Results in Engineering 16 (2022) 100711

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Results in Engineering
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Methanol synthesis from CO2: A mechanistic overview

Noerma J. Azhari a, 1, Denanti Erika b, 1, St Mardiana b, Thalabul Ilmi c, Melia L. Gunawan a, c,
I.G.B.N. Makertihartha a, c, Grandprix T.M. Kadja b, c, d, *
a
Department of Chemical Engineering, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung, 40132, Indonesia
b
Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung, 40132,
Indonesia
c
Center for Catalysis and Reaction Engineering, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung, 40132, Indonesia
d
Research Center for Nanosciences and Nanotechnology, Institut Teknologi Bandung, Jl. Ganesha No. 10, Bandung, 40132, Indonesia

A R T I C L E I N F O A B S T R A C T

Keywords: Currently, energy demand is growing swiftly with global economic growth. The combustion of fossil fuels is one
Methanol synthesis of the major environmental threats due to the release of CO2 into the atmosphere. Reducing greenhouse gases is
CO2 hydrogenation one of the most critical challenges facing society today. It has been proposed that converting CO2 into fuels and
Reaction pathway
valuable chemicals such as methanol for reducing greenhouse gas emissions can be a favorable solution. This
Cu-based catalyst
Precious metal-based catalyst
review describes the recent development of methanol synthesis from CO2 from a mechanistic point of view.
Oxide-based catalyst Several proposed reaction pathways for methanol formation over various catalysts will be emphasized, i.e., Cu-
Oxygen deficient-based catalyst based catalyst, precious metal-based catalyst, and other catalysts, including oxide-, oxygen deficient-, and
Composite-based catalyst composite-based catalysts such as metal alloys, and supported metal alloys. Additionally, the intermediate
involved, active site, and several aspects affecting the catalytic behavior are also provided. Finally, a remaining
challenge and the perspective for compelling the energy future vision is emphasized.

1. Introduction
In recent years, many industrial fields used fossil fuels, which
contribute to greenhouse gas (GHG) emissions, especially carbon diox­
ide (CO2) [1–3]. Consequently, it raises climate change issues, an urgent
global challenge to resolve [4,5]. Compared with the GHG level in 2010,
CO2 reduction of 41–72% by 2050 and 78–118% by 2100 is necessary to
preserve the temperature change below 2 ◦ C relative to preindustrial
levels [6]. In this case, converting CO2 into valuable products through
several processes is one of the promising strategies for reducing its
emission. For instance, electrocatalytic and photocatalytic CO2 reduc­
tion is subjected as a potential process for future. However, the recent
techniques are still incapable to meet large-scale industrial applications
requirements. At present, thermo-catalytic is still a more feasible
method for industrial application.
In the thermo-catalytic reaction process, CO2 hydrogenation has
gained much attention. Hydrogen (H2) is a suitable reagent to assist the
CO2 conversion, in which it can be generated from the electrolysis of
water using renewable energies, e.g., wind, geothermal, hydro, and solar
[7]. Several important chemical products could be obtained from this
process, e.g., methane [8,9], alkanes [10], carbon monoxide [11], ole­
fins [12], and alcohol [13]. Among the possible CO2 reduction products,
methanol is one of the important compounds of C1 chemistry because
approximately more than 110 Mt/year of methanol is required to fulfill
its demand in many areas. For instance, methanol acts as a chemical
intermediate and molecule platform for the synthesis of important
commodities and products such as formaldehyde, acetic acid, methyl
tert-butyl ether (MTBE), and gasoline (MTG) [14,15] (Fig. 1). It also
could be an excellent substitute or additive for fuel and modified diesel
engines due to their high octane rating [15]. Furthermore, methanol
could generate electricity in direct oxidation methanol fuel cells (DMFC)
[16]. Therefore, methanol production from CO2 benefits from environ­
mental and economic points of view. Generally, a catalyst is needed to
transform the CO2 into a methanol product because CO2 is a highly
stable molecule. Many types of catalysts can assist the CO2 conversion
into methanol, but metal and/or metal oxide-based catalysts are mostly

* Corresponding author. Division of Inorganic and Physical Chemistry, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jl. Ganesha No.
10, Bandung, 40132, Indonesia.
E-mail address: grandprix.thomryes@itb.ac.id (G.T.M. Kadja).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.rineng.2022.100711
Received 9 August 2022; Received in revised form 12 October 2022; Accepted 16 October 2022
Available online 19 October 2022
2590-1230/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
N.J. Azhari et al.
Fig. 1. Methanol consumption by industries.
used to facilitate the redox reaction, i.e., Cu [17–21], Zn [22–25], Cr
[26,27], and Pd [28–30]. Furthermore, other materials for the promoter
of support have been reported.
Many researchers have made significant progress on the CO2 hy­
drogenation to methanol products. The publications related to these
topics gradually grew year by year (Fig. 2). Also, Several reviews are
already available to provide extensive insight from various points of
view. Some reviews only focused on one type of catalyst [31–33]. Others
provide a broader range of catalyst types [34,35]. Furthermore, the
review based on the catalyst design, thermodynamic, kinetic, and the
development of technical aspects of this reaction has also been provided
[15,36–38]. Herein, we intend to focus on the mechanistic aspect of the
methanol synthesis from CO2 hydrogenation over metal-based catalysts,
including Cu-, precious metal-, and other catalysts (composite-, Oxygen
deficient- and oxide-based catalyst).
Furthermore, the active site, the intermediate involved, and several
factors affecting the reaction pathways will be discussed. An in-depth
understanding of this aspect is crucial since it could be used to
improve many aspects of this process. For instance, the build of an
appropriate synthesis strategy to design an efficient catalyst or the ki­
netic model for industrial-scale development could be generated. In that
sense, this review benefits from bringing various perspectives regarding
the catalytic behavior of several types of catalysts through the recent
development from the mechanistic point of view. Finally, challenges and
insight for future development regarding the sustainable development of
CO2 hydrogenation to methanol will be emphasized.
Fig. 2. Numbers of published papers related to CO2 hydrogenation and metal catalyst topics indexed by Scopus on January 25, 2022.
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Results in Engineering 16 (2022) 100711
2. Methanol synthesis from CO2
Commercially, methanol is synthesized from natural gas through the
syngas route. It contains two processes, i.e., (i) the steam reforming of
methane and (ii) methanol production. The former is the most expensive
step in the production process chain since it proceeds at very high
temperatures (1173 K) and pressure (16–30 bar) [39]. This reaction
follows eqs. (1) and (2), resulting in a mixture of CO, CO2, and H2. Also,
CO2 may form through WGS (Water-Gas Shift) reaction (eq. (4)) [15].
This reaction is usually used to adjust the CO2/H2 ratio in the feed for the
methanol synthesis reaction [40]. The latter process is usually per­
formed at 250–300 ◦ C, 5–10 MPa, in the presence of CuO/ZnO/Al2O3 as
a catalyst [15]. In this case, the methanol product could be obtained
either from CO or CO2 as the reactant (eq. (3) and (5)).
CH4 + H2 O ↔ CO + 3H2 ΔH ◦ = 206 kJ/mol (1)
CH4 + 2H2 O ↔ CO2 + 4H2 ΔH◦ = 165 kJ/mol (2)
CO2 + 3H2 ↔ CH3 OH + H2 O ΔH◦ = − 49.5 kJ/mol (3)
CO + H2 O ↔ CO2 + H2 ΔH◦ = − 41 kJ/mol (4)
CO + 2H2 ↔ CH3 OH ΔH◦ = − 90.5 kJ/mol (5)
Producing methanol from CO2 is a promising pathway because it
benefits both the economics and environmental point of view. It con­
tributes to resolving climate change issues by reducing greenhouse gas
emissions. Moreover, it could produce various high-value-added prod­
ucts with remarkable economic value although the realization of this
process still faces many challenges. From the thermodynamic point of
view, CO2 is more stable than CO. The heat formation of CO2 was − 393
kJ/mol. Meanwhile, CO is − 110 kJ/mol. Also, CO2 has the high bond
energy of the C– – O double bond (750 kJ/mol). It is larger than that of
C–C (336 kJ/mol), C–O (327 kJ/mol), or C–H bond (411 kJ/mol) [41].
Therefore, activating the CO2 molecule needs a much higher energy
input, appropriate reaction conditions, and the presence of the catalyst
[34].
In addition, the CO2 to methanol reaction is very exothermic and
kinetically limited to 15–25% conversion [42]. CO2 may also convert
into CO product through RWGS reaction, which is endothermic. In that
sense, the reactor model should be designed efficiently. The reactor
should be capable of removing heat released from the methanol syn­
thesis reaction to keep the reactor in isothermal condition [43].
Furthermore, water is produced as a byproduct of the methanol syn­
thesis from CO2. Its presence can cause the deactivation of the catalyst,
especially for the conventional copper-based catalyst [44]. Therefore,
catalyst and reactor design, as well as kinetic study, are crucial for
realizing the methanol production from CO2.
N.J. Azhari et al.
Various kinetic models were currently reported in the literature
using either Eley-Rideal (ER) or Langmuir – Hinshelwood (LH) mecha­
nism. The conversion of CO2 into methanol products generally could
occur via formate, RWGS, or trans-COOH* pathway (Fig. 3). For the
classical formate pathway, CO2 reacted with adsorbed atomic H and
formed the formate (HCOO*). Then, it gradually transforms into
dioxomethylene (H2COO*), formaldehyde (H2CO*), methoxy (CH3O*),
and methanol (CH3OH), respectively. However, others reported that
instead of dioxomethylene (H2COO*), formate species are preferentially
hydrogenated into formic acid (HCOOH*). Then, it transforms into
H2COOH*, which continuously splits to generate formaldehyde and OH
species. Finally, methanol was produced from this formaldehyde species
via methoxy intermediate [45,46].
On the other hand, methanol formation via the RWGS pathway began
from the transformation of CO2 into CO* species, then it subsequently
hydrogenated into methanol through the formation of formyl (HCO*) →
formaldehyde (H2CO*) → methoxy H3CO* species. This pathway could
also proceed with the hydrocarboxyl species formation (COOH*) fol­
lowed by the CO* and the same species with the previous pathway. The
hydrocarboxyl (COOH*) species was generated from the reaction be­
tween CO2 with H atoms which is provided by H2O. Therefore, some­
times it is called an H2O-mediated mechanism. Some researchers
reported that rather than CO* species production, dihydroxycarbene
(COHOH*) was formed as an active species after hydrocarboxyl for­
mation. Then, dihydroxycarbene was dissociated into the hydrox­
ymethylidyne (COH*) species. It further transforms into
hydroxymethylene (HCOH*) → hydroxymethyl (H2COH*), and finally,
methanol product. This pathway was then known as the trans-COOH
mechanism [45,46]. The mechanisms above were affected by various
factors, such as the catalyst properties and reaction conditions. We will
bring these discussions to the following section.
3. Catalysts for conversion of CO2 into methanol
3.1. Cu-based catalysts
Cu-based catalyst is the most used catalyst in methanol synthesis. It is
usually synthesized from its salt through the coprecipitation method in
the presence of basic precipitation agents, such as carbonates, bi­
carbonates, or hydroxides. This reaction was conducted in an aqueous
medium. Also, the following process, such as aging, calcination, and
reduction, may be performed [46]. Currently, Cu-based catalyst with
various support and promoter for methanol synthesis from CO2 has been
reported, e.g., Cu/ZnO, Cu/CeO2, Cu-ZO/ZrO2. Although much progress
Fig. 3. Schematic representation of several proposed reaction mechanisms of
methanol formation from CO2.
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Results in Engineering 16 (2022) 100711
on catalyst design has been made, deeper insight into the mechanistic
aspect of the catalysis system should gain serious attention since it
provides essential information to generate rational strategies for the
design of the next-generation catalyst.
In the Cu-based-catalyst, Cu provides the active sites. Meanwhile,
support facilitates the dispersion of active metal Cu. During the catalysis
process, Cu should be reduced to generate Cu0 or Cu+ as a dominant
species in the catalyst, which is believed to be an active site for methanol
synthesis. In that sense, the reaction could occur either on one or two of
those surfaces. Moreover, it has been reported that other active centers
may generate from the interaction between active metal and its support
[47]. Therefore, it further improved the catalytic performance. For
instance, the formation of the Cu–ZrO2 interface could enhance the
methanol production rate by facilitating CO2 activation and stabilizing
the intermediates, such as CO and formaldehyde [48]. The synergetic
effect between metal-support interfaces was also demonstrated by Arena
et al. [49] using Cu–ZnO/ZrO2 as the catalyst. The promotion effect was
related to the excellent capability of ZrO2 and ZnO to enhance the CO2
affinity and increase the surface availability for generating the reactive
formate intermediate.
Further, the effect of the zirconia phase in Cu-based catalyst was
investigated by Witoon and Coworker [50]. In this work, they used three
different phases of ZrO2, i.e., amorphous (a-), tetragonal (t-), and
monoclinic (m-) phases, on Cu/ZrO2 catalyst for converting CO2 to
methanol. The amorphous Cu/ZrO2 exhibits the highest yield of meth­
anol related to its highest Cu surface area. However, the highest turn­
over frequency was owned by the Cu/t-ZrO2 catalyst. As demonstrated
by Cu K-edges XANES spectra in Fig. 4a, only the monoclinic phase of
ZrO2 resembles the CuO reference spectra. Contrarily, both amorphous
and tetragonal phases of ZrO2 exhibit the change of the local catalyst
structure toward the octahedral structure (also convinced by the shifting
of the derivative XANES spectra). Therefore, it is further justified that
these two phases have a stronger interaction with Cu. It facilitates the
spillover of H2 from Cu on the ZrO2 surface, leading to high adsorption
of H2 (high ratio of hydrogen to CO2) as revealed by CO2- and H2-TPD
characterization results (Fig. 4b and c).
Generally, CO2 hydrogenation towards methanol over Cu-based
catalyst was believed to occur via the formate mechanism. Grabow
and Mavrikakis [21] performed the DFT calculation of the methanol
production on commercial Cu-based catalysts, i.e., Cu/ZnO/Al2O3,
especially on the Cu (111) site. This experiment used CO2 and CO as
reactants to investigate each component’s role in the reaction. Then, the
microkinetic model was built from the DFT calculation. The result
showed that the CO2 hydrogenation occurs via the formate pathway
(CO2* → HCOO* → HCOOH* → CH3O2* → CH2O* → CH3O* →
CH3OH*). Meanwhile, the methanol production from CO follows the
sequence of CO* → HCO* → CH2O* → CH3O* → CH3OH*. For the
CO2-rich feed, the hydrogenation of CH3O* is the rate-determining step.
Meanwhile, the formation of CH3O* is the RDS in CO-rich feed. The
reaction network of methanol synthesis and WGS reaction is shown in
Fig. 5.
Moreover, based on the DFT calculation, CO2 hydrogenation con­
tributes 2/3 of the methanol product. This result was the opposite of the
potential energy surface (PES) analysis (Fig. 6a), which showed that
methanol should be more produced from CO hydrogenation. It is
reasonable because CO hydrogenation is more exothermic than CO2
hydrogenation, and the high energy barrier was owned by CO2 hydro­
genation (CH3O* hydrogenation (black line) and OH* hydrogenation to
form H2O* (blue line after state 3). These phenomena were related to the
promotional effect of CO on CO2 hydrogenation. CO* is more consumed
for the HCO* production, and it could be the H-donor to assists the CO2
hydrogenation [21].
On the other hand, Zhao et al. [52] emphasize the role of water in
methanol synthesis. They demonstrated that in the presence of water,
the formation of hydrocarboxyl (trans-COOH) species on the Cu (111)
site is kinetically favorable than formate species. It occurs via a hydrogen
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

Fig. 4. (a) Cu K-edges XANES Spectra of Cu/ZrO2 catalyst and reference compound. (b) H2-TPD (c) CO2-TPD profiles of Cu/ZrO2 catalysts. Reproduced with
permission from Ref. [50]. Copyright 2016 Elsevier.

Fig. 5. The reaction network of methanol synthesis and WGS reaction over Cu
catalyst. Reproduced with permission from Ref. [21], Copyright 2011 American
Chemical Society.

transfer mechanism. This intermediate is then transformed step by step

Fig. 6. (a) Potential energy surface for methanol synthesis reaction from CO
into dihydroxycarbene (COHOH) → hydroxymethylidyne (COH) →
and CO2. Reproduced with permission from Ref. [21], Copyright 2011 Amer­
hydroxymethylene (HCOH) → hydroxymethyl (H2COH), and finally,
ican Chemical Society. (b) Potential energy surface for the most probable re­
methanol product. This result was confirmed by computational and action pathway in CO2 hydrogenation to methanol over Cu-based catalyst with
experimental methods. The DFT calculation showed that the decompo­ a different promoter. Reproduced with permission from Ref. [51], Copyright
sition of COHOH to COH and OH is the rate-determining step with an 2017 Royal Society of Chemistry.
energy barrier of 0.68 eV. It is much lower than the formate mechanism,
in which the two highest energy barriers are 1.20 and 1.17 eV. Further,
the mechanism of methanol synthesis in other facets of Cu catalyst, i.e.,

4
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

Cu (100) and Cu (110) surfaces, have also been reported by Higham
et al. [53] using the density functional calculation. Results show that
those two facets play a role in CO2 activation. Methanol synthesis could
occur via HCOO* and COOH*. Furthermore, the barrier energy of the
initial hydrogenation process on those sites shows a significantly lower
value, resulting in improved catalytic behavior for CO2 dissociation and
hydrogenation.
Huš et al. [51] investigated the mechanism of the Cu-based catalyst
with the different promoters, i.e., Zn3O3/Cu, Cr3O3/Cu, Fe3O3/Cu, and
Mg3O3/Cu, using Ab initio plane-wave density functional theory cal­
culations and the Kinetic Monte Carlo simulations. The result showed
that all the catalyst follows the formate pathway mechanism, although

Fig. 7. (a) Methanol and CO concentration of outlet on the temporal of the reaction and the phase-resolved DRIFT spectra obtained from a modulated-excitation
experiment for the catalyst which was first pre-treated with CO/H2 (i, iii) and CO2/H2 (iii, iv). Reproduced with permission from Ref. [59], Copyright Wiley
2016. (c) Schematic proposed mechanism of methanol formation over CuO/CeO2/ZrO2. Reproduced with permission from Ref. [60], Copyright Elsevier 2022.

