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Heterogeneous Catalytic Systems for Carbon Dioxide

Hydrogenation to Value-Added Chemicals
Sara Mirzakhani,[a, b] Ben Hang Yin,[c, d] Majid Masteri-Farahani,[e] and Alex C. K. Yip*[a]

Utilizing renewable energy to hydrogenate carbon dioxide into mechanistic insights. This paper summarizes recent advances in
fuels eliminates massive CO2 emissions from the atmosphere CO2 hydrogenation and its conversion into various hydro-
and diminishes our need for using fossil fuels. This review carbons such as formate, methanol, and C2 + products. As for
presents the most recent developments for designing heteroge- formate production, Au and Ru nanocatalysts show superior
neous catalysts for the hydrogenation of CO2 to formate, activity. However, considering the catalyst cost, Cu-based
methanol, and C2 + hydrocarbons. Thermodynamic challenges catalysts have an excellent prospect for methanol production,
and mechanistic insights are discussed, providing a strong among other catalysts. Ultra-small nanoparticles and nano-
foundation to propose a suitable catalyst. The main body of this clusters appear promising to provide highly active cost-effective
review focuses on nanostructured catalysts for constructing catalysts. A growing number of researchers are investigating
efficient heterogeneous systems. The most important factors the possibility of directly synthesizing C2 + products through
affecting catalytic performance are highlighted, including active CO2 hydrogenation. The major challenge in producing heavy
metals, supports and promoters that can potentially be used. hydrocarbons is breaking the ASF limitations, which have been
The summary of the results and the outlook are presented in achieved over bifunctional catalysts using zeolites. Using
the final section. During the past few decades, heterogeneous suitable support and promoter can lead to a superior activity,
CO2 hydrogenation has gained much attention and made ascribed to structural, electronic, and chemical promotional
tremendous progress. Thus, many highly efficient catalysts have effects.
been studied to discover their active sites and provide

1. Introduction processes for converting CO2, as a major contributor to air

pollution and greenhouse activity to valuable chemicals, is
Research in photosynthetically-inspired technologies for con- important for the chemical industry as these technologies
verting CO2 to valuable hydrocarbons is driven by two key effectively reduce CO2 emission by adding value to a waste
motivations: avoiding further global warming due to increasing stream, and simultaneously decreasing the exploitation of fossil
greenhouse gases and the need for alternative fuel sources due fuels. Hydrogenation of CO2 is a feasible strategy for producing
to the depletion of fossil fuel resources. Developing chemical high-value fuels and chemicals that can be done even on
industrial scales. For example, we can take the “George Olah
Carbon Dioxide to Renewable Methanol Plant”, Carbon Recy-
[a] S. Mirzakhani, Prof. A. C. K. Yip cling International (CRI), which operates based on local geo-
Department of Chemical and Process Engineering
thermal energy. The first worldwide plant which commercially
University of Canterbury
Christchurch,(New Zealand) recycles CO2 uses a heterogeneous catalyst system and geo-
E-mail: [email protected] thermal energy for the annual production of 4,000 t of
[b] S. Mirzakhani
methanol. In CRI, the CO2 comes from the flue gases of the
School of Physical and Chemical Sciences
University of Canterbury nearby geothermal energy plant, and H2 is produced by
Christchurch (New Zealand) electrolysing alkaline waters with electricity.[1]
[c] Dr. B. H. Yin
In recent years, various catalytic systems have been
Robinson Research Institute
Faculty of Engineering proposed to accelerate the hydrogenation of carbon dioxide.
Victoria University of Wellington However, investigations continue to produce more selective
Wellington (New Zealand)
and active catalytic systems for this process. Due to the
[d] Dr. B. H. Yin
The MacDiarmid Institute for Advanced Materials and Nanotechnology advantages of heterogeneous catalysts, including easy separa-
(New Zealand) tion from the reaction mixture and high stability as opposed to
[e] Prof. M. Masteri-Farahani
the homogeneous catalysts,[2] we have limited the scope of this
Faculty of Chemistry
Kharazmi University review to heterogeneous catalytic systems. The nature of active
Tehran (Iran) sites in a catalyst is the key variable factor that can affect its
Part of a Special Collection on Green Chemistry activity in heterogeneous catalysis. This is affected by the
© 2023 The Authors. ChemPlusChem published by Wiley-VCH GmbH. This is nature of catalytically active metal(s) used, the size and,
an open access article under the terms of the Creative Commons Attribution
License, which permits use, distribution and reproduction in any medium, sometimes, the shape of metal particles comprising an active
provided the original work is properly cited. site, interaction of such catalytically active particles with

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support material and promoters. Therefore, how a catalyst is solvation effects, alcoholic solvents also provide further benefits
prepared controls its catalytic performance.[3] Many studies as they can form alkyl formate. As a result, esterification in the
have been conducted on CO2 hydrogenation via heterogeneous presence of formic acid (Eq. 3), thus shifting the reaction
catalysis using different methods. The rational design of these equilibrium toward the formation of alkyl formate. In reactions
catalytic systems can also be organized according to the involving base additives, in the subsequent deprotonation by
products, consisting of C1 products (e. g., formate or methanol) base, formic acid is converted to formic acid/amine or formate
and C2 + products. adducts with intensely negative enthalpy ( 84.3. kJ mol 1)
This review discusses the thermodynamic challenges and (Eq. 4).[6] This way, the entropic factor can be compensated and
mechanistic insights into CO2 hydrogenation, providing a strong the overall reaction towards formate is triggered.
foundation for the rational design of the catalysts. Unlike other
review papers that summarized the applications of various
catalysts in CO2 hydrogenation, this review specifically focuses 2.1. Reaction mechanism
on the effect of the catalyst formulation and its correlation with
the most critical mechanisms in producing high-valued prod- Due to the gaseous reactants (H2/CO2), solid catalyst, and liquid
ucts from CO2. medium (combination of solvent and a base), heterogeneous
CO2 reduction to formate is a complex multiphase catalytic
process. Consequently, few heterogeneous catalysts in this field
2. CO2 to CHOO have been thoroughly investigated to unravel their mecha-
nisms, despite the wide range of catalytic studies available
At the laboratory and industrial scale, scientists have developed today.[8] Heterogeneous catalytic CO2 reduction to formate is
various synthetic approaches for converting CO2 into value- typically started by H2 and CO2 diffusion into liquid and then to
added hydrocarbons, including formate, methanol, methane, the active site on the solid catalyst. It is generally accepted that
and other hydrocarbons.[4] Among them, formate, a versatile C1 H2 undergoes heterolytic cleavage and dissociates to hydride
molecule, has recently gained considerable attention due to its species and protons. As suggested by theoretical studies and
growing importance as an environmentally friendly energy spectroscopic evidence, hydride species are thought to fulfