2020 Nov Hydrogenation of Carbon Dioxide To Methanol Over Non-Cu

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
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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
REVIEW
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: [email protected]
[email protected]
Accepted Manuscript
1
This article is protected by copyright. All rights reserved.
REVIEW
Abstract: The increasing atmospheric CO2 level makes CO2 renewable energy with CO2-neutrality.[6] On the other hand, the
reduction an urgent challenge facing the world. Catalytic combination of CO2 and H2 can synthesize a variety of
transformation of CO2 into chemicals and fuels utilizing renewable chemicals such as oxygenates (alcohols, carboxylic acid, and
energy is one of the promising approaches toward alleviating CO2 dimethyl ether) and hydrocarbons (olefins, liquid hydrocarbons,
emissions. In particular, the selective hydrogenation of CO2 to and aromatics).[7]
methanol utilizing renewable hydrogen potentially enables large This challenge still exists in the combined CO2 capture and
scale transformation of CO2. The Cu-based catalysts have been utilization. The gas effluents releasing from the most energy-
extensively investigated in CO2 hydrogenation. However, it is not intensive industrial processes not only contains CO2, but also
only limited by long-term instability but also displays unsatisfactory accompanies with other components arising from combustion
catalytic performance. The supported metal-based catalysts (Pd, Pt, such as H2O, N2, unreacted O2, dust, sulphur and nitrogen
Au, and Ag) can achieve high methanol selectivity at low oxides, which would result in the CO2 hydrogenation catalysts
temperatures. The mixed oxide catalysts represented by MaZrOx (Ma deactivate rapidly. Thus, CO2 adsorption and purification for the
= Zn, Ga, and Cd) solid solution catalysts present high methanol direct application of CO2 hydrogenation in those streams is
selectivity and catalytic activity as well as excellent stability. This important. Amine scrubbers such as monoethanolamine,
Accepted Manuscript
review focuses on the recent advances in developing non-Cu-based diethanolamine and methyl diethanolamine as well as amine
heterogeneous catalysts and current understandings of catalyst blend solutions have been commonly employed industrially for
design and catalytic performance. First, the thermodynamics of CO2 post-combustion CO2 capture, but the considerable energy
hydrogenation to methanol is discussed. Then, the progress in penalty for desorbing CO2 from liquids.[8] Solid sorbents such as
supported metal-based catalysts, bimetallic alloys or intermetallic zeolites, carbon-based adsorbents, layered double hydroxides,
compounds catalysts, and mixed oxide catalysts is discussed. and metal-organic frameworks are considered to be good
Finally, a summary and a perspective are presented. 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
1. Introduction CO2 solubility, good thermal stability and tuneable structures,
hence they have also been proposed as promising solvents to
Carbon dioxide (CO2), a greenhouse gas, is closely replace the existing amine-based solvents.[10] The another
associated with the growing fossil energy consumption and the method of CO2 adsorption and purification is membrane
consequent climate change. Although the advances in science system.[11] The potential to perform separations at low energy
and technology have led to the increasing proportion of clean penalties makes membrane strategies attractive for practical
energy, fossil resources such as coal and petroleum are still the CO2 removal applications. On the other hand, Debecker et al
main source of energy supply, which are accompanied by an highlights the types of formulations of adsorbents, catalysts and
enormous CO2 emission to the atmosphere. Continued dual functional materials that have been proposed, some basic
economic and population growth further drive the increase in process engineering aspects, and the reported performance for
CO2 emissions. The atmospheric CO2 levels have increased the combined CO2 capture on solid adsorbents and CO2
sharply from the pre-industrial level of 280 ppm to 412 ppm in methanation on metal-based catalysts.[12] Two solids in two
2020.[1] Therefore, there is a pressing need to efficiently reduce separate units is a first option that will mostly require process
both the dependence on fossil resources and CO2 emissions. optimization, which allows not only to treat complex gas effluents
It has been proposed that the carbon capture and storage but also to perform the methanation under clean conditions. One
(CCS) could reduce CO2 emissions via absorption and unit with two solids constitutes a second option, in which the
adsorption trapping.[2] However, CCS is limited by high cost, catalysts have to exhibit high performance in its normal
intensive energy requirements for CO2 separation, the operating conditions and withstand the operating conditions that
uncertainty of CO2 storage time in sites, and the impact of large are applied during capture. One unit and one bifunctional solid is
volumes of CO2 on natural systems.[3] Carbon capture, storage, the use of dual functional materials, bearing both a capture
and utilization (CCSU), by contrast, is getting more and more function and a reduction function. Overall, the capture of CO2 by
attention since it not only alleviates CO2 emissions, but also adsorption and purification and its subsequent hydrogenation to
utilizes CO2 as an environmentally friendly carbon-resource to chemicals and fuels are promising line of research and
produce value-added chemicals, fuels, and even materials. development.
CCSU opens a new field in the conversion of “exhaust carbon” It is worth noting that methanol is an important platform
into “working carbon” and has a great significance in sustainable chemical as well as an ideal liquid fuel. The direct synthesis of
development.[4] But, a widely accepted opinion is that CO2 is so methanol from the hydrogenation of CO2 has thus attracted
thermodynamically stable that it is rarely used to its fullest great interest. According to the idea of liquid sunshine proposed
potential due to its low chemical potential. Therefore, CO2 by Shih and co-workers,[13] synthesis of methanol from CO2 and
conversion requires a high-energy input. To achieve energy- hydrogen is the first target. The “methanol economy” proposed
demanding synthetic protocols using CO2 as the C1 building by George Olah also positions CO2 hydrogenation to methanol
block, the specific substrate with high-energy, such as H2, is and derived products at its core.[14] Nowadays, methanol is one
needed. More importantly, the hydrogenation reaction has been of the top five commodity chemicals shipped around the world
considered as a feasible and powerful process among various each year. It is a primary raw material for the chemical industry,
chemical conversions of CO2 since it offers a good opportunity increasingly used in the methanol-to-olefins and methanol-to-
for sustainable development.[5] On the one hand, H2 could be aromatics processes.[15] Additionally, the market demand for
obtained from photocatalytic water splitting under direct methanol-derived fuels has been dramatically increased from
irradiation of sunlight and water electrolysis via electricity 6% in 2011 to 22% in 2016.[16] Thus, CO2 hydrogenation to
generated from solar and photovoltaic cells as well as other methanol is one of the attractive and potentially profitable routes
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in CCSU to mitigate CO2 emissions and reduce the dependence 2. The Properties and Activation of CO2
on fossil resources.
The research progress on catalytic hydrogenation of CO2 into CO2 is a linear molecule. Despite overall a non-polar molecule,
fuels and chemicals through both homogeneous and CO2 has two polar bonds due to the electronegativity difference
heterogeneous catalysis has been summarized in several between C and O atoms. The electronic structure of CO2 can be
excellent reviews and perspectives.[3, 6d, 7h, 17] Although some marked as O−δ−C+2δ−O−δ, implying that CO2 can be treated as a
homogeneous catalysts show high activity and selectivity,[17a, 18] bi-functional molecule with two different reaction sites. The
they are confronted with difficulties in recovery and regeneration carbon atom can be attacked by nucleophiles, while the oxygen
of the catalysts. By contrast, heterogeneous catalysts are atoms can be attacked by electrophilic reagents. Meanwhile,
preferable due to their advantages in stability, separation, CO2 can react with base since it can form carbonic acid in water.
handling, and reuse, as well as reactor design which helps to The physical state of CO2 changes with temperature and
fulfill large-scale production with lower costs.[7h, 18] Besides, pressure. CO2 becomes solid at low temperature and sublimes
these publications mainly focused on the general aspects of CO2 on warming below 5.1 bar. When the temperature and pressure
conversion and the discussion on Cu-based catalysts for CO2 exceed critical point (304 K, 73.9 bar), CO2 reaches the
Accepted Manuscript
hydrogenation to methanol. This review emphasizes on the supercritical state, where the density is close to liquid while the
progress in developing non-Cu-based heterogeneous catalysts viscosity is similar to gas. This state is often applied in the
for CO2-to-methanol conversion and tries to provide a current pharmaceutical industry.
understanding of catalysts design and catalysts advances. The Although CO2 reacts readily with strong nucleophiles, it is
studies concerning the homogeneous catalysis, photocatalysis, generally considered to be an “inert” molecule. This is caused by
and electrocatalysis as well as the indirect hydrogenation of CO2 the high kinetic energy barrier for the synthetic transformations
to methanol are beyond the scope of this review. In this paper, (C-H, C-C, and C-O bond formations) as well as the
we firstly discuss the chemical property and activation of CO2. thermodynamic constraints imposed by the extremely low
Then, the thermodynamic analysis of CO2 hydrogenation to chemical potential of the CO2 molecule. On the one hand, CO2 is
methanol is discussed. That is followed by discussions on the thermodynamically stable (ΔGf0 = −394.4 kJ·mol−1). Thus the
progress in non-Cu-based heterogeneous catalysts, including conversion of CO2 requires huge amount of energy, which
supported metal-based catalysts, bimetallic alloys or depends upon the downward steps of the oxidation state of
intermetallic compounds catalysts, and mixed oxide catalysts carbon from +4 in CO2 to the value in the target chemicals. On
represented by MaZrOx (Ma = Zn, Ga, and Cd) solid solution the other hand, the use of high-energy molecular reagents can
catalysts. Finally, a summary and a perspective are presented. provide driving forces to make the transformations
thermodynamically feasible. Hence, CO2 chemical
Feng Sha received his Master degree from Inner transformation and utilization face huge scientific and technical
Mongolia University of Technology in 2017. He is challenges.
currently a PhD candidate under the supervision CO2 is a green, abundant, and renewable carbon source.
of Prof. Can Li in the School of Materials Science However, it is not used widely as a raw material in current
and Engineering at Nankai University and the industrial practices. The reason for this is that the carbon atom
State Key Laboratory of Catalysis at Dalian in CO2 is in its highest oxidation state and is therefore relatively
Institute of Chemical Physics. His research inactive, which means a considerable energy input is required to
interests focus on the heterogeneous catalysts transform CO2 into useful chemicals. There are mainly four ways
for CO2 hydrogenation to methanol. to achieve CO2 transformation: (i) use high energy starting
materials such as hydrogen and chemically unsaturated
Ji-Jie Wang received his Ph.D. degree from
compounds, (ii) choose low energy synthetic targets, (iii) remove
Xiamen University in 2013. He did his
by-products to drive the equilibrium shift to the products, and (iv)
postdoctoral work at Dalian Institute of Chemical
supply other energy such as light or electricity. Selecting the
Physics in 2013–2017. Currently, he is an
right conditions for the CO2 transformation is crucial in order to
associate professor in the State Key Laboratory
achieve a negative Gibbs free energy change and low kinetic
of Catalysis at Dalian Institute of Chemical
energy barrier for the reaction.[19]
Physics. His research interests include (1) CO2
hydrogenation to chemicals and fuels, (2)
methanol steam reforming to hydrogenation, and
(3) liquid solar fuel synthesis. 3. Thermodynamics of CO2 hydrogenation
Can Li received his Ph.D. degree in Physical
Chemistry from Dalian Institute of Chemical It is well known that CO2 is a highly stable molecule with
Physics in 1989. He was promoted to full almost the lowest Gibbs free energy. Therefore, it is more
professor in 1993 and has been a visiting energy-demanding if CO2 is used as the sole substrate.
professor at the Université Pierre et Marie Curie However, it becomes thermodynamically easier if CO2 is used as
(Paris VI), the Lehigh University, the University of a co-reactant with another reactant with higher Gibbs free
Liverpool, and the Queensland University. He did energy, such as H2. The products of CO2 hydrogenation reaction
his postdoctoral work at Northwestern University are closely related to the type of catalyst and reaction conditions.
in 1994–1996. Currently, he is the head of Solar Methane, the easiest C1 hydrocarbon of CO2 conversion,
Energy Research Division and the director of the mainly products from the CO2 methanation. CO2 methanation is
Dalian National Laboratory for Clean Energy. His research interests include (1) a highly favorable process with large negative values of enthalpy
environmental and green catalysis, (2) UV Raman spectroscopy and time- and Gibbs free energy (eq. 1). Ni, Rh, and Ru with various
resolved spectroscopy, (3) chiral catalysis and bio-catalysis, and (4) solar supports (such as SiO2, Al2O3, TiO2, CeO2, ZrO2) are the most
energy utilization based on photo(electro)catalysis and photovoltaic cells. widely researched reported catalysts as their stronger
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hydrogenation ability for reaction intermediate species to form liquid phase and phase separation.[24] Equilibrium CO2
methane.[20] Fixed-bed reactors at atmospheric pressure, 320- conversion increases with rising temperature at low pressure (<
400 oC, and a 4:1 ratio of H2 to CO2 are generally employed for 100 bar), and decreases at high pressure. Methanol selectivity
the CO2 methanation. Compared to the methanol, methane is decreases with rising temperature, which is caused by the
much more stable and less reactive. As one of the most enhancement of endothermic RWGS reaction. It could be seen
important products of CO2 reduction, transition metal-based that high reaction pressure is advantagous in CO2 hydrogenation
systems like Cu, Pd, Pt, Au, and Ag have been proved to be to methanol, which has been verified experimentally by Gaikwad
good catalysts for methanol synthesis, which are discussed in and co-workers.[25] The equilibrium CO2 conversion and
the corresponding parts in the following. The hydrogenation methanol selectivity are enhanced at higher H2/CO2 ratio (Fig. 1).
ability of these metals to the reaction intermediate species is Bansode et al. found that the CO2 conversion was 37% with
moderate, not enough for further hydrogenation to generate methanol selectivity of 72% at the H2/CO2 molar ratio of 3, but
hydrocarbons. It is worth noting that the catalytic behavior of CO2 conversion rose drastically to 95% with methanol selectivity
these metals is also depended on the type of support. Methanol of 98% when H2/CO2 molar ratio was increased to 10 while other
production is favored by a 3:1 ratio of H2 to CO2 and a operating conditions remained unchanged.[25b] The
Accepted Manuscript
temperature around 200-300 oC with a pressure of 30-50 bar. experimentally observed outstanding CO2 conversion and
Thus, CO2 hydrogenation to methanol is more attractive and methanol selectivity at high molar ratio of H2/CO2 mainly result
profitable than CO2 methanation. from the high H2 partial pressure that enhances the reaction rate.
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).
Figure 1. Equilibrium CO2 conversion and methanol selectivity at different
In view of thermodynamics, methanol formation (eqs 2 and 4) temperatures with initial H2/CO2 mixtures of 3 (A) and 10 (B), and at (a) 10 bar,
is exothermic while RWGS reaction (eq 3) is endothermic. (b) 30 bar, (c) 100 bar, (d) 200 bar, (e) 300 bar, (f) 400 bar, and (g) 500 bar.
According to Le Ch telier s principle, decreasing reaction Reproduced with permission from Ref. [17d]; copyright 2017, American
temperatures and increasing reaction pressures are more Chemical Society.
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 4. Supported Metal Catalysts for CO2
also favors methanol synthesis taking the two equilibria into Hydrogenation to Methanol
consideration.[21] Therefore, the overall process becomes
equilibrium limited, where thermodynamics and equilibrium shifts Heterogeneous metal-based catalysts for methanol synthesis
interplay to determine the conversion and selectivity of the from CO2 hydrogenation mainly use Cu and noble metals such
products. as Pd, Pt, Au, and Ag. Álvarez et al.[17d] analyzed the research
Thermodynamically, high pressure and low temperature are articles published in the past ten years on CO2 hydrogenation to
favorable for methanol synthesis, as discussed above. Reaction methanol. The results show that 79% of the reports are related
temperature higher than 513 K facilitates CO2 activation and to Cu-based catalysts. It could be seen that Cu-based catalysts
subsequent methanol formation.[17a, 22] Van Bennekom et al. are still the focus of current research. Although there still exist
developed a model to simultaneously calculate the phase debates in identifying the active sites and understanding the
equilibrium and chemical equilibrium for high-pressure methanol mechanism, the structure-activity relationship of Cu-based
synthesis (P = 20 MPa, 463-553 K) based on a modified Soave- catalysts has been well established. However, Cu-based
Redlich-Kwong equation of state.[23] The calculated gas catalysts present poor activity at low temperatures compared
composition and equilibrium conversion, with and without the with other catalysts,[26] where methanol synthesis is more
formation of a liquid phase, are verified by the experimental thermodynamically favorable. Moreover, Cu-based catalysts
results obtained in a packed bed methanol synthesis reactor. also face severe deactivation over time. Due to these reasons,
They found that the condensation of reaction products (mainly noble metal catalysts are explored to improve the activity and
methanol and water) drove the equilibrium reactions nearly to carried out for CO2 hydrogenation to methanol at low
completion. temperatures, which is instrumental for the methanol synthesis
As shown in Fig.1, equilibrium CO2 conversion notably according to thermodynamics. The representative supported
changes with pressure in a wide range of temperatures, metal-based catalysts are summarized in Table 1. The catalytic
especially at 100-300 bar. This is caused by the formation of a
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performances are discussed in the corresponding parts in the
following.
Accepted Manuscript
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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]
Au/ZnO
3:1 240 0.5 4800 (G) 0.4 50.6 - [41a]
Au/Al2O3
3:1 240 0.5 4800 (G) 3.7 0.4 - [41a]
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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explained by the formation of PdZn alloys, which act as active
4.1 Pd-based catalysts sites for the direct synthesis of methanol.
Hong et al. synthesized ZnO-supported Ag@Pd core@shell
Pd supported on different supports have been studied for structure and found that electron transfer from Ag to the Pd
CO2 hydrogenation to methanol. At present, supports mainly shell significantly enhanced methanol selectivity.[28c] This offers
focus on Ga2O3,[27] ZnO,[28] CeO2,[28f, 28g, 29] In2O3,[30] carbon an alternative chance to enhance the catalytic performance and
materials,[28h, 31] and silica materials (SBA-15, MCM-41)[28b, 30c, 32] reduce the Pd loading.
to modify the electronic state of Pd for improving CO2 Díez-Ramírez et al. studied the catalytic performance of
adsorption and activation.[33] Pd/ZnO catalyst in the hydrogenation of CO2 to methanol under
atmospheric pressure as PdZn alloys were well known to give
4.1.1 Pd supported on Ga2O3 good performance in this reaction.[28d] The influence of
reduction temperature, calcination condition, metal loading, and
Pd/Ga2O3 catalysts are active for the CO2 hydrogenation to Pd precursor on the catalytic performance was studied. The
methanol, but not selective. The selectivity can be further results show that higher reduction temperature and higher
Accepted Manuscript
enhanced by tuning the interaction between Pd and Ga2O3 and metal loading are helpful to the formation of more PdZn alloy
the shape of catalysts. The study by Fujitani et al. showed that particles, which lead to higher methanol production. In contrast,
Pd/Ga2O3 was two times higher than Cu/ZnO in yield for fast calcination and insoluble metal precursor result in larger
methanol synthesis from CO2 hydrogenation.[27a] The excellent metallic palladium particles, hindering PdZn alloy formation and
activity of Pd/Ga2O3 is attributed to the optimal amount of Pdn+ suppressing methanol production.
(0 < n < 2) stabilized by GaxOy. Subsequently, a sustained Bowker et al. investigated the formation of PdZn alloy
research effort has been conducted to the Pd/Ga system for catalysts using chemical vapor impregnation to investigate their
CO2 hydrogenation to methanol.[27b-g] It is suggested that Pd/Ga activity in the CO2 hydrogenation reaction.[28e] PdZn supported
catalysts mainly transform CO2 into methanol via a bifunctional on TiO2 exhibits a high methanol yield of 1730 mmol·kgcat-1·h-1,
pathway. The reaction intermediates chemisorbed on the which is associated with the high dispersion of the supported
surface of Ga2O3 are hydrogenated from (bi)carbonates to PdZn alloy nanoparticles with a narrow size distribution.
formate (mono and bidentate and bridged), methylenebisoxy, Detailed analysis reveals that the PdZn alloy phase stabilizes
and methoxy step by step to give methanol, while hydrogen the formate intermediate and hence gives high activity for
supply is accomplished via spillover from the palladium metal methanol formation from the CO2 hydrogenation.
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
Figure 2. (a) CO2 conversion, (b) methanol selectivity and (c) proposed
interaction between Pd and the polar (002) surface of β-Ga2O3 reaction mechanism over Ca-doped PdZn/CeO2 catalysts. Reaction
plate is stronger than other non-polar surfaces. This stronger conditions: P=30 bar, H2/CO2=3/1, GHSV=2400 mL/(g h). Reproduced with
metal-support interaction gives rise to higher metal dispersion permission from Ref. [28g]; copyright 2018, Elsevier.
and facilitates electron transfer, leading to the formation of
PdGax and higher activity for methanol production from CO2
hydrogenation. Zaman et al. developed highly selective PdZn/CeO2 and Ca-
doped PdZn/CeO2 catalysts for methanol synthesis from CO2
4.1.2 Pd supported on ZnO hydrogenation under mild reaction conditions.[28f, 28g] The
PdZn/CeO2 catalysts give maximum CO2 conversion of 14%,
Pd/ZnO catalysts are active in CO2 hydrogenation to which is close to thermodynamic equilibrium, and high
methanol. The product selectivity depends on support types, methanol selectivity of 95% (220 oC, 20 bar, 2400 h−1 GHSV).
preparation methods, and Pd precursors.[28a] Pd has a strong The Ca-doped PdZn/CeO2 catalysts exhibit about 100%
inclination to form alloy species with ZnO when exposed to high selectivity to methanol with CO2 conversion of 7.7% (220 oC, 30
temperature under reducing environment,[34] which are bar, 2400 h−1 GHSV) (Fig. 2a,b). The reason for the high
correlated with catalytic activity and methanol selectivity.[28b-h] selectivity and activity lay in the excellent H2 dissociation ability
Iwasa et al. reported that Pd supported on ZnO showed the of PdZn alloy and the increased amount of oxygen-vacant sites
highest activity and selectivity to methanol among the Pd on CeO2, as illustrated in Fig. 2c. The amount of oxygen-vacant
supported on Ga2O3, In2O3, SiO2, MgO, and ZrO2.[28b] This is sites on CeO2 could be modified by the surface morphology of
9
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] Figure 3. Schematic representation of the distinct role of palladium in
Li et al. found that Pd/CeO2 catalyst reduced with hydrogen 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
REVIEW
Wang et al. incorporated Pd nanoparticles inside and outside the SiO2-supported PtW and PtCr bimetallic catalysts prepared
the CNTs, as shown in Fig. 4, and carefully examined these by using bimetal carbonyl hydride complexes exhibited very
catalysts in the reaction of CO2 hydrogenation to methanol.[31b] high selectivity and long lifetime for methanol synthesis.[36] In
The CO2 conversion of the Pd/CNTs-in catalyst is 1.3 times contrast, the conventionally impregnated monometallic and
than that of the Pd/CNTs-out catalyst, and the methanol bimetallic catalysts are almost inert or produced mainly CO. W
selectivity of the Pd/CNTs-in catalyst is 3.6 times than that of and Cr, as additives, can interact with Pt to suppress the
the Pd/CNTs-out catalyst (Fig. 4c). These difference are sintering of Pt and provide active bimetallic ensemble sites,
caused by the channel structure and electronic density which are responsible for the high activity and methanol
differences between the inside and outside of CNTs, which selectivity.
result in slightly smaller Pd nanoparticles size, more Pdδ+ Jeong et al. examined the impact of acidity on the
species, and higher H2 pressure inside the CNTs than outside. hydrogenation of CO2 to methanol and dimethyl ether using Pt
This work shows that the Pd0-Pdδ+ sites are responsible for CO2 supported on Nb2O5.[37] The increase of support acidity
hydrogenation to methanol, in which Pd0 activates H2 and Pdδ+ enhances the metal-support interaction and metal dispersion,
species activated CO2. At the same time, the locally higher H2 improves the CO2 conversion, while it is detrimental for the
Accepted Manuscript
pressure inside CNTs increases the hydrogenation rate. 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
Figure 4. TEM images and particle size distribution of catalysts: (a) Reduced the long time reaction. At the same time, the drop of CO2
Pd/CNTs-in catalyst, (b) Reduced Pd/CNTs-out catalyst; (c) Space time yield conversion is mitigated, indicating that the introduction of Pt
and selectivity of methanol at varied temperatures on Pd/CNTs-in and could increase the stability of the catalysts.
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 Figure 5. (a, d) HRTEM and (b, e) STEM images of (a, b) as-prepared 0.58
methanol synthesis from CO2 and H2.[28b, 35] Alkali and alkaline 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
earth metals are known as effective promoters for enhancing and circles, respectively, in the STEM images. (c) XPS Pt 4d spectra of the
the methanol synthesis activity of Pd/SiO2 catalyst.[32a] Song et as-prepared and used 0.58 wt.% Pt/In2O3. Reproduced with permission from