5
N.J. Azhari et al.
with the variation in the surface intermediate fraction and
rate-determining step (Fig. 6b). Also, Zn3O3/Cu catalyst results in high
catalytic activity. The understanding of the active site of the Cu–Zn
catalyst has also been studied by Kattel et al. [54]. In this experiment,
they used ZnCu and ZnO/Cu as model catalysts to carefully study the
active site during the methanol production from CO2. The result showed
that methanol formation over both catalysts is via formate intermediate.
Furthermore, the presence of Zn or ZnO in ZnCu and ZnO/Cu catalysts
assists the system in stabilizing the *HCOOH intermediates via Zn–O
interaction. Also, it enhances the *HCOO activation via the hydroge­
nation process. Lam et al. [55] pointed out that the excellent activity in
Cu-based catalysts originated from the metal-oxide interface, although
the type of support may affect the selectivity and product distribution.
For instance, using Al2O3 for Cu support could further convert methanol
to dimethyl ether due to the Lewis acid availability.
In commercial methanol synthesis, adding a certain amount of CO2
to the syngas feed could enhance the methanol synthesis rate [56–58].
Pérez-Ramírez and Co-Worker [59] found that the volcano-type diagram
was obtained when partially replacing the CO with CO2 feed. The
space-time yield of methanol achieved a maximum value when the CO2
volume content in the feed was 2.4%. Under this optimal mixture, the
sintering between the components of the catalysts could be avoided;
therefore, it enhances the activity of methanol production. Further, they
investigated the effect of this CO2 promotion. In their work, the com­
mercial methanol catalyst, Cu–ZnO–Al2O3, was employed. Meanwhile,
the operando synchrotron x-ray powder diffraction and
modulated-excitation infrared spectroscopy were applied to elucidate
the promotion mechanism. Fig. 7a shows the time-dependant trans­
formation of CO and methanol during the hydrogenation reaction of CO2
and the optimum mixture of CO + CO2. The catalyst was first pre-treated
with CO2/H2 (Fig. 7a (i & ii)) and CO/H2 (Fig. 7a (iii & iv)). Under the
CO2/H2, the catalyst size increase and the platelet-like structures of ZnO
was formed, in which it contains a high amount of polar facets. It further
enhances the electronic interaction with Cu and preventing the forma­
tion of active sites. Therefore, the RWGS reaction could be suppressed. It
also confirmed by the Phase-resolved DRIFT spectra obtained from a
modulated-excitation experiment (Fig. 7a (ii & iv)) which reveal that
smaller CO adsorption was observed in the CO2/H2-pretreated sample.
Christensen and Coworker [61] have also investigated the role of CO
and CO2 at varying conversion levels over Cu/ZnO/Al2O3 catalysts. The
result shows that under very low conversion, CO inhibits Raney Cu
because of the competitive adsorption at the Cu surface. Conversely, the
beneficial impact of CO was obtained at higher conversion conditions by
lowering the gas space velocity. It was assigned to the water removal
capability of CO through the water-gas shift reaction because water is a
stronger inhibitor at higher conversion conditions than CO. They also
imply that at the lower conversion condition, the effect of both oxygen
vacancy in ZnO and Cu–Zn surface alloy sites from the ZnO is not
critical.
On the contrary, Zhu et al. [62] have demonstrated the opposite
effect of CO2 addition in the syngas feed of the methanol synthesis over
Cu–CeO2 catalyst. The presence of CO2 retarded the reaction due to the
formation of carbonate-like species on the interface site of Cu–CeO2.
Besides, this active site was needed to hydrogenate CO to obtain
methanol products via a formyl intermediate. The methanol was ob­
tained from two processes, i.e., the direct hydrogenation of CO2, which
occurred on the copper site, and the CO intermediate-mediated hydro­
genation, which involved the Cu–CeO2 interface as the active site. The
latter reaction was much faster. However, it is worth noting that the
mechanism should be affected by the reaction condition, as recently
reported by Poto et al. [60], in which CuO/CeO2/ZrO2 catalyst was used.
A similar contribution of CO2 and CO (51.5% and 47.4%) was found at
30 bar, 200 ◦ C, and 3 of the H2: CO2 molar ratio. While at higher tem­
peratures and H2: CO2 ratio, the contribution of CO is predominant due
to the Cu0 site saturation. The oxygen vacancy of CeO2–ZrO2 was
responsible for CO2 adsorption, and the metallic copper facilitated the
6
Results in Engineering 16 (2022) 100711
adsorption and dissociation of H2. As the hydrogen is dissociated, it will
hydrogenate the adsorbed CO2 to form a formate intermediate.
Sequentially, methanol was generated from a series of hydrogenation
processes of CO2 or CO which is produced by RWGS (Fig. 7c). Besides
ZnO, ZrO2, and CeO2, Au has also been reported to enhance the catalytic
activity of Cu-based catalysts on CO2 hydrogenation to methanol.
Adding 1% wt of Au could decrease the 10% mass of CO selectivity. This
improvement was assigned to the formation of copper-gold interfaces,
which facilitate the hydrogen spillover and enhance the CO and H2
adsorption capacities [63].
Engineering the catalyst surface properties is one of the crucial fac­
tors in obtaining the selective intermediate. Generally, it relates to the
availability of oxygen vacancy and the density of basic site. In the study
reported by Marcos et al. [64], preparing CuO–ZnO–ZrO2 catalyst
through the coprecipitation method assisted with Pluronic P123 suc­
cessfully improves its catalytic activity. The number of basic sites
increased with the surfactant/Cu–Zn–Zr molar ratio, which is beneficial
for CO2 adsorption. Based on the investigation by Singh et al. [65], a
high density of basic site and oxygen vacancies are needed to obtain high
selectivity in the hydrogenation reaction of CO2 to methanol. Among
oxides of CeO2, ZnO, and ZrO2, the combination of Cu with CeO2
resulted in the highest basicity and oxygen vacancy. This basicity plays a
role in species formation during the reaction (Fig. 8) [66]. In low ba­
sicity materials, CO2 adsorption generates bicarbonate species which are
very easy to desorb into CO2. At materials with medium basicity, CO2
adsorption produces bidentate carbonate species with hydrogen atoms
adsorbed on Cu, producing CO and H2O through the RWGS reaction
[67]. While the absorption of CO2 on the materials with higher basicity
results in unidentate carbonate species where hydrogenation of this
species will produce methanol through the formate pathway involving
H2COO, H2COOH, and H3COOH intermediates [68].
Very recently, Han et al. [69]. reported that a surface with a large
amount of basic site could be obtained by generating the hollow struc­
tured of Cu@ZrO2 from the Cu-loaded Zr-MOF pyrolysis process. This
structure could improve the adsorption capacity, CO2 activation, and
selective hydrogenation toward methanol products due to the highly
dispersed Cu nanoparticles coupled with the balanced Cu0/Cu+ sites and
the abundances of Cu–ZrO2 interfaces. This interface is crucial for the
intermediate formation, in which it facilitates the CO2 adsorption to
form the carbonate (CO3*) and/or bicarbonates (HCO3*) species as
observed by in situ FTIR spectroscopy. Furthermore, the appearance
peak associated with formate, methoxy, and methanol species with
exposure of time suggests the occurrence of methanol synthesis via
HCOO intermediate.
Despite all the factors mentioned above, the size of the Cu cluster was
also mentioned to affect the catalytic activity of the Cu-based catalyst in
methanol synthesis. To investigate this behavior, Yang et al. [70] syn­
thesized the Cun/Al2O3 with different clusters of Cu, i.e., n = 3, 4, and
20. Results showed that the catalytic activity of the catalyst on CO2
hydrogenation is strongly related to the Cu cluster with the order of Cu3
< Cu20 < Cu4. Furthermore, it was related to the reduced phase in the
catalyst. In this case, the temperature needed for each catalyst to
initially reduce is Cu3 > Cu20 > Cu4. Furthermore, the catalyst activity
was also correlated to its charge state. The higher charge state of Cu in
Cun/Al2O3 catalyst leads to weaker binding with intermediates, thus
resulting in low activity per atom. In the nano-sized scale of the
Cu-based catalyst, the methanol selectivity was reduced with the
decrease of the copper clusters. The larger copper dan ZnO particles
could generate the new active sites, leading to a higher intrinsic meth­
anol production rate and simultaneously suppressing the RWGS reaction
[71].
From the numerous development and the mechanism proposed,
designing the Cu-based catalyst for CO2 hydrogenation to methanol
product is still challenging regarding the low stability of Cu in the
presence of water byproduct and coke formation. Furthermore, the
presence of another strong competitive reaction, i.e., RWGS, makes Cu-
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

