
methanol in industry.
The selective conversion of CO2 to methanol over
heterogeneous catalysis utilizing renewable hydrogen has
being attracted great attention. Although various heterogeneous
catalysts have been investigated, many inherent issues remain
to achieve large-scale industrialization of methanol synthesis
from CO2. Challenges always coexist with opportunities,
several issues merit particular attention in the near future.
(1) More attention to the fundamental study regarding the
nature of the active sites and interactions between active
components, promoter, and supports are encouraged. There is
great potential for the improvement of activity and selectivity of
the catalyst via tuning catalyst composition and engineering
surface structures. The selection of suitable precursors of
active components and preparation methods are also important.
With the development of nanoscience and nanotechnology,
designing catalysts with well-defined structures in nanoscale
18
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10.1002/cssc.202002054
would be feasible for achieving higher catalytic performance.
(2) The understanding of reaction mechanisms and the
identification of active sites and key reaction intermediates on
the surface as well as their evolution under reaction conditions
are still needed to be studied in depth. It could be learned from
the methanol synthesis from CO hydrogenation and CO2
hydrogenation over the Cu-based catalysts. In order to obtain
the true reaction kinetics results under reaction conditions, in
situ and operando techniques with high sensitivity in detecting
active sites and reaction intermediates should be employed.
Meanwhile, study on model catalytic systems is also necessary
to simplify the research procedure, as it could improve the
understanding of the active sites and structure-activity
relationships.
Accepted Manuscript
(3) Although high temperature facilitates CO2 activation, CO
is also competitively produced via RWGS reaction, leading to
low methanol selectivity. In view of thermodynamics, methanol
formation is favored at lower temperatures. Therefore, catalysts
with methanol synthesis ability at low temperatures as well as
high activity and selectivity are highly expected. This requires
overcoming CO2 activation energy barriers at low temperatures
and designing catalysts system based on theoretical and
experimental studies.
(4) An excellent catalyst for CO2 hydrogenation to methanol
should possess good stability besides high activity and
selectivity. This mainly reflects in the resistance to water and
sulfur-containing molecules in the stream as well as sintering at
higher temperatures. Water is the by-product in methanol
synthesis from CO2 hydrogenation. Sulfur-containing molecules
always present in CO2 from flue gas sources produced from
coal or biomass burning. The catalysts easily suffer from
serious deactivation with water and sulfur-containing molecules
due to sintering and poisoning at the reaction conditions. The
catalysts easily suffer from serious deactivation with water and
sulfur-containing molecules due to sintering and poisoning at
the reaction conditions, especially the supported metal catalysts.
For the mixed oxide catalysts, the effect of water on the
catalytic activity is rarely reported. Therefore, research about
this aspect needs to be further explored deeply. Although In2O3
exhibits better water tolerance upon water addition into the
feeds and long-term stability in the presence of water,[58a, 30c]
and ZnO-ZrO2 shows no deterioration in methanol selectivity for
more than 500 hours on stream,[7a] more in-depth
understanding of reaction mechanisms and active sites would
be required for their further development and implementation.
More attention should be paid to designing catalysts with
hydrophobic properties to remove water under reaction
conditions, which may not only protect catalysts from
deactivation or sintering but also shift the equilibrium to obtain
higher methanol yield. Alternatively, membrane reactor could
satisfy this requirement by selectively removing condensable
products and shifting equilibrium limited reaction toward
desirable products. But it also faces the challenges from
selective water permeation and withstand harsh reaction
conditions such as high pressure based on good methanol yield.
Zeolite-based membrane is a potential candidate in this regard
since its thermal and chemical stability. Moreover, it has been
proven to achieve higher CO2 conversion and methanol yield.[65]
As for the stability of the catalysts toward sulfur-containing
molecules, ZnO-ZrO2 exhibits sulfur tolerance making the
catalyst viable in industrial processes, it could bee seen that the
mixed oxide catalysts are superior to supported metal-based
catalysts.
ChemSusChem
REVIEW
Acknowledgements
This work was supported by grants from National Key R&D
Program of China (2017YFB0702800), Transformational
Technologies for Clean Energy and Demonstration
(XDA21090202), and National Natural Science Foundation of
China (21802139)
Keywords: Carbon Dioxide • Heterogeneous Catalysts •
Hydrogenation • Methanol • Non-Cu based catalysts
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ChemSusChem 10.1002/cssc.202002054

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Entry for the Table of Contents

Accepted Manuscript
Combining the captured CO2 and hydrogen produced from renewable energy to synthesize green methanol has great potential for
mitigating energy crises and climate change. This review emphasizes on the recent developments of non-Cu-based heterogeneous
catalysts (supported metal, intermetallic compounds, and mixed oxide catalysts represented by solid solution catalysts) for CO2-to-
methanol conversion.

21
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