al. studied the cooperative effects of nano-structured Ref. [38]; copyright 2020, Elsevier.
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 The Pt species in the 0.58 wt.% Pt/In2O3 before and after
nanoparticles and lead to the higher activities for CH3OH used in CO2 hydrogenation were studied by atomic-resolution
formation than the conventional amorphous silica. Pd supported TEM and XPS (Fig. 5). Atomic-resolution TEM images proves
on MCM-41and SBA-15 without any promoters exhibit weak that the Pt species in the as-prepared 0.58 wt.% Pt/In2O3 is in
activities for methanol formation, while the addition of K, Mg, the atomically dispersed state. After used in CO2 hydrogenation,
and Ca enhances activities significantly. a small amount of Pt nanoparticles form from the sintering of
the atomically dispersed Pt species, while there is still a
4.2 Pt-based catalysts significant amount of atomically dispersed Pt species. XPS
results show that the atomically dispersed Pt species in the as-
Pt is active in hydrogenation reactions and has also been prepared 0.58 wt.% Pt/In2O3 are in the cationic state, while the
studied for methanol synthesis from CO2 and H2. The catalytic Pt species in the used catalysts are in the mixed metallic state
performance can be improved by incorporating the additives and cationic state, in agreement with TEM results. Combined
and increasing the Pt dispersion. Fujimoto et al. reported that with the reaction results, they propose that the atomically
dispersed Ptn+ species are responsible for the increased
11
REVIEW
methanol selectivity while the Pt nanoparticles forming during Au/ZnO > Au/TiO2 > Au/Al2O3. The Au/ZnO catalyst exhibits
CO2 hydrogenation mainly promote the RWGS reaction. high selectivity (> 50%). The difference in activity and selectivity
The role of Pt in the Pt/In2O3 catalysts during CO2 for various catalysts is attributed to the nature of the support.
hydrogenation was further studied by H2-TPD and H2-D2 Konsolakis et al. reported that Au nanoparticles supported on
isotopic exchange reaction. H2-TPD results show that the ZnO and CeO2 were highly selective towards methanol. TiO2-
introduction of Pt into In2O3 changes the adsorption strength of and Fe2O3-based catalysts almost catalyze exclusively the
H2 on the catalysts. New adsorption sites are also created after production of CO and/or CH4 with high CO2 conversion, while
the introduction of Pt. The results of the H2-D2 isotopic Au/Al2O3 is practically inactive in the investigated temperature
exchange reaction prove that the Ptn+ species are active in the range (200 oC - 350oC).[41b] It is obvious that Au NPs must be
activation of H2. They propose that the oxidation effect of the combined with particular reducible metal oxides (such as CeO2
CO2 and the product H2O, as well as the interaction between Pt or ZnO) to obtain high methanol formation rates. These results
and In2O3 lattice, could help in the stabilization of Pt in the imply the existence of SMSI (either geometric or electronic)
cationic state against reduction during CO2 hydrogenation. under working conditions, which are able to tune the local
Therefore, a significant amount of atomically dispersed Ptn+ surface chemistry of active sites finely. The synergistic
Accepted Manuscript
species are preserved after CO2 hydrogenation. interaction between oxygen vacancies on the Au-CeO2 (Au-
Liu et al. prepared Pt/In2O3 catalyst by the deposition- ZnO) interface and SMSI are accounted for the enhanced
precipitation method and tested the catalytic performance for performance.
CO2 hydrogenation to methanol over the Pt/In2O3 catalyst and Chen et al. found that the electronic polarization at the metal-
the pure In2O3 catalyst.[39] When the reaction temperature oxide interface of Au nanoparticles, which were anchored and
increases from 200 to 300 oC, the selectivity towards methanol stabilized on CeOx/TiO2 substrate, promoted CO2 adsorption
maintains ca. 100% at temperatures below 225 °C, 74% at and activation, and further improved the selectivity toward
275 °C and 54% at 300 °C, respectively. Compared with pure methanol.[46] This illustrates the importance of localized
In2O3 catalyst, the activity and the stability of the Pt/In2O3 electronic properties and structure in catalysis for CO2
catalyst are highly improved. The BET, XRD, and TEM results hydrogenation.
of the catalysts indicates that the Pt nanoparticles are well- The research of Ag catalysts in methanol synthesis from CO2
dispersed with an average particle size of 1.47 nm. More hydrogenation is relatively less. In general, Ag is used as a
importantly, TEM and H2-TPR results show that there are SMSI promoter in catalysts to play a key role for CO2 hydrogenation
between Pt and In2O3. The SMSI inhibits the over-reduction of to methanol.[45, 47] Grabowski et al. investigated the polymorphic
In2O3, resulting in the improved stability of the catalyst. The ZrO2 phases and the Ag electronic state in Ag/ZrO2 and
synergy between the supported Pt nanoparticles and In2O3 also Ag/ZrO2/ZnO catalysts.[48] The oxygen vacancies existing in the
balances the hydrogen activation and the density of the surface ZrO2 sublayer stabilize the thermodynamically unstable t-ZrO2
oxygen vacancies in In2O3, which lead to the high activity for phase and the Ag+ cations, which act as the active phase for
CO2 hydrogenation and enhanced stability of the Pt/In2O3 methanol synthesis. The methanol formation rate increases
catalyst. with increasing t-ZrO2 phase and Ag+ content.
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 5. Bimetallic Catalysts for CO2 Hydrogenation
using a dielectric barrier discharge plasma reactor.[40] The high to Methanol
dispersion of Pt nanoparticles and the film, which suppresses
the aggregation of Pt nanoparticles and transfers the electrons Bimetallic catalysts such as alloys and intermetallic
from the catalyst to CO2, promotes the adsorption of CO2 and compounds (IMCs) have emerged as an important kind of
enhances the hydrogenation of CO2 to methanol. As described catalysts for CO2 hydrogenation to methanol, due to the tunable
by the FTIR spectra, Pt/film/In2O3 has a higher ability in electronic, geometric, and chemical properties caused by
producing methoxy species from CO2 hydrogenation, which strong synergies.[9] Precious metal-based alloy catalysts hold
could also be an origin for the enhanced methanol production of the potential of low-temperature hydrogenation capacity owning
Pt/film/In2O3. This would be helpful for efficient methanol to the alloy active sites. But the atomic ratios of alloys are easily
production from CO2 hydrogenation under atmospheric affected by the reduction conditions and metal composition so
pressure and room temperature. that it is difficult to obtain an ideal alloy structure with uniform
atomic ratios. The IMCs provide a potential solution to this
4.3 Au/Ag-based catalysts issue and can form a stable bimetallic catalysts with
controllable and homogeneous atomic ratios.[49] IMCs have
Au is also beneficial for methanol synthesis. Au supported on unique advantages: (i) uniform, stable geometric and electronic
various metal oxide such as ZnO,[41] ZrO2,[41a, 42] CeO2,[41b] structures; (ii) electronic structure of active metals can be
TiC,[43] ZnO-TiO2,[44] ZnO/ZrO2,[45] CeOx/TiO2[46] are active for modified by neighboring atoms.[50] Therefore, IMCs have
methanol formation. Smaller Au particles are shown to give attracted extensive attention for methanol synthesis. Notably,
higher methanol productivity.[42, 44] Besides the Au nanoparticle PdGa,[51] PdIn,[30d, 52] and NiGa[53] IMCs have been reported as
size, the activity of Au catalysts also strongly depends on the highly active and selective catalysts for CO2 hydrogenation to
support. methanol.
Behm et al. investigated the activity and selectivity of different Manrique et al studied that the promotion of Pd with Ga and
Au catalysts with an almost identical Au particle size (Au/TiO2, Zn in the hydrogenation of CO2 to methanol.[51a, 51b] Mono and
Au/ZrO2, Au/ZnO, and Au/Al2O3) for methanol formation at 5 bar intermetallic catalysts (Pd/SiO2, PdeGa/SiO2 and PdeZn/SiO2)
and temperatures between 220oC and 240oC.[41a] The results with similar average metal particle sizes (between 9 and 12 nm)
show that the activity decreases in the order of Au/ZrO2 > were synthesized via incipient wetness impregnation to
12
REVIEW
eliminate the cluster size effects of Pd. The catalytic results Collins et al. found that Ga-Pd bimetallic particles formed
shows the selectivity to methanol increases from 3% for under reductive atmosphere above 523 K using quasi in-situ
Pd/SiO2 to 12% for Pd-Ga/SiO2 and 30% for Pd-Zn/SiO2. The high resolution transmission electron microscopy, as shown in
activity increase towards the methanol synthesis probably Fig. 6.[51d] But the Ga-Pd bimetallic particles were unstable and
results from the formation of intermetallic compounds Pd2Ga suffered from dramatic and extensive encapsulation by Ga2O3
and PdZn, as evidenced by a combination of XRD, XPS and upon air exposure. The Ga-Pd bimetallic particles mainly
CO-IR adsorption experiments. Recent work further reveals that dissociate and spill over H to the gallium sites, where the
the existence of bimetallic Pd-Ga sites is responsible for the stepwise hydrogenation of reaction intermediates takes place