Fig. 8. CO2 adsorption at the surface of materials with different basic streght. Reproduced with permission from Ref. [65], Copyright 2021 Elsevier.

based catalyst difficult to obtain a simultaneously high conversion and
selectivity of methanol product. In that sense, combining Cu with suit­
able support could enhance its ability to activate the very stable CO2
molecule. The strong interaction between Cu and support could enhance
the reducibility of the catalyst. Furthermore, the metal-support inter­
action generates the interface that could stabilize the intermediates
involved during the reaction. Therefore, finding other new support
materials and/or alternative preparation method are still needed.
Wang et al. [72] introduced a new method called a facile microfluid
film-assisted coprecipitation method to improve the Cu dispersion on
the Zr–Ce oxide solution catalyst. The rapid nucleation of ternary
Cu–Zr–Ce is assisted by the H2 bubble obtained from the hydrolysis of
NaBH4 in the micro-liquid film reactor, resulting in the formation of
uniform nanoparticles (Fig. 9a). Moreover, Cu nanoparticles are highly
dispersed and surrounded by the Zr–Ce oxide solid solution. The inti­
mate contact between these two components produces strong metal
support interaction (SMSI) without aggregation. Meanwhile, Cu nano­
particle aggregation was observed for coprecipitation and impregnation
methods. Further analysis also demonstrated the presence of defective
Ce3+− Ov–Zr4+ structures (Ov: Oxygen vacancy) and Cu+− O− M (M =
Ce, Zr), leading to enhanced methanol formation because of the
improved formate intermediate transformation. Meanwhile, the
medium-strength and strong basic sites of Ce3+− O and Cu+− O pairs
were responsible for CO2 adsorption, and Cu0 sites play a role in the
activation of hydrogen species (Fig. 9b).
Very recently, the dual mechanism has also been reported for a new

Fig. 9. (a) Schematic description of the microfluid film assisted coprecipitation for synthesis Zr–Ce oxide solid solution surrounded by Cu nanoparticles (b) the
proposed mechanism of methanol for mation from CO2 hydrogenation over Zr–Ce oxide solid solution surrounded by Cu nanoparticles. Reproduced with permission
from Ref. [72] Copyright 2021 American Chemical Society.

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N.J. Azhari et al.
Cu-based catalyst, Cu–ZnO/nanosheet Pr2O3. The RWGS pathway and
formate pathway were believed to simultaneously occur based on the in-
situ DRIFT analysis. Similar to the previous results, the Cu0 was
responsible for the hydrogen dissociation at the initial step. Meanwhile,
the Cu–Pr2O3 interface facilitates the CO2 adsorption and reacts with the
adsorb hydrogen to form formate species through the for­
mate→methoxy→methanol route (blue route) (Fig. 10). On the other
hand, the Cu–Pr2O3 interface could also adsorb the CO from the RWGS
reaction in the meantime. Continuously, a series of hydrogenation of this
species generates formyl, formaldehyde, methoxy, and finally, meth­
anol. The occurrence of the CO transformation is associated with the
abundance of surface oxygen vacancy and metal-support interfacial site.
The existence of the oxygen vacancy could be able to generate metal
atoms with low-coordination numbers and more dangling bonds,
resulting in enhanced adsorption energy. The increase of the adsorption
energy of CO and CO2 at these surfaces reveals that those species could
be easily adsorbed, accelerating the methanol formation [73].
3.2. Precious metal-based catalysts
Aside from Cu-based catalysts, precious metal-based catalysts (e.g.,
Au, Pd, and Pt) have also been tested in the methanol synthesis from CO2
hydrogenation. These precious metals have attracted significant atten­
tion in CO2 to methanol conversion thanks to their high activity in the
adsorption and dissociation of H2 [74]. As the active metal, palladium
(Pd) exhibits expectant results for methanol synthesis [75,76]. However,
it is hard to produce methanol using the pure Pd site. Thus, usually, it
combines with other metals as promoters or support. In this sense, the
catalytic activity and methanol selectivity are influenced by the type of
promoters and support [29].
Several oxides have been used as support for Pd-based catalysts, e.g.,
ZnO [77], CeO2 [78], and Ga2O3 [75,79]. The research on Ga2O3-­
supported palladium (Pd/Ga2O3) for methanol synthesis from CO2 hy­
drogenation was pioneered by Fujitani et al. [79]. In their work, the
catalyst was prepared through the coprecipitation method. The result
showed that Pd/Ga2O3 catalyst generates better results (turnover fre­
quency (TOF) 20-fold higher) than Cu/ZnO. This result is also higher
than those of Pd on other metal oxide support materials such as Al2O3,
Fig. 10. Proposed mechanism of the CO2 hydrogenation toward methanol over Cu–ZnO/nanosheet Pr2O3. Reproduced with permission form Ref. [73], Copyright
2022 American Chemical Society.
8
Results in Engineering 16 (2022) 100711
Cr2O3, SiO2, TiO2, ZnO, and ZrO2. The different activity between these
oxides is associated to their ability to stabilize the Pdn+ (0 < n < 2)
species. Also, it provides an optimal amount of Pdn+. Other researchers
suggested that the enhanced catalytic activity of Pd/Ga2O3 catalyst was
related to the Pd− Ga intermetallic site, which facilitates the methanol
formation [80], especially the hydrogenation of bidentate formate
(b-HCOO) intermediates [81]. Moreover, further study revealed that the
formation of intermetallic PdxGa species depends on the reduction
temperature and the different phases of Ga2O3. For instance, on β-Ga2O3,
Pd2Ga was observed at temperature 673 K, and PdGa was detected if the
reduction was performed at 773 K. Meanwhile, almost 100% Pd2Ga was
observed on α-Ga2O3 and γ-Ga2O3 at the 523 K and 673 K temperature
reduction, respectively [82,83]. It is reasonable because the different
phases of Ga2O3 may have different stability under the reduction
condition.
García-Trenco et al. [75] developed colloidal Pd2Ga nanoparticle
catalysts to hydrogenate CO2 to methanol. This catalyst was prepared
through a two-step procedure, i.e., thermal decomposition reaction of
Pd(OAc)2 (palladium acetate) and Ga(OSt)3 (gallium stearate), which
heating to 190 ◦ C using N2 flow, followed by the reduction of the colloid
(Pd/Ga mixture) that utilize a dilute H2 flow (5% H2/N2, 0.5 MPa) at a
selected temperature (Fig. 11a). As a result, Pd2Ga nanoparticles were
successfully synthesized with an average size of 5–6 nm. Results show
that the rate of methanol and the TOF increase with the increase of Ga
content in the catalyst (maximum at Pd: Ga molar ratio = 1:2) (Fig. 11b
and c). Both Pd2Ga and Ga2O3 phase has a crucial role in methanol
formation. However, their work did not provide a detailed mechanism
and the role of each active phase. The previous study by other re­
searchers suggests that the Ga2O3 surface facilitates CO2 adsorption to
form bicarbonate species. This species was sequentially transformed into
methanol through the formates, methylenebisoxy, and methoxy inter­
mediate species. This ability was related to its excellence in the disso­
ciation and chemisorption of H2. Meanwhile, the Pd–Ga promote the
spillover for hydrogen supply and increase the bonded carbonaceous to
Ga2O3 phase [84,85].
More recently, Collins et al. [86] reported the Pd-Ga-supported
mesoporous SiO2 as an efficient catalyst for methanol production from
CO2. Pd–Ga/SiO2 has a lower activation energy (~40 kJ/mol) than
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

Fig. 11. (a) Representation of synthesis Pd2Ga nanoparticles. (b) Methanol rate and selectivity and (c) TOF for samples with varying the Pd:Ga molar ratios at
290 ◦ C. Cu–ZnO–Al2O3 data was included as the benchmark. Adapted with permission from Ref. [75], Copyright 2017 American Chemical Society.

Pd/SiO2 (60 kJ/mol), with a 200-fold turnover frequency. Character­
ization using in situ transmission infrared spectroscopy suggests that thin
layer gallium oxide (Ga2O3) facilitates CO2 adsorption to form poly­
dentate carbonate species, which are further transformed into methanol
via hydrogen spillover. Additionally, Pd2Ga bimetallic particles act as
the catalytic site for H2 dissociation for providing atomic hydrogen to
the Ga2O3 site. Thus, the intimacy between Ga2O3 and Pd2Ga surface is
essential for enhancing catalytic performance.
Although the synergetic effect between Pd and Ga has been reported,
it should be noted that adjusting the molar ratio between the two
components is also essential. Manrique et al. [81] found that the molar
ratio 1 of Pd/Ga is the optimum value for obtaining the improved cat­
alytic activity of the Pd–Ga/SiO2 catalyst. This result was confirmed
using XPS and Operando DRIFTS analysis, and the schematic illustration
of the catalyst surface with various Pd/Ga molar ratios was depicted in
Fig. 12. At the high Pd/Ga ratio, the Pd phase was detected as the
monometallic form along with the Ga2O3 phase covered the Pd sites,
thus inhibiting the methanol formation since Pd was responsible for
bidentate formate adsorption. On the other hand, the intermetallic
Pd–Ga was formed only for Pd/Ga ≤ 1. This was followed by a
significant increase of the formation methano rate, suggesting the
importance of the intermetallic site in methanol formation. However, at
the ratio Pd/Ga <1, the exact stoichiometry could not be achieved,
resulting in a higher amount of Ga2O3 on the surface; thus, the exposed
intermetallic surface was reduced, and the lower reaction rate was
observed.
The spillover capability of Pd benefits methanol production; there­
fore, Pd has also been used for promoters in Cu-based catalysts, as re­
ported by Choi et al. [78]. Pd addition on methanol catalyst, Cu/CeO2,
could enhance the catalytic activity due to the improvement of the Cu
site reducibility through hydrogen spillover property. This electron-rich
metal site tends to be more favorable to interacting with CO2 resulting in
the formation of the O– – C–O− group and COOH intermediates (RWGS
pathway). As studied by Liu and coworkers [42], the formate pathway
was dominant only for Au-doped Cu(111). Meanwhile, for the Pd, Rh Pt,
and Ni, the RWGS pathway is faster.
Conversely, the formate pathway is more acceptable for Pd–Zn
catalyst. In the study reported by Bahruji et al. [76], PdZn could stabilize
the formate intermediate, leading to high methanol production. PdZn
also impedes the CO formations. Meanwhile, Pd metal induces the

Fig. 12. Schematic Illustration of the effect Pd: Ga ratio on the Pd–Ga/SiO2 catalyst surface during CO2 hydrogenation (a) Pd/Ga >1.0 (b) Pd/Ga = 1.0, (c) Pd/Ga
<1. Reproduced with permission from Ref. [81] Copyright 2020 Royal Society of Chemistry.

9
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

decomposition of formate intermediates due to its ability to dissociate
H2 but is unlikely to adsorb CO2. Moreover, the controlling of Pd and
PdZn particle size was very crucial for the improvement of their catalytic
performance. In this case, the choice of a suitable synthesis procedure is
essential. For instance, the sol-immobilized method for Pd/ZnO syn­
thesis presents a more eminent way of controlling Pd and PdZn particles
size than the impregnation method, resulting in a higher CO2
conversion.
The formate pathway of the Pd–Zn catalyst was also convinced by
Zabilskiy et al. [77] through FTIR, XAS, and XRD characterization. The
FTIR results show peaks at 1596 cm− 1 and 1376 cm− 1, corresponding to
the active formate species attached to Zn. Moreover, the XAS result
suggests the formation of possible intermediates of Pd-formate, in which
there is no Pd–Zn de-alloying or Pd’s surface oxidation. Notably, the CO2
activation occurs in ZnO site. The Pd–Zn alloy phase did not provide the
active site for direct methanol formation from CO2. Instead, it is
responsible for H2 activation phase and allows the subsequent hydro­
genation process of formate into methanol on Zinc oxide surfaces. This
proposed mechanism is similar to that of Cu/ZnO based system.
In the case of the combination of PdZn with other metals, such as
CdSe, the formate pathway is still reported as the dominant pathway
[87]. The combination of CdSe and PdZn renders the stronger interac­
tion of Pd/Zn and more stable HCOO* species as intermediate over
COOH*. In this sense, it led to the enhancement of methanol production.
Furthermore, the XPS result showed that the increment of CdSe con­
centration is associated with the ZnO concentration enhancement. Also,
they found that the methanol selectivity over Pd@Zn is 80%, which was
significantly higher than that of the commercial Cu catalyst (10%) in the
same reaction condition. Moreover, it reveals that the Pd@Zn catalyst
inhibits the CO production over RWGS reaction.
Another precious metal, such as Au, is also the catalyst candidate for
CO2 hydrogenation to methanol. Nevertheless, it still needs a deeper
understanding of its mechanism reaction. Generally, Au-based catalysts
are widely used thanks to their high catalytic activity for many reactions
with mild conditions, including the selective hydrogenation of various
organic molecules, the water gas shift (WGS) reaction, and CO oxidation
[88]. For CO2 hydrogenation, metal oxide-supported Au catalysts were
reported as a potential catalyst to form methanol [89]. The Au/ZnO
catalysts result in the selectivity of methanol product >50%, compara­
ble to Cu/ZnO/Al2O3 catalyst (37%). Besides, the results also showed
the catalyst stability with no deactivation throughout >6 h of reaction.
Furthermore, other oxides have also been reported to support the Au-
based catalyst for CO2 hydrogenation. Rezvani et al. [90] reported the
remarkable activity of Au/CeO2 catalysts. Also, the mechanistic aspect
was investigated through diffuse reflectance infrared fourier transform
spectroscopy (DRIFTS). This catalyst has similar properties to Au/ZnO
catalysts, i.e., a partial reduction of the support as the activation phase as
well as the Auδ− sites formation and the reaction pathways through the
formation with the hydrogenation of surface formate and methoxy
species. Fig. 13 exhibits the in situ DRIFTS spectra of the Au/CeO2
catalyst for observing the temporal evolution of the nature and relative
coverages of the different adsorbed species.
As seen, the temporal evolution of DRIFT spectra was correlated to
their catalytic performance (Fig. 13). For the first 15 min, the band at
~3853 cm related to the O–H group from adsorbed carboxylic group
was enhanced, then it decreased after a longer reaction time. It agrees
with the methanol formation rate (Fig. 13f and g). It is correlated with
the band at 2850 cm− 1 (v (C − H) stretch mode of formate-like species),
as depicted in Fig. 13b. The weak band at 2711-2720 cm− 1 shows the
intensity enhancement through the first 10 min of reaction, which is

Fig. 13. The sequence DRIFT of CO2 hydrogenation over 1 wt % Au/CeO2 on the regions: (a) O–H region, (b) C–H region, (c) C–H region, (d) C– –O region, (e) OCO
bending region with the time scale 5 s, 80 s, 95 s, 110 s, 125 s, 140 s, 4.5 min, 7.5 min, 13 min, 15 min, 30 min, 1 h, 2 h, 5 h, 11 h, and 15 h. This measurement was
conducted at 5 bar. (f) Au-mass-normalized formation rates of methanol on Au/CeO2. (g) Normalized peak intensity of DRIFT spectra and Au-mass-normalized
formation rates of methanol and CO of Au/CeO2 catalyst. Adapted with permission from Ref. [90], Copyright 2020 American Chemical Society.

10
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

assigned to the CH vibration of adsorbed formyl group. Unfortunately, it
is tough to discover if this band disappears due to the strong band at
2609 cm− 1. The CO stretch and OCO bending regions exhibit an in­
tensity increment (Fig. 13d and e). It is noteworthy that the slow
deactivation is caused by the blocking site through adsorbed carbonate
species. Moreover, the Au/CeO2 catalyst denotes lower selectivity for
methanol and longer reaction times than Au/ZnO.
Rui et al. [91] reported the Auδ+− In2O3-x catalyst for hydrogenating
CO2 to methanol. The Au electronic structure affects the reactant
adsorption and activation regarding the hydrogenation activity.
Furthermore, the interfacial sites of Au and its support are also essential
in the product distribution determination by adjusting the intermediate
stabilization. The results show that the methanol selectivity is 100% and
over 70% at temperatures below 225 ◦ C and 275 ◦ C, respectively. This
result is almost 20 times higher than the previously reported Au catalyst
supported by other oxides, such as CeO2 and ZnO, due to the strong
interaction of Au and its support. This work concluded that Au/In2O3
could enhance the catalytic performance of Au catalysts.
The different surface properties of the catalyst could significantly
impact the catalytic activity because it directly interacts with the reac­
tant molecules and proceeds the reaction. In that sense, the choice of
preparation strategy is essential. Sagar et al. [92] investigate the effect
of different preparation methods on the catalyst surface and catalytic
performance of Au/ZrO2. Results showed that the best methanol pro­
ductivity was obtained for the catalyst prepared by deposition rather
than the impregnation method since it produces a large surface area and

Fig. 14. (a) The products acquired by using MIL-101, Pt1@MIL (1 = Pt single atom), Ptn@MIL (n = nanocrystal counterparts), and Cu/ZnO/Al2O3 (as a benchmark)
in CO2:H2 = 1:3 at 150 ◦ C 32 bar after 1 h. (b) Accumulation products obtained by in-situ cycles over Pt1@MIL. (c) The mechanistic insight of Pt1@MIL activity. (d)
Quasi-situ XPS spectra for MIL-101, Pt1@MIL, and Ptn@MIL. (e) and (f) Before/after C and O K-edge XANES spectra for MIL-101, Pt1@MIL, and Ptn@MIL,
respectively. Adapted with permission from Ref [94], Copyright 2019 Nature.