increase in activity towards methanol synthesis.[51b] The from (bi)carbonate, formate, methoxy to methanol. The
separate phases of Pd and Ga (Pd and Ga2O3) are not as bimetallic sites also hamper methanol decomposition and CO
active for methanol formation. A significant increase in the production. Similarly, Cardona-Martinez et al. reported that the
methanol formation rate and selectivity is observed after catalytic activity of methanol synthesis improved with the
promotion of Pd with Ga comparing to those of the unpromoted increasing amount of Pd2Ga intermetallic compound using Pd
SiO2-supported Pd catalyst. Characterization by quasi in situ catalysts supported on Ga2O3 with various crystalline
Accepted Manuscript
XPS, XRD, CO adsorption DRIFTS and TEM-EDS phases.[49e] The Pd2Ga content varies depending on the Ga2O3
demonstrates that the primary cause for the increase in activity polymorphs. The catalytic activity is also influenced by the CO2
towards methanol synthesis is the formation of intermetallic adsorption properties on the different Ga2O3 polymorphs.
compounds of Pd2Ga, rather than a cooperative mechanism Yang et al. studied the reaction mechanism of methanol
between Pd and Ga2O3. The variation of the Pd/Ga ratio synthesis over the intermetallic PdIn catalyst through DFT
defines the surface concentration of Ga2O3, where the calculations and microkinetic analysis.[52] They found that
deposition of excess Ga in its oxidized form on the mono or methanol formation occurs via HCOO → HCOOH → H2COOH
bimetallic phases of the catalysts inhibits their catalytic → CH2O + OH → CH3O + OH → CH3OH(g) + H2O(g) on both
performance. Operando DRIFTS characterization shows the surfaces. The dominant surface species is HCOO. The rate-
formation of bidentate formate species on the metallic Pd or Pd- controlling transition state for methanol formation is HCOOH
Ga sites acting as intermediates in the hydrogenation of CO2 to hydrogenation on PdIn(110), while on PdIn(211) it changes
methanol. from H2COOH dissociation to HCOOH hydrogenation with
Behrens et al. synthesized supported PdZn, Pd2Ga, and Pd increase in temperature.
catalysts via reductive decomposition of ternary hydrotalcite-like Ni-Ga IMCs have been identified as catalysts with interesting
compounds.[51c] They observe that the PdZn and Pd2Ga IMCs activity, selectivity, and stability for ambient pressure CO2
are present in the form of nanoparticles with an average hydrogenation to methanol. As shown in Fig. 7a, Nørskov et al.
diameter of 6 nm or less after reducing the PdZnAl and first predicted the catalytic activity of Ni-Ga IMCs by
PdMgGa precursors. The monometallic Pd nanoparticles is computational methods and the descriptor-based analysis of
obtained by reducing the analogous PdMgAl precursors without the process, and further compared with Cu-Zn, Cu, Ni, and Pd
second reducible species. The catalytic properties of Pd are as benchmark catalysts.[53a] Then, they synthesized and tested
positively affected by PdZn and Pd2Ga IMCs formation for a series of Ni-Ga catalysts with different Ni:Ga ratios supported
methanol synthesis. The PdZnAl and PdMgGa show similar on silica. The results show that Ni5Ga3/SiO2 expresses
steady-state activities for methanol synthesis of 17.6 and 18.7 particularly activity and selectivity. The Ni5Ga3/SiO2 displays
μmol/(gcat·min), respectively. These activities amounted to same or better methanol synthesis activity, as well as
nearly 30 times the methanol synthesis activity of 0.65 considerably lower production of CO compared with
μmol/(gcat·min) for PdMgAl. The presence of Zn and Ga also conventional Cu/ZnO/Al2O3 catalysts (Fig. 7b,c). The difference
improves the selectivity to methanol. 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
Figure 6. HRTEM image of the postreaction Pd/β-Ga2O3 catalyst (inset: [101]
reduced Ni5Ga3 for methanol synthesis. The resultant Ga-rich
zone axis simulation image of a β-Ga2O3 crystal). Reproduced with surface and the synergy between remaining Ga2O3 and Ni-Ga
permission from Ref. [51d]; copyright 2012, Elsevier. IMCs make surface oxidized Ni5Ga3 more active than fully
reduced Ni5Ga3 for methanol synthesis.
13
REVIEW
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.
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
Accepted Manuscript
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 Figure 8. Catalytic performance of the ZnO-ZrO2 catalyst. (a) Dependence of
involved in the hydrogenation process, except for the O atom, 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
prefer to bond with surface Ni sites along the step edge. The
area; dark yellow, normalized activities for mechanically mixed ZnO and ZrO2
dissociative adsorption of H2 on the Ga3Ni5(221) surface is in the same composition. (b) Catalytic performance at the reaction
spontaneous and highly exothermic. Moreover, the introduction temperatures from 200° to 380°C with H2/CO2 = 3:1 and 4:1. (c) Catalyst
of Ga indeed promotes H2 dissociative adsorption on the 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
surface, which is verified by the projected density of states
MPa, H2/CO2 = 3:1, 320°C, GHSV = 24000 ml/(g hour), using a tubular fixed-
analysis.[53d] In recent work, they studied the impacts of the size bed reactor with the 13% ZnO-ZrO2 catalyst. Reproduced with permission
and support of Ga-Ni clusters, including Ga3Ni5, Ga6Ni10, from Ref. [7a]; copyright 2017, Science.
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 As shown in Fig. 8b, CO2 conversion increases while
results indicate that cluster size has a significant impact on the methanol selectivity decreases with rising reaction
activation barrier of the rate-limiting step of hydrogenation temperatures. Methanol selectivity can still be kept at 86% with
process. Among the studied Ga-Ni clusters, the Ga6Ni10 cluster excellent CO2 single-pass conversion of 10% even though the
has the lowest activation barrier resulted from the d-band temperature is increased to 320oC. Higher pressure, space
center location and the exposed active sites. Meanwhile, the velocity, and H2/CO2 ratio are beneficial to the methanol
support with increasing electron transfer abilities is preferable selectivity. More importantly, this catalyst presents high stability
for decreasing activation barriers. 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
6. Mixed Oxide Catalysts for CO2 the catalyst viable in industrial processes.
Hydrogenation to Methanol XRD patterns show that there is no ZnO phase. At the same
time, the phase of ZrO2 changes from monoclinic to tetragonal
In recent years, mixed oxide catalysts represented by solid when ZnO (5 to 33%) is incorporated, indicating that the ZnO-
solutions and In2O3-based oxides are emerging as active and ZrO2 solid solution might form (Fig. 9a). From Fig. 9b, the
cost-effective catalysts and developing rapidly for CO2 interplanar spacing of 13% ZnO-ZrO2 is ca. 0.294 nm, which is
hydrogenation to methanol. The MaZrOx (Ma = Zn, Ga, Cd) solid attributed to the (011) surface of tetragonal ZrO2. As the ionic
solution catalysts and indium-based oxide catalysts as well as radius of Zn2+ (0.74 Å) is smaller than that of Zr4+ (0.82 Å), the
Co-based oxide catalysts have been investigated in the thermal interplanar spacing would decrease when Zn2+ is incorporated
hydrogenation of CO2 to methanol. into the lattice of ZrO2. This is confirmed by XRD as the
diffraction peak corresponding to the (011) plans of ZrO2 shifts
6.1 Solid Solution Catalysts towards high angle with the increasing amount of Zn added
from 5 to 33%. The element distribution analysis proves that Zn
Wang et al. reported that the binary metal oxide ZnO-ZrO2 in is highly dispersed in ZrO2 (Fig. 9c). XPS results also show that
the solid solution state was an active catalyst for CO2 the Zn is relatively rich on the surface since Zn concentration in
hydrogenation to methanol with high selectivity and stability.[7a] the surface region is higher than the theoretical value (Fig. 9d).
As shown in Fig. 8a, the CO2 conversion of 13% ZnO-ZrO2 is These characterization results further affirms that ZnO-ZrO2 is
in a solid solution state with Zn incorporating into the ZrO2
14
REVIEW
lattice, as schematically depicted in Fig. 9e. Combining detailed Figure 10. DFT calculations. Reaction diagram [energy (E) and Gibbs free
energy (G) at a typical reaction temperature of 593 K] of CO2 hydrogenation
characterization with CO2-TPD and H2-D2 exchange reaction, it
to methanol on the (101) surface of the tetragonal ZnO-ZrO2 model. Adapted
could be concluded that the satisfactory catalytic performance with permission from Ref. [7a]; copyright 2017, Science.
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. 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 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.
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,
In situ DRIFTS and DFT calculations were performed to Cd, In, La, Ce) catalysts. The reaction conditions: H2/CO2 = 3/1, 24000h−1, 2
understand the reaction mechanisms. In situ DRIFTS results MPa, 300 °C. Reproduced with permission from Ref. [7c]; copyright 2019,
indicate that the surface HCOO* and H3CO* species on the American Chemical Society.
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 As shown in Fig. 11, most of ZnMbOx (Mb = Mg, Ca, Sc, Ti, V,