11
N.J. Azhari et al.
high-loading Au with controllable particle size. Moreover, the trans­
formation of amorphous to cubic ZrO2 and the enhanced acid and basic
site generated from the deposition method provide the appropriate
environment for stabilizing the critical intermediate involved in meth­
anol synthesis, i.e., HCOO*, dioxomethylene, and H3CO*. Whilst the low
CO2 uptake was observed for the catalyst prepared by the impregnation
method due to the presence of bulk Au cluster, rendering the lower
methanol formation rate.
Another precious metal catalyst was reported by Tran et al. [93]
using platinum impregnated onto Nb2O5. The precursor of Pt was pre­
pared from H2PtCl6 dissolution in water and subsequently added into
Nb2O5 synthesized. The characterization exhibit that Pt nanoparticles
are distributed homogeneously on the surface of Nb2O5 as support.
Furthermore, the result showed that the acidity controlled by different
calcination temperatures could increase the metal-support interaction
and metal dispersion. Hence, it enhances CO2 conversion and has the
highest selectivity of 0.8% at temperatures of 200 ◦ C.
Furthermore, rather than nanoparticle form, the single atom form of
Pt was reported to be more reactive for methanol production from CO2.
The work reported by Y. Chen et al. [94] reveal that Pt single atoms
coordinated with the oxygen atom in MIL-101 (Pt1@MIL) generate
methanol selectivity up to 90.3% with the formic acid as a byproduct. It
is higher than that of Pt as the nanoparticle (Ptn@MIL) and the com­
mercial Cu/ZnO/Al2O3 (Fig. 14a). Moreover, the activation energy of
Pt1@MIL (76.4 kJ/mol) was much lower than that of Ptn@MIL(119.7
kJ/mol). Pt1@MIL also exhibits the long-term stability shown by pro­
ducing 14.6 mmol of methanol and 1.4 mmol of formic acid After 16
in-situ cycles (96 h) (Fig. 14b).
Fig. 14c and d shows that HCOO* and COOH* are not detected in
MIL-101, which are considered intermediates for Pt1@MIL and
Ptn@MIL, respectively. In the reaction using Pt1@MIL as a catalyst, the
first H atom adds to the C atom, followed by HCOO* formation as the
stable intermediates. Meanwhile, in Ptn@MIL, the formation of COOH*
is favored, which acquires CO as the major product. The C K-edge
XANES (Fig. 14e) shows that before treatment with H2 and CO2,
Pt1@MIL and Ptn@MIL exhibit the same XANES profile. However, after
treatment, it exhibits the more robust feature of C–– O (π*) indicating the
formation of CO2. Moreover, the σ* (O–H) ends up significantly more
intense for Ptn@MIL but stays the same for Pt1@MIL (Fig. 14f). Thereby,
Ptn@MIL with COOH* intermediates could lead to gaseous products’
formation.
Sun et al. [95] reported Pt/In2O3 for catalyzing the methanol for­
mation from CO2. Notably, In2O3 enriched with oxygen vacancies
showed high activity and selectivity for CO2 activation and hydroge­
nation to methanol. Moreover, the support Pt catalyst also exposition a
promising activity for CO2 hydrogenation. This work exhibited that the
Pt/In2O3 catalyst has a remarkable selectivity in the CO2 hydrogenation
reaction with methanol selectivity of ca. 100%, 74%, and 54% at tem­
peratures <225 ◦ C, 275 ◦ C, and 300 ◦ C, respectively. Moreover, this
catalyst shows high stability, in which the activity decreases to 95%
after 5 h.
Han et al. [96] evaluated the effect of Pt amount on the In2O3 per­
formance and its mechanism for methanol synthesis. The result showed
that a small amount of Pt addition into In2O3 through coprecipitation
could enhance both activity and selectivity to methanol products. Dur­
ing CO2 hydrogenation, a part of the Pt species with a positive charge is
reduced and sintered, resulting in the formation of Pt nanoparticles,
while the other remains dispersed at the atomic level in a positively
charged state (Ptn+). Both species actively assist in more oxygen vacancy
formation, on which CO2 is activated. On the other hand, the Ptn +
species served as Lewis acid sites in promoting the heterolytic dissoci­
ation of H2 and the methanol formation. Contrarily, Pt nanoparticles
primarily encourage the RWGS reaction, which predominately assists
the CO formation and reduces the selectivity to methanol.
Apart from the excellent performance of precious metal based, pro­
ducing the Nobel-based catalyst is still expensive, especially for
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Results in Engineering 16 (2022) 100711
realization on an industrial scale. Furthermore, even if the atomic scale
of metal species could be obtained and showed remarkable activity, it
might change its state during the CO2 hydrogenation process toward the
larger species due to the reduction or sintering process. Therefore,
creating a noble catalyst, especially a single-atom noble metal catalyst
that stabilizes its phase and state during the reaction process, is chal­
lenging. In that sense, the search for an appropriate synthesis strategy
and/or the improvement of reaction conditions is absolutely needed.
3.3. Other catalysts
CO2 hydrogenation to methanol is equilibrium-limited by high
temperature. Generally, a catalyst efficiently operates at high tempera­
tures, which requires exceptional thermal stability [54,97–100].
Therefore, if catalysts other than Cu and precious metal-based catalysts
are to be used, they must strictly follow the thermal stability require­
ment. In this sense, other catalytic systems with novel catalytic struc­
tures, such as composite-based catalysts (metal alloys and supported
metal-alloys), oxygen-deficient materials, or oxide-based catalysts,
have been reported as effective catalysts for CO2 hydrogenation to
methanol.
In terms of composite-based catalysts, several elements, such as Ni,
In, and Mo, have been investigated. Richard and Fan [101] synthesized a
composite catalyst, NiaInbAl (NIA)/SiO2, using the
deposition-precipitation method for the CO2 hydrogenation to methanol
at ambient pressure. Fig. 15a depicts the methanol formation using a
series of NIA catalysts compared to the common CuO/ZnO/Al2O3 (CZA)
catalyst. As seen, NIA/SiO2 catalyst with a Ni: In ratio of 0.7 and 15 wt%
of NIA phase (15 wt% NIA-0.7) exhibits the highest catalytic activity
with a methanol formation rate of 0.33 mol h− 1 mol catalyst metal− 1
(Fig. 15a). Combining the Ni with In results in higher methanol synthesis
activity than Ni or In alone and allows it to be reduced at lower tem­
peratures. Furthermore, the optimal composition of the Ni and In cata­
lyst was crucial for the catalyst structure formation with a high particle
dispersion and appropriate particle size distribution after the process of
the catalyst reduction.
The time-dependent infrared spectroscopy was utilized to elucidate
the reaction mechanism over 15 wt% NIA-0.7 catalysts (Fig. 15b). The
peak located at 1662 cm− 1 is assigned to the monodentate formate (m-
HCOO) species. Meanwhile, the peaks at 1377 cm− 1, 1576 cm− 1, and
2857 cm− 1 correspond to the asymmetric- (vas (CO2)), symmetric
stretching vibrations of CO2 (vs (CO2)), and stretching vibration of C–H
bonding (v(CH)) within the bidentate formate (b-HCOO) species,
respectively. Furthermore, the peaks at 1549 cm− 1 and 1384 cm− 1 are
attributed to the asymmetric- (vas (CO3)), symmetric stretching vibra­
tions of carbonate (vs (CO3)) within the monodentate carbonate (m-
CO2− 2−
3 ) species. Other carbonate species, bidentate (b-CO3 ) and poly­
dentate (p-CO3 ), are indicated by the presence of peaks at 1597 cm− 1
2−
(vas (CO3) of b-CO2−3 )), 1478 cm
− 1
(vas (CO3) of p-CO2−
3 )), 1437 cm
− 1
(vs
(CO3) of p-CO2− 3 ). These results revealed that CO2 hydrogenation over
NIA/SiO2 catalyst occurs via monodentate carbonate, followed by the
formation of bigger carbonate species, i.e., bidentate and polydentate
carbonates. Moreover, changing the reactant feed from CO2/H2 to CO/
H2 changes the primary hydrocarbon product from methanol to
propane.
Differently, Ren at al [102]. suggested the CO2 → CO3* → HCOO*
pathway for the methanol synthesis over unsupported bimetallic Ni–Cu
(100) catalyst. Detail characterization using Near-Ambient Pressure
X-Ray Photoelectron spectroscopy reveals that the Ni/Cu(100) facili­
tates the CO2 dissociation into CO and atomic oxygen, which chemisorb
at the surface. During the CO2 activation, the CO3* species will be
formed due to the reaction between CO2 and surface oxygen. This spe­
cies was further converted into formate in the presence of hydrogen.
Furthermore, introducing CO to the CO2 hydrogenation system could
help maintain the catalyst activity because the CO capability reduces the
surface oxide that has been proved to retain the CO2 activation.
N.J. Azhari et al.
Fig. 15. (a) The catalytic performance of NIA-0.5 and NIA-0.7 catalyst at 5–20 wt % loading, and the commercial CuO/ZnO/Al2O3 catalyst in methanol production at
elevated temperature and ambient pressure, (b) Infrared spectra of isothermal CO2 hydrogenation over NIA-0.7 catalyst at 15% loading as a function of time.
Reproduced with permission from Ref. [101]. Copyright 2017 American Chemical Society.
Indium, as the nano-intermetallic form, was also a potential catalyst
for methanol production from CO2. Chen et al. [103] synthesized
InNi-based catalysts through RWGS reaction-oriented pre-design com­
bined with experimental verifications and atomistic-theoretical calcu­
lations. Based on the DFT calculations, nano-intermetallic InNi3C0.5 can
reduce the reaction temperature from 400 ◦ C–600 ◦ C–300 ◦ C and below.
The transition metal carbides have a good capability for adsorbing CO2
and breaking the C–O either by themselves or aided by hydrogen. Re­
sults show that the 1–8% CO2 conversion could be obtained with
methanol selectivity of 60%–98% under 200–300 ◦ C. Initially, CO2 was
adsorbed on 3Ni–In site and dissociated into CO* and O* on 3Ni–C sites
and 3Ni–In sites, respectively. This CO intermediate is further converted
into methanol product via HCO* → CH2O* → CH2OH* → CH3OH*.
Molybdenum carbide (Mo2C) is also reported as a good candidate for
methanol production from CO2. Adding alkali promoters was expected
to enhance the catalytic performance of Mo2C. Dongil et al. [104]
evaluated the addition of Cu and Cs to the Mo2C catalyst system. In their
work, Cs is expected to enhance the methanol formation since it has a
large ionic radius; thus, it can be a better electron donor [105–107].
However, results show the opposite effect due to the occurrence of redox
surface transformation under the reaction condition. XRD analysis ex­
hibits the presence of the Mo0 phase in the Cs–Mo2C catalyst, which has
poor ability in CO2 hydrogenation. Although, recent reports have found
that supporting the molybdenum carbide in appropriate materials could
improve their catalytic performance in methanol formation.
Figureas et al. [108] reported that by supporting the nanoparticles of
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Results in Engineering 16 (2022) 100711
molybdenum carbide (MoC) at Au, its catalytic performance could be
improved, showed by its smaller activation energy (14 kcal/mol) than
that of its bulk phase (17 kcal/mol) and Cu catalyst system (25 kcal/­
mol). Furthermore, the composition between carbon and metal is very
crucial. For the carbon-poor (MoC0.6) carbide nanomaterials supported
Au, the CO2 decomposition tends to produce CO and CH4. In contrast,
the carbon-rich one ((MoC1.1)/Au(111)) could produce a significant
amount of methanol with no methane. Methanol formation occurs via
the formate pathway with the Eley Riedel mechanism. The direction of
product selectivity by engineering the catalyst structure properties has
also been documented by Zhou et al. [109]. A two-dimensional multi­
layered molybdenum carbide (2D-Mo2C) synthesized from Mo2CTx
Mxene family is the potential catalyst for producing methanol from CO2.
The terminal Tx group could be tuned to selectively direct the reaction
toward the target, although recent reports suggest that under the H2
pretreatment, the 2D-Mo2C is still more favorable for RWGS reaction.
However, the broad chance for a methanol catalyst is still opened.
Besides the metallic composite catalyst, the oxide catalyst, such as
Indium (In)-based catalyst, also showed promising results. Indium oxide
(In2O3) was first tested in 2016 and had an extremely high methanol
selectivity [110–112]. Martin et al. [110] reported that In2O3 has a
highly efficient catalytic system and outstanding activity under indus­
trial conditions for the CO2 to methanol with 100% selectivity at all
temperatures. It is much higher than that of the conventional ternary
catalyst (Cu/ZnO/Al2O3), which only reached 47% selectivity at 473 K.
The surface oxygen vacancies of indium oxide promote the selectivity of
N.J. Azhari et al.
CO2 hydrogenation to methanol, and it could be increased through CO
co-feeding into the gas feed or using support, e.g., ZrO2. Furthermore,
this hybrid catalyst is stable even after a 1000 h reaction and could be
upgraded to a technical form with similar catalytic performance.
Ye et al. [111] previously predicted the excellent catalytic perfor­
mance of the In2O3 catalyst in methanol synthesis from CO2 using pe­
riodic DFT calculations. The initial reaction of CO2 hydrogenation to
HCOO shows that the calculated reaction energies and activation bar­
riers are thermodynamically and kinetically favorable on the D4
defective In2O3 (110) surface (Fig. 16b). Afterward, the HCOO hydro­
genation reaction to H2CO has a slightly endothermic reaction, then the
H2CO hydrogenation reaction that produced CH3O is more favorable for
methanol formation. The oxygen vacancy assists the activation and
hydrogenation of CO2 as well as stabilizes the critical intermediate re­
action involved in CO2 hydrogenation to methanol (Fig. 16a). The main
issue in the CO2 hydrogenation to methanol is the C═O bond cleavage,
which can only occur by dissociating intermediates. Furthermore, in the
In2O3 system, it can only be achieved by filling the oxygen vacancy with
one of the O atoms and making this step much easier than on the surface
of the metal catalyst. Detail reaction steps and their calculated energies
are provided in eq. (6)-(11).
[CO2 + H]* → mono-HCOO* ΔE = − 0.21 eV; Ea = 0.15 eV (6)
[HCOO + H]* → bi-H2CO*+Surface O ΔE = +0.05 eV; Ea = 0.57 eV (7)
[mono-H2CO + H]* → H3CO* ΔE = − 0.60 eV; Ea = 1.14 eV (8)
Fig. 16. (a) Proposed mechanism of methanol formation from CO2 on the
defective In2O3 (110) surface with surface oxygen vacancies, (b) Profiles of
potential energy for the generation of oxygen vacancy, 1st and 2nd step of CO2
hydrogenation on the D1 (red line) and the D4 surfaces (blue line). Reproduced
with permission from Ref. [111]. Copyright 2013 American Chemical Society.
14
Results in Engineering 16 (2022) 100711
[bi-H2CO + H]* → H2COH* ΔE = +0.83 eV; Ea = 1.33 eV (9)
[H3CO + H]* → CH3OH* ΔE = +0.21 eV; Ea = 0.33 eV (10)
[H2COH + H]* → CH3OH* ΔE = − 0.59 eV; Ea = 2.52 eV (11)
Because of their excellent performance, many studies have been
conducted to improve their catalyst performance. Perez-Ramirez and
Coworker [113] evaluate the behavior of In2O3 with different forms, i.e.,
bulk-form, In2O3 supported ZrO2, and In2O3 promoted with Pd and Ni.
Additionally, the effect of CO in the feed stream was evaluated. Results
show that the presence of CO could alter the surface properties of the
catalyst. The improvement of methanol productivity upon CO addition
was obtained for the In2O3 supported on the monoclinic ZrO2 catalyst. It
was attributed to the controlled formation of oxygen vacancies and the
ability to restrict sintering during the reaction. Meanwhile, the bulk
In2O3-form remains unaffected. For the Ni- and Pd-promoted indium
oxide form, moderate-to-substantial deactivation was observed due to
the strong ability of Pd to adsorb CO, the over-reduction, and the sin­
tering between metal promoters and oxide.
Furthermore, the different phase of In2O3 was also reported to pro­
duce different catalytic behavior in methanol synthesis. Dang et al.
[114] evaluate the CO2 hydrogenation pathway over the In2O3 catalyst
with different phases, i.e., cubic In2O3 (c-In2O3) and corundum-type
hexagonal phase (h-In2O3). Additionally, various exposed surfaces
were also investigated, i.e., (110) and (111) surfaces for c-In2O3 and
(104) and (012) surfaces for h-In2O3. The best catalytic performance for
methanol synthesis (CO2 conversion >17% with 92.4% methanol
selectivity) was owned by h-In2O3, with the abundance of exposed (104)
surface confirming the DFT calculation results. In situ DRIFT charac­
terization reveals the stronger ability of h-In2O3 (104) to stabilize the
HCOO* and CH3O* species as the key intermediate; thus, higher meth­
anol selectivity could be gained.
Aside from the oxygen vacancy that has been explained previously,
the sulfur vacancies have shown a promising result recently. For
instance, MoS2 is considerably reported as the dominant active center
because of its edge sites in many catalytic reactions [115–119]. Hu et al.
[120] proved that the in-plane sulfur vacancies of MoS2 is the excellent
active centers for CO2 hydrogenation to methanol at the
low-temperature reaction (180 ◦ C). Sulfur vacancies in MoS2 nanosheets
facilitate the dissociation of the CO2 molecule to produce surface-bound
CO and O at ambient temperature, thus enabling the CO2 hydrogenation
reaction to methanol at low temperatures. Notably, methanol selectivity
and CO2 conversion of 94.3% and 12.5%, respectively, were obtained
over the surface of in-plane sulfur vacancy-rich MoS2 nanosheets, which
are specifically higher than previously reported catalysts. Moreover, this
catalyst has high stability, which could be used for over 3000 h without
deactivation.
Molybdenum in the atomic form was also accounted for producing
methanol from CO2 hydrogenation. In the reported work by Len et al.
[121], the atomically dispersed and reducible oxomolybdate species on
TiO2 support results in 35 gMeOH.kg− 1. h− 1 of STY under 275 ◦ C and 3
MPa. Again, the phase of the support affects the catalytic behavior due to
the different oxidation states of Mo. Characterization using
synchrotron-based NAP-XPS shows that the rutile phase of TiO2 support
possesses more reduced Mo than the anatase phase. Under reaction
conditions, TiO2 with a rutile structure has a more labile oxygen envi­
ronment; thus, the methanol productivity is higher.
The recent development of the non-Cu-based and non-precious-
based catalysts that have been enormously studied, i.e., the pure oxide
catalyst, intermetallic, and transition metal carbide catalyst, showed
that these catalysts provide a more promising result regarding lowering
the operation condition. For instance, the sulfur vacancies catalyst could
be operated for the reaction under 200 ◦ C. Therefore, many explorations
of these types of catalysts should be under shed light. One should be paid
attention is the catalyst mechanism, both in the reaction process and the
deactivation mechanism. Also, developing a synthesis strategy to
N.J. Azhari et al. Results in Engineering 16 (2022) 100711

selectively produce the catalyst with a particular phase or exposed facet
surface is essential. Therefore, the pre-design-based development will be
more visible.
4. Conclusion and outlook
CO2 conversion to methanol is a promising way to realize a sus­
tainable energy future. Although Cu-based catalyst was commonly used
for this process, this catalyst often suffered from the drawback of low
stability; therefore, other catalysts should be considered. Other than Cu,
several types of catalysts have been used for directly producing meth­
anol from CO2, i.e., precious metal-based catalysts and other catalysts,
such as composite-based catalysts (metal alloys and supported metal-
alloys), oxygen-deficient materials, or oxide-based catalyst. Although
all these catalysts show remarkable catalytic performance, the occurring
mechanism remains elusive.
Lately, researchers have conducted numerous experiments focusing
on the mechanistic aspect of the reaction since it is crucial information
for developing the next-generation catalyst. At least three plausible
mechanisms have been proposed, i.e., via formate, RWGS, and trans-
COOH* pathways. Table 1 summarizes the various catalysts used for
methanol synthesis from CO2. As seen, the formate pathway is consid­
ered the most common route. However, several researchers have sug­
gested the preference for the trans-COOH* pathway. This is because the
hydrogenation of CO2 commonly results in water as the byproduct that
could react with CO2 to generate hydrocarboxyl species. On the other
hand, the RWGS, usually called RWGS + CO hydro pathway, is also
reported for several precious metal-based catalysts, such as Pd–Cu/CeO2
and Pt/Nb2O5. However, catalytic behavior is affected by many factors;
therefore, it is difficult to classify catalytic behavior precisely. For
instance, the physicochemical properties of the metal and support used,
i.e., state, cluster size, phase, composition, morphology, and basicity, is
strongly related to their catalytic performance, in which the discussion
of each component effect has been provided in the previous section.
Furthermore, the operation condition, such as the different tempera­
tures and pressure, CO2: H2 ratio, and the presence of CO co-feed in the
stream, was also reported to affect the catalytic behavior.
Finally, after the immense development of CO2 conversion to
methanol from the mechanistic point of view, several concerns for future
direction could be formulated. The catalyst species should be precisely
adjusted to conveniently activate CO2 molecules and stabilize a specific
intermediate of the reaction. The addition of suitable promoters and
supports may assist the stability of the intermediate species involved in
the reaction through the metal-support interaction. Moreover, the
structural evolution of the catalyst and its active sites during the reaction
is also crucial in improving the catalytic performance. Notably, it is
essential to adjust the morphology, particle shape, and size, as well as
the phase of each component, since it affects the electronic structure and
the activity performance of the catalyst. In that sense, developing the
synthesis strategy is crucial to be encouraged. For instance, escalating
the nanocrystal catalyst to single atoms [94] exhibits a much higher
catalytic activity. However, it is still challenging to engineer the struc­
tures and accessibility of the high density of single atoms while pre­
venting aggregation towards a large particle. Moreover, powerful
characterization techniques, such as X-ray absorption spectroscopy
(XAS) and/or high-angle annular dark-field scanning transmission
electron microscopy (HAADF-STEM), are inevitable. On the other hand,
developing catalysts that could be operated in milder conditions is also
still wide-opened.
Computational studies, such as DFT-based calculations and molec­
ular dynamics simulations, have shed light on the plausible mechanisms
of selective CO2 conversion to methanol. In addition, several in-situ
characterizations should be involved to characterize the intermediate
species and the behavior of the catalyst during the reaction. Meanwhile,
machine learning (either unsupervised or supervised) could be utilized
to predict and pre-design the catalyst, as well as determine the appro­
priate reaction condition to produce a more efficient route. From the
technological perspective, combining other units, such as the CO2 cap­
ture units [122], the in-situ water removal [123], or the heat-released
equipment, may improve the thermodynamic equilibrium and other
aspects for compelling the vision of a sustainable energy future.
Last but not least, the industrialization of the methanol synthesis
process from CO2 is still challenging, although significant progress has
been attained on the laboratory scale. The challenge comes from several
aspects, especially from the techno-economics point of view. Studies
that have been conducted by several researchers show that the current
process of methanol production from syngas is still more advantageous
related to the techno-economics and life cyle analysis consideration.