pathway rather than the CO pathway, as illustrated in Fig. 10. Cr, Mn, Ga, Y, Zr, Cd, In, Sn, La, Ta, Pb) catalysts show higher
H2 is adsorbed and dissociated on the Zn site, and CO2 is methanol selectivity than ZnO (29%), except ZnCrOx and
adsorbed on the coordination unsaturated Zr site. The CO2* ZnTaOx. The CO2 conversion of ZnMbOx strongly depends on
transforms into HCOO* species via hydrogenation. The HCOO* the type of Mb, only ZnTiOx, ZnCrOx, ZnGaOx, ZnZrOx, and
species is further hydrogenated to the H2COO* species. The ZnInOx display higher CO2 conversion than ZnO (1.1%). For
H2COO* species is protonated by an OH* group and forms MaZrOx (Ma = Mg, Al, Ca, Sc, Ti, V, Cr, Mn, Zn, Ga, Y, Mo, Cd,
H2COOH* species, in which the C-O bond is cleaved and In, La, Ce) catalysts, most of them represent similar CO2
thereby generating H2CO* and OH* bound on Zr and Zn sites, conversion and methanol selectivity to ZrO2 (X(CO2) = 0.14%,
respectively. The generated H2CO* is hydrogenated to H3CO* S(CH3OH) = 26%). However, the CdZrOx and GaZrOx catalysts,
and methanol forms from the H3CO* protonation. 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.
15
REVIEW
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
Figure 12. The CO2 conversions and methanol selectivities on (A) CdO, hydrogenation to methanol, with prospects for industrial
11.5%CdZrOx, and ZrO2, (B) Ga2O3, 11.5%GaZrOx, and ZrO2. The effect of deployment.[57-61]
reaction temperature and pressure on the CO2 conversions (C) and methanol Ge et al demonstrated that the oxygen vacancy on the In2O3
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
(110) surface assisted CO2 activation and hydrogenation and
with permission from Ref. [7c]; copyright 2019, American Chemical Society. 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
There is no doubt that MaZrOx (Ma = Cd, Ga) catalysts show hydrogenation to methanol.[57b] Pérez-Ramírez et al found that
an obvious enhancement in catalytic activity and methanol the apparent activation energy determined experimentally for
selectivity, compared with the individual oxides (Fig. 12). When CO2 hydrogenation to methanol over bulk In2O3 was lower than
the temperature increases from 280oC to 360oC, the CO2 the one for the RWGS reaction by elucidating the mechanistic
conversion increases, while the methanol selectivity decreases and kinetic fingerprints in detail, which is in line with the high
possibly resulting from the intensification of the RWGS reaction. methanol selectivity observe.[57c] M5ller and coworkers probed
Both the CO2 conversion and methanol selectivity increase with the structural evolution of In2O3 nanoparticles with time on
the reaction pressure. stream by operando XAS-XRD, and the results showed that
XRD, high-resolution transmission electron microscopy, high- In2O3-x was the active phase while the catalyst deactivation was
angle annular dark-field scanning transmission electron due to the formation of In0.[57d] More recently, Sun and Gao et al
microscopy, and low-energy ion scattering spectrum prove that successfully designed a much higher performance In2O3
MaZrOx (Ma = Cd, Ga) forms solid solution structure with the nanocatalyst for CO2 hydrogenation to methanol under the
incorporation of Ma (Ma = Cd, Ga) into the ZrO2 lattice and guide of computational study.[57e] The authors first performs
affords two sites (Ma and Zr) on the surface. CO2-TPD results extensive DFT calculations to establish the catalytic
deduce that the Zr site is mainly responsible for CO2 adsorption mechanisms of the In2O3 catalyst during CO2 hydrogenation to
and activation. H2-D2 exchange reaction concludes that there is methanol and to CO by identifying the preferred pathways and
a strong synergetic effect in the H2 activation between the two rate-determining steps. The computational results show that the
sites, (Ma = Cd, Ga) and Zr in MaZrOx catalysts. XPS results hexagonal-phase In2O3(104) surface has the best catalytic
show that the oxygen vacancy contents of MaZrOx (Ma = Cd, Ga) performance in terms of reactivity and selectivity. According to
are much more than that of individual ZrO2 (31.6%(31.2%) vs the computational results, authors prepare pure cubic-phase
12.4%), which is attributed to the additional oxygen vacancies In2O3 and hexagonal-phase In2O3 nanoparticles with different
created by the introduction of Ma2+/3+ (Ma = Cd, Ga) cations into morphologies and evaluate their performance for CO2
the matrix of ZrO2. Based on the results of CO2-TPD, XPS and hydrogenation to methanol. The experimental results
H2-D2 exchange reaction, the electronic property of Ma (Cd, Ga) demonstrate that the catalytic performance is related to the
is modified via the interaction between Ma and Zr in the solid shape of In2O3 nanoparticles due to their different phases and
solution structure, which enhances the ability for activation of exposed facets. As shown in Fig.13, the hexagonal-phase In2O3
H2 and further improves the selectivity and activity for CO2 nanomaterial with high proportion of the exposed (104) surface
hydrogenation to methanol. DFT calculations also suggest that displays the highest activity and methanol selectivity with high
two different surface sites of the MaZrOx (Ma = Cd, Ga) are catalytic stability, confirming the theoretical prediction. Under
responsible for CO2 and H2 activation, respectively, which is in the reaction conditions of 300 oC, 5.0 MPa, 9000 mL/(gcat−1·h−1),
good agreement with the CO2-TPD, XPS, and H2-D2 exchange and H2/CO2 = 6, methanol selectivity achieves 92.4% with a
results. In summary, solid solution catalysts offer alternatives to single-pass CO2 conversion of more than 17%. This work may
metal-based catalysts and opportunities in developing active, open new avenues toward computer-aided rational design of
selective, and cost-effective catalysts. efficient catalysts for methanol synthesis.
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 Figure 13. Catalytic performance of various In2O3 for CO2 hydrogenation. (A)
CO2 conversion and methanol selectivity over In2O3 with different crystal
temperatures of dried ZrO2 support influenced the phase,
phases and morphologies. Insert: Normalized activities for cubic-phase In2O3-
crystallinity, and adsorptive properties of ZnOx/ZrO2 solid S, cubic-phase In2O3-P, hexagonal-phase In2O3-L, and hexagonal-phase
solution catalysts prepared by impregnation method.[56] It could In2O3-R by specific surface area after pretreatment in pure Ar at 300°C for 44
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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
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REVIEW
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.
Figure 15. Synthesis and catalysis strategies of Co@Six catalysts. The
Accepted Manuscript
(3) Although high temperature facilitates CO2 activation, CO
procedures with cobalt phyllosilicates as intermediates for synthesizing
Co@Six. Within the highlighted square, the CO2-to-methanol transformation is also competitively produced via RWGS reaction, leading to
on Co@Six catalysts. Adapted with permission from Ref. [64]; copyright 2020, low methanol selectivity. In view of thermodynamics, methanol
Springer Nature. 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
7. Summary and Perspectives overcoming CO2 activation energy barriers at low temperatures
and designing catalysts system based on theoretical and
Combining the captured CO2 and hydrogen produced from experimental studies.
renewable energy to synthesize green methanol, as highlighted (4) An excellent catalyst for CO2 hydrogenation to methanol
as “methanol economy”[14] and named as “liquid sunshine”[13], should possess good stability besides high activity and
has great potential for mitigating energy crises and climate selectivity. This mainly reflects in the resistance to water and
change. In the past decades, there has been considerable sulfur-containing molecules in the stream as well as sintering at
progress in developing various heterogeneous catalysts for higher temperatures. Water is the by-product in methanol
CO2 hydrogenation to methanol. Among metals, alloys or synthesis from CO2 hydrogenation. Sulfur-containing molecules
intermetallic compounds, and metal oxide heterogeneous always present in CO2 from flue gas sources produced from
catalysts, the non-Cu based catalysts with good performance coal or biomass burning. The catalysts easily suffer from
and high stability are developing rapidly. The supported metal serious deactivation with water and sulfur-containing molecules
catalysts (Pd, Pt, Au, Ag) can achieve higher methanol due to sintering and poisoning at the reaction conditions. The
selectivity at low temperatures, depending on the support types catalysts easily suffer from serious deactivation with water and
and preparation methods as well as metal precursors, but face sulfur-containing molecules due to sintering and poisoning at
the problems of low activity and high cost. Although alloys or the reaction conditions, especially the supported metal catalysts.
IMCs catalysts have some advantages in tunable electronic, For the mixed oxide catalysts, the effect of water on the
geometric, and chemical properties, alloys or IMCs catalysts catalytic activity is rarely reported. Therefore, research about
with ideal and uniform atomic ratios are difficult to obtain since this aspect needs to be further explored deeply. Although In2O3
the atomic ratios are easily affected by the reduction conditions exhibits better water tolerance upon water addition into the
and metal composition of the catalyst. The newly emerging feeds and long-term stability in the presence of water,[58a, 30c]
mixed oxide catalysts represented by MaZrOx (Ma = Zn, Ga, Cd) and ZnO-ZrO2 shows no deterioration in methanol selectivity for
solid solution catalysts and indium-based hybrid oxide catalysts more than 500 hours on stream,[7a] more in-depth
as well as Co-based hybrid oxide catalysts present higher understanding of reaction mechanisms and active sites would
methanol selectivity and catalytic activity as well as good be required for their further development and implementation.
stability, which are promising for the conversion of CO2 to More attention should be paid to designing catalysts with
methanol in industry. hydrophobic properties to remove water under reaction
The selective conversion of CO2 to methanol over conditions, which may not only protect catalysts from
heterogeneous catalysis utilizing renewable hydrogen has deactivation or sintering but also shift the equilibrium to obtain
being attracted great attention. Although various heterogeneous higher methanol yield. Alternatively, membrane reactor could
catalysts have been investigated, many inherent issues remain satisfy this requirement by selectively removing condensable
to achieve large-scale industrialization of methanol synthesis products and shifting equilibrium limited reaction toward
from CO2. Challenges always coexist with opportunities, desirable products. But it also faces the challenges from
several issues merit particular attention in the near future. selective water permeation and withstand harsh reaction
(1) More attention to the fundamental study regarding the conditions such as high pressure based on good methanol yield.
nature of the active sites and interactions between active Zeolite-based membrane is a potential candidate in this regard
components, promoter, and supports are encouraged. There is since its thermal and chemical stability. Moreover, it has been
great potential for the improvement of activity and selectivity of proven to achieve higher CO2 conversion and methanol yield.[65]
the catalyst via tuning catalyst composition and engineering As for the stability of the catalysts toward sulfur-containing
surface structures. The selection of suitable precursors of molecules, ZnO-ZrO2 exhibits sulfur tolerance making the
active components and preparation methods are also important. catalyst viable in industrial processes, it could bee seen that the
With the development of nanoscience and nanotechnology, mixed oxide catalysts are superior to supported metal-based
designing catalysts with well-defined structures in nanoscale catalysts.
18
REVIEW
Acknowledgements 2016, 273, 234-243; c) G. L. Zhou, H. R. Liu, K. K. Cui, A. P. Jia, G. S.
Hu, Z. J. Jiao, Y. Q. Liu, X. M. Zhang, Appl. Surf. Sci. 2016, 383, 248-
252; d) D. C. D. da Silva, S. Letichevsky, L. E. P. Borges, L. G. Appel,
This work was supported by grants from National Key R&D
Int. J. Hydrogen Energy 2012, 37, 8923-8928; e) J. C. Matsubu, V. N.
Program of China (2017YFB0702800), Transformational Yang, P. Christopher, J. Am. Chem. Soc. 2015, 137, 3076-3084; f) T.
Technologies for Clean Energy and Demonstration Abe, M. Tanizawa, K. Watanabe, A. Taguchi, Energy Environ. Sci.
(XDA21090202), and National Natural Science Foundation of 2009, 2, 315-321; g) D. C. Upham, A. R. Derk, S. Sharma, H. Metiu, E.
China (21802139) W. McFarland, Catal. Sci. Technol. 2015, 5, 1783-1791.
[21] W. J. Shen, K. W. Jun, H. S. Choi, K. W. Lee, Korean J. Chem. Eng.
2000, 17, 210-216.
Keywords: Carbon Dioxide • Heterogeneous Catalysts •
[22] M. Aresta, A. Dibenedetto, E. Quaranta, J. Catal. 2016, 343, 2-45.
Hydrogenation • Methanol • Non-Cu based catalysts [23] J. G. v. Bennekom, J. G. M. Winkelman, R. H. Venderbosch, S. D. G.
B. Nieland, H. J. Heeres, Ind. Eng. Chem. Res. 2012, 51, 12233-
[1] Global Greenhouse Gas Reference Network-Trends in Atmospheric 12243.
Carbon Dioxide. National Oceanic and Atmospheric Administration, [24] J. G. van Bennekom, R. H. Venderbosch, J. G. M. Winkelman, E.
Earth System Research Laboratory, Global Monitoring Division; U.S. Wilbers, D. Assink, K. P. J. Lemmens, H. J. Heeres, Chem. Eng. Sci.
Accepted Manuscript
Department of Commerce: Global, March 5, 2020. 2013, 87, 204-208.
[2] a) S. A. Didas, S. Choi, W. Chaikittisilp, C. W. Jones, Accounts Chem. [25] a) R. Gaikwad, A. Bansode, A. Urakawa, J. Catal. 2016, 343, 127-132;
Res. 2015, 48, 2680-2687; b) G. T. Rochelle, Science 2009, 325, 1652; b) A. Bansode, A. Urakawa, J. Catal. 2014, 309, 66-70.
c) M. Pera-Titus, Chem. Rev. 2014, 114, 1413-1492. [26] a) F. Studt, M. Behrens, E. L. Kunkes, N. Thomas, S. Zander, A. Tarasov,
[3] M. Aresta, A. Dibenedetto, A. Angelini, Chem. Rev. 2014, 114, 1709- J. Schumann, E. Frei, J. B. Varley, F. Abild-Pedersen, J. K. Nørskov, R.
1742. Schlogl, ChemCatChem 2015, 7, 1105-1111; b) E. L. Kunkes, F. Studt,
[4] J. Artz, T. E. M5ller, K. Thenert, J. Kleinekorte, R. Meys, A. Sternberg, F. Abild-Pedersen, R. Schlogl, M. Behrens, J. Catal. 2015, 328, 43-48;
A. Bardow, W. Leitner, Chem. Rev. 2018, 118, 434-504. c) M. B. Fichtl, D. Schlereth, N. Jacobsen, I. Kasatkin, J. Schumann,
[5] S. Saeidi, N. A. S. Amin, M. R. Rahimpour, J. CO2 Util. 2014, 5, 66-81. M. Behrens, R. Schlogl, O. Hinrichsen, Appl. Catal. A 2015, 502, 262-
[6] a) Y. Zhao, C. Ding, J. Zhu, W. Qin, X. Tao, F. Fan, R. Li, C. Li, Angew. 270; d) J. Xiao, D. Mao, X. Guo, J. Yu, Appl. Surf. Sci. 2015, 338, 146-
Chem. Int. Edit. 2020, 59, 9653-9658; b) C. Ding, J. Shi, Z. Wang, C. 153; e) K. Samson, M. Sliwa, R. P. Socha, K. Gora-Marek, D. Mucha,
Li, ACS Catal. 2017, 7, 675-688; c) Q. Wang, K. Domen, Chem. Rev. D. Rutkowska-Zbik, J. F. Paul, M. Ruggiero-Mikołajczyk, R. Grabowski,
2020, 120, 919-985; d) E. V. Kondratenko, G. Mul, J. Baltrusaitis, G. O. J. Słoczynski, ACS Catal. 2014, 4, 3730-3741; f) F. Arena, G
Larrazábal, J. Pérez-Ramírez, Energy Environ. Sci. 2013, 6, 3112- Mezzatesta, G. Zafarana, G. Trunfio, F. Frusteri, L. Spadaro, Catal.
3135. Today 2013, 210, 39-46; g) W. Wu, K. Xie, D Sun,. X. Li, F. Fang, Ind.
[7] a) J. Wang, G. Li, Z. Li, C. Tang, Z. Feng, H. An, H. Liu, T. Liu, C. Li, Eng. Chem. Res. 2017, 56, 8216-8223; h) J. Toyir, P. R. de la Piscina,
Sci. Adv. 2017, 3, e1701290; b) Z. Li, Y. Qu, J. Wang, H. Liu, M. Li, S. J. L. G. Fierro, N. S. Homs, Appl. Catal. B 2001, 34, 255-266.
Miao, C. Li, Joule 2019, 3, 570-583; c) J. Wang, C. Tang, G. Li, Z. Han, [27] a) T. Fujitani, M. Saito, Y. Kanai, T. Watanabe, J. Nakamura, T.
Z. Li, H. Liu, F. Cheng, C. Li, ACS Catal. 2019, 9, 10253-10259; d) Z. Uchijima, Appl. Catal. A 1995, 125, L199-L202; b) S. E. Collins, L. E.
Li, J. Wang, Y. Qu, H. Liu, C. Tang, S. Miao, Z. Feng, H. An, C. Li, ACS Briand, L. A. Gambaro, M. A. Baltanás, A. L. Bonivardi, J. Phys. Chem.
Catal. 2017, 7, 8544-8548; e) P. Gao, S. Li, X. Bu, S. Dang, Z. Liu, H. C 2008, 112, 14988-15000; c) D. L. Chiavassa, S. E. Collins, A. L.
Wang, L. Zhong, M. Qiu, C. Yang, J. Cai, W. Wei, Y. Sun, Nat. Chem. Bonivardi, M. A. Baltanás, Chem. Eng. J. 2009, 150, 204-212; d) S. E.
2017, 9, 1019-1024; f) Y. Ni, Z. Chen, Y. Fu, Y. Liu, W. Zhu, Z. Liu, Nat. Collins, M. A. Baltanás, A. L. Bonivardi, J. Catal. 2004, 226, 410-421;
Commun. 2018, 9, 3457; g) X. Shao, X. Yang, J. Xu, S. Liu, S. Miao, X. e) D. L. Chiavassa, J. Barrandeguy, A. L. Bonivardi, M. A. Baltanás,
Liu, X. Su, H. Duan, Y. Huang, T. Zhang, Chem 2019, 5, 693-705; h) W. Catal. Today 2008, 133-135, 780-786; f) J. Qu, X. Zhou, F. Xu, X.-Q.
Wang, Y. Himeda, J. T. Muckerman, G. F. Manbeck, E. Fujita, Chem. Gong, S. C. E. Tsang, J. Phys. Chem. C 2014, 118, 24452-24466; g) X.
Rev. 2015, 115, 12936-12973. Zhou, J. Qu, F. Xu, J. Hu, J. S. Foord, Z. Zeng, X. Hong, S. C. Edman
[8] S. Chu, Science 2009, 325, 1599. Tsang, Chem. Commun. 2013, 49, 1747-1749.
[9] M. M. J. Li, S. C. E. Tsang, Catal. Sci. Technol. 2018, 8, 3450-3464. [28] a) H. Bahruji, M. Bowker, G. Hutchings, N. Dimitratos, P. Wells, E.
[10] E. D. Bates, R. D. Mayton, I. Ntai, J. H. Davis, J. Am. Chem. Soc. Gibson, W. Jones, C. Brookes, D. Morgan, G. Lalev, J. Catal. 2016,
2002, 124, 926-927. 343, 133-146; b) N. Iwasa, H. Suzuki, M. Terashita, M. Arai, N.
[11] R. Khalilpour, K. Mumford, H. Zhai, A. Abbas, G. Stevens, E. S. Rubin, Takezawa, Catal. Lett. 2004, 96, 75-78; c) X. Li, Z. Zeng, B. Hu, L.
J. Cleaner Prod. 2015, 103, 286-300. Qian, X. Hong, ChemCatChem 2017, 9, 924-928. d) J. Díez-Ramírez,
[12] P. Melo Bravo, D. P. Debecker, Waste Dispos. Sustain. Energy, 2019, J. L. Valverde, P. Sánchez, F. Dorado, Catal. Lett. 2016, 146, 373-382;
1, 53-65. e) H. Bahruji, M. Bowker, W. Jones, J. Hayward, J. Ruiz Esquius, D. J.
[13] C. F. Shih, T. Zhang, J. Li, C. Bai, Joule 2018, 2, 1925-1949. Morgan, G. J. Hutchings, Faraday Discuss. 2017, 197, 309-324; f) O.
[14] G. A. Olah, Angew. Chem. Int. Edit. 2005, 44, 2636-2639. A. Ojelade, S. F. Zaman, M. A. Daous, A. A. Al-Zahrani, A. S. Malik, H.
[15] G. A. Olah, A. Goeppert, G. K. S. Prakash, J. Org. Chem. 2009, 74, Driss, G. Shterk, J. Gascon, Appl. Catal. A 2019, 584, 117185; g) A. S.