Table 1
Various catalyst that have been reported for CO2 hydrogenation to methanol and their correspondingctalytic performance.
Type of catalyst Active site Reaction condition (MPa; Gas ratio (CO2: Conversion Selectivity Ref.
◦
C) H2) (%) (%)

Formate pathway
Cu–ZnO/ZrO2 Cu+/Cu0; oxide-metal interface 1.0; 180 1: 3 ~1.5 ~83 [49]
Cu/tetragonal ZrO2 ZrO2; Cu–ZrO interfaces 3.0; 240 1: 3 ~2 ~80 [50]
hollow structured of Cu0/Cu+ sites; Cu–ZrO2 interfaces 3.0; 150 - 300 1: 3 ~2–18 80–20 [69]
Cu@ZrO2
Cu–CeO2 Cu–CeO2 interfacial site; copper site 3.0; 250 1: 3 ~1.5 ~50 [62]
CuO/CeO2/ZrO2 CeO2–ZrO2; metallic copper 3.0; 200 1: 3 ~5 – [60]
Pd/ZnO PdZn bimetallic phase 2.0; 250 1: 3 11 60 [76]
Pd/ZnO ZnO and palladium-zinc alloy 3.0; 260 1: 3 3.6 49.8 [77]
Au/ZrO2 Zr4+/O2− 4.0; 240 3: 1 5.7 72.5 [92]
Pt1@MIL Pt 3.2; 150 1: 3 – 90.3 [94]
In2O3 (110)* D4 surface (O defective site) – – – – [111]
Bimetallic Ni–Cu (100) Ni–Cu surface 4.0 x 10-4 ; 27–277 ◦ C 1: 3 – – [102]
Cu–Ce–Zr oxide solid Cu0, Cu–O-M (M; Zr, Ce) interfacial sites, and 3.0; 240 1:3 ~6 ~60 [72]
solution Ce3+− Ov–Zr4
Pd2Ga and Ga2O3 phase 5.0; 210 3:1 – 60 [75]
Pd/Ga 3.0; 250 3: 1 – 65 [85]
Au 0.5; 240 1: 3 – 53 [90]
RWGS pathway
Pd–Cu/CeO2 Cu sites 3.0; 190 3: 1 16.1 26.7 [78]
Pt/Nb2O5 Pt 0.5; 280 1: 3 5.7 0.8 [93]
Nano-intermetallic 3Ni–In; 3Ni–C 4.0; 220–310 1: 3 1–8% 60–98 [103]
InNi3C0.5
Trans-COOH* pathway
Cu (111)* Cu (111) – – – – [52]

15
N.J. Azhari et al.
Under the current techno-economic condition, methanol production
from CO2 did not meet the lower cost compared with the current
methanol market price due to the electricity and hydrogen requirements
[124]. However, the environmental benefits will be gained if the elec­
tricity source comes from low-carbon energy, suggesting the importance
of renewable energy to be swiftly developed.
Credit author statement
Noerma J. Azhari: Writing – original draft, Visualization, Denanti
Erika: Writing – original draft, Visualization, St Mardiana: Writing –
original draft, Visualization, Thalabul Ilmi: Writing – review & editing,
Melia L. Gunawan: Writing – review & editing, Supervision, I.G.B.N.
Makertihartha: Writing – review & editing, Supervision. Grandprix T.
M. Kadja: Writing – review & editing, Supervision, Conceptualization,
Resources.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work is supported by the Ministry of Education, Culture,
Research and Technology of the Republic of Indonesia through PDUPT
Research Funding (first year) 2022. We dedicate this work to the
retirement of Prof. Subagjo, who has made an outstanding contribution
to the development of catalyst and catalysis science in Indonesia.
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