487-498. Malik, S. F. Zaman, A. A. Al-Zahrani, M. A. Daous, H. Driss, L. A.
[16] X. Jiang, X. Nie, X. Guo, C. Song, J. G. Chen, Chem. Rev. 2020, 120, Petrov, Appl. Catal. A 2018, 560, 42-53; h) X. Liang, X. Dong, G. Lin,
7984-8034. H. Zhang, Appl. Catal. B 2009, 88, 315-322.
[17] a) W. Wang, S. Wang, X. Ma, J. Gong, Chem. Soc. Rev. 2011, 40, [29] L. Fan, K. Fujimoto, Appl. Catal. A 1993, 106, L1-L7.
3703-3727; b) X. Du, Z. Jiang, D. Su, J. Wang, ChemSusChem 2016, [30] a) J. Ye, C. Liu, D. Mei, Q. Ge, J. Catal. 2014, 317, 44-53; b) N. Rui, Z.
9, 322-332; c) M. D. Porosoff, B. Yan, J. G. Chen, Energy Environ. Sci. Wang, K. Sun, J. Ye, Q. Ge, C. Liu, Appl. Catal. B 2017, 218, 488-497;
2016, 9, 62-73; d) A. Álvarez, A. Bansode, A. Urakawa, A. V. Bavykina, c) M. S. Frei, C. Mondelli, R. García-Muelas, K. S. Kley, B. Puértolas,
T. A. Wezendonk, M. Makkee, J. Gascon, F. Kapteijn, Chem. Rev. N. López, O. V. Safonova, J. A. Stewart, D. Curulla. Ferré, J. Pérez-
2017, 117, 9804-9838; e) Y. Li, R. Ma, L. He, Z. Diao, Catal. Sci. Ramírez, Nat. Commun. 2019, 10, 3377; d) H. Jiang, J. Lin, X. Wu, W.
Technol. 2014, 4, 1498-1512; f) S. Dang, H. Yang, P. Gao, H. Wang, X. Wang, Y. Chen, M. Zhang, J. CO2 Util. 2020, 36, 33-39; e) J. L. Snider,
Li, W. Wei, Y. Sun, Catal. Today 2019, 330, 61-75. V. Streibel, M. A. Hubert, T. S. Choksi, E. Valle, D. C. Upham, J.
[18] J. Klankermayer, S. Wesselbaum, K. Beydoun, W. Leitner, Angew. Schumann, M. S. Duyar, A. Gallo, F. Abild-Pedersen, T. F. Jaramillo,
Chem. Int. Edit. 2016, 55, 7296-7343. ACS Catal. 2019, 9, 3399-3412.
[19] T. Sakakura, J. C. Choi, H. Yasuda, Chem. Rev. 2007, 107, 2365-2387. [31] a) H. Kong, H. Li, G. Lin, H. Zhang, Catal. Lett. 2011, 141, 886-894; b)
[20] a) M. A. A. Aziz, A. A. Jalil, S. Triwahyono, R. R. Mukti, Y. H. Taufiq-Yap, J. Wang, S. Lu, J. Li, C. Li, Chem. Commun. 2015, 51, 17615-17618.
M. R. Sazegar, Appl. Catal. B 2014, 147, 359-368; b) S. Danaci, L. [32] a) A. Gotti, R. Prins, J. Catal. 1998, 175, 302-311; b) N. Koizumi, X.
Protasova, J. Lefevere, L. Bedel, R. Guilet, P. Marty, Catal. Today Jiang, J. Kugai, C. Song, Catal. Today 2012, 194, 16-24.
19
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[33] J. H. Kwak, L. Kovarik, J. Szanyi, ACS Catal. 2013, 3, 2094-2100. D. Gardini, G. L. Chiarello, C. D. Damsgaard, J. B. Wagner, J. D.
[34] Z. Zsoldos, A. Sarkany, L. Guczi, J. Catal. 1994, 145, 235-238. Grunwaldt, S. Dahl, I. Chorkendorff, J. Catal. 2014, 320, 77-88; c) A.
[35] A. Erdöhelyi, M. Pásztor, F. Solymosi, J. Catal. 1986, 98, 166-177. Gallo, J. L. Snider, D. Sokaras, D. Nordlund, T. Kroll, H. Ogasawara, L.
[36] C. Shao, L. Fan, K. Fujimoto, Y. Iwasawa, Appl. Catal. A 1995, 128, Kovarik, M. S. Duyar, T. F. Jaramillo, Appl. Catal. B 2020, 267, 118369;
L1-L6. d) Q. Tang, Z. Shen, L. Huang, T. He, H. Adidharma, A. G. Russell, M.
[37] S. B. T. Tran, H. Choi, S. Oh, J. Y. Park, Catal. Lett. 2019, 149, 2823- Fan, Phys. Chem. Chem. Phys. 2017, 19, 18539-18555; e) Q. Tang, W.
2835. Ji, C. K. Russell, Z. Cheng, Y. Zhang, M. Fan, Z. Shen, Appl. Energy
[38] Z. Han, C. Tang, J. Wang, L. Li, C. Li, J. Catal. 2020, doi: 2019, 253, 113623.
10.1016/j.jcat.2020.06.018. [54] W. Li, K. Wang, J. Huang, X. Liu, D. Fu, J. Huang, Q. Li, G. Zhan, ACS
[39] K. Sun, N. Rui, Z. Zhang, Z. Sun, Q. Ge, C. Liu, Green Chem. 2020, Appl. Mater. Inter. 2019, 11, 33263-33272.
22, 5059-5066 [55] X. Wang, Y. Wang, C. Yang, Y. Yi, X. Wang, F. Liu, J. Cao, H. Pan,
[40] Y. Men, Y. Liu, Q. Wang, Z. Luo, S. Shao, Y. Li, Y. Pan, Chem. Eng. Appl. Catal. A 2020, 595, 117507.
Sci. 2019, 200, 167-175. [56] C. Temvuttirojn, Y. Poo-arporn, N. Chanlek, C. K. Cheng, C. C. Chong,
[41] a) Y. Hartadi, D. Widmann, R. J. Behm, ChemSusChem 2015, 8, 456- J. Limtrakul, T. Witoon, Ind. Eng. Chem. Res. 2020, 59, 5525-5535.
465; b) A. Vourros, I. Garagounis, V. Kyriakou, S. A. C. Carabineiro, F. [57] a) J. Ye, C. Liu, D. Mei, Q. Ge, ACS Catal. 2013, 3, 1296-1306; b) K.
J. Maldonado-Hódar, G. E. Marnellos, M. Konsolakis, J. CO2 Util. 2017, Sun Z. Fan, J. Ye, J. Yan, Q. Ge, Y. Li, W. He, W. Yang, C. Liu, J.
Accepted Manuscript
19, 247-256. CO2 Util. 2015, 12, 1-6; c) M. S. Frei, M. Capdevila-Cortada, R.
[42] C. Wu, P. Zhang, Z. Zhang, L. Zhang, G. Yang, B. Han, García-Muelas, C. Mondelli, N. López, J. A. Stewart, D. Curulla Ferré,
ChemCatChem 2017, 9, 3691-3696. J. Pérez-Ramírez, J. Catal. 2018, 361, 313-321; d) A. Tsoukalou, P.
[43] A. B. Vidal, L. Feria, J. Evans, Y. Takahashi, P. Liu, K. Nakamura, F. M. Abdala, D. Stoian, X. Huang, M. G. Willinger, A. Fedorov, C. R.
Illas, J. A. Rodriguez, J. Phys. Chem. Lett. 2012, 3, 2275-2280. M5ller, J. Am. Chem. Soc. 2019, 141, 13497-13505; e) S. Dang B. Qin,
[44] H. Sakurai, M. Haruta, Catal. Today 1996, 29, 361-365. Y. Yang, H. Wang, J. Cai, Y. Han, S. Li, P. Gao, Y. Sun, Sci. Adv.
[45] J. Słoczyński, R. Grabowski, A. Kozłowska, P. Olszewski, J. Stoch, J. 2020, 6, eaaz2060.
Skrzypek, M. Lachowska, Appl. Catal. A 2004, 278, 11-23. [58] a) O. Martin, A. J. Martín, C. Mondelli, S. Mitchell, T. F. Segawa, R.
[46] X. Yang, S. Kattel, S. D. Senanayake, J. A. Boscoboinik, X. Nie, J. Hauert, C. Drouilly, D. Curulla-Ferré, J. Pérez-Ramírez, Angew. Chem.
Graciani, J. A. Rodriguez, P. Liu, D. J. Stacchiola, J. G. Chen, J. Am. Int. Edit. 2016, 55, 6261-6265; b) M. S. Frei, C. Mondelli, A. Cesarini, F.
Chem. Soc. 2015, 137, 10104-10107. Krumeich, R. Hauert, J. A. Stewart, D. Curulla Ferré, J. Pérez-Ramírez,
[47] S. Tada, F. Watanabe, K. Kiyota, N. Shimoda, R. Hayashi, M. ACS Catal. 2020, 10, 1133-1145; c) T. Chen, C. Cao, T. Chen, X. Ding,
Takahashi, A. Nariyuki, A. Igarashi, S. Satokawa, J. Catal. 2017, 351, H. Huang, L. Shen, X. Cao, M. Zhu, J. Xu, J. Gao, Y. Han, ACS Catal.
107-118. 2019, 9, 8785-8797; d) C. Chou, R. F. Lobo, Appl. Catal. A 2019, 583,
[48] R. Grabowski, J. Słoczyński, M. Śliwa, D. Mucha, R. P. Socha, M. 117144.
Lachowska, J. Skrzypek, ACS Catal. 2011, 1, 266-278. [59] M. Dou, M. Zhang, Y. Chen, Y. Yu, Surf. Sci. 2018, 672-673, 7-12.
[49] H. Choi, S. Oh, S. B. Trung Tran, J. Y. Park, J. Catal. 2019, 376, 68-76. [60] N. Akkharaphatthawon, N. Chanlek, C. K. Cheng, M. Chareonpanich,
[50] S. Furukawa, T. Komatsu, ACS Catal. 2017, 7, 735-765. J. Limtrakul, T. Witoon, Appl. Surf. Sci. 2019, 489, 278-286.
[51] a) R. Manrique, R. Jiménez, J. Rodríguez-Pereira, V. G. Baldovino- [61] A. Bavykina, I. Yarulina, A. J. Al Abdulghani, L. Gevers, M. N. Hedhili,
Medrano, A. Karelovic Int. J. Hydrogen energy 2019, 44, 16526- X. Miao, A. R. Galilea, A. Pustovarenko, A. Dikhtiarenko, A. Cadiau, A.
16536.; b) R. Manrique, J. Rodríguez-Pereira, S. A. Rincón-Ortiz, J. J. Aguilar-Tapia, J. L. Hazemann, S. M. Kozlov, S. Oud-Chikh, L. Cavallo,
Bravo-Suárez, V. G. Baldovino-Medrano, R. Jiménez, A. Karelovic, J. Gascon, ACS Catal. 2019, 9, 6910-6918.
Catal. Sci. Technol. 2020, doi: 10.1039/d0cy00956c; c) A. Ota, E. L. [62] C. Li, G. Melaet, W. T. Ralston, K. An, C. Brooks, Y. Ye, Y. Liu, J. Zhu,
Kunkes, I. Kasatkin, E. Groppo, D. Ferri, B. Poceiro, R. M. Navarro J. Guo, S. Alayoglu, G. A. Somorjai, Nat. Commun. 2015, 6, 6538.
Yerga, M. Behrens, J. Catal. 2012, 293, 27-38; d) S. E. Collins, J. J. [63] K. Stangeland, D. Y. Kalai, Y. Ding, Z. Yu, J. CO2 Util. 2019, 32, 146-
Delgado, C. Mira, J. J. Calvino, S. Bernal, D. L. Chiavassa, M. A. 154.
Baltanás, A. L. Bonivardi, J. Catal. 2012, 292, 90-98; e) O. Oyola- [64] L. Wang, E. Guan, Y. Wang, L. Wang, Z. Gong, Yi Cui, X. Meng, B. C.
Rivera, M. A. Baltanás, N. Cardona-Martínez, J. CO2 Util. 2015, 9, 8- Gates, F. Xiao, Nat. Commun. 2020, 11, 1033.
15. [65] a) F. Gallucci, A. Basile, Int. J. Hydrogen Energy 2007, 32, 5050-5058;
[52] P. Wu, B. Yang, Catal. Sci. Technol. 2019, 9, 6102-6113. b) F. Gallucci, L. Paturzo, A. Basile, Chem. Eng. Process. 2004, 43,
[53] a) F. Studt, I. Sharafutdinov, F. Abild-Pedersen, C. F. Elkjær, J. S. 1029-1036; c) A. Tavolaro, P. Tavolaro, Catal. Commun. 2007, 8, 789-
Hummelshøj, S. Dahl, I. Chorkendorff, J. K. Nørskov, Nat. Chem. 2014, 794.
6, 320-324; b) I. Sharafutdinov, C. F. Elkjær, H. W. Pereira de Carvalho,
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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.
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2020 Nov Hydrogenation of Carbon Dioxide To Methanol Over Non-Cu

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Chemistry–Sustainability–Energy–Materials

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

To be cited as: ChemSusChem 10.1002/cssc.202002054

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

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-

favorable for methanol synthesis due to the exothermic nature

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

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

4.1.3 Pd supported on CeO2 and In2O3

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

4.1.5 Pd supported on silica materials

Supporting Pd-based catalysts on mesoporous silica

Figure 7. (a) Theoretical activity volcano for CO2 hydrogenation to methanol.

Shen et al. investigated the reaction mechanisms of CO2

13% ZnO-ZrO2 solid solution catalyst can be hydrogenated to

6.2 In2O3-based Oxide Catalysts

Recently, In2O3 and In2O3-based oxide catalysts have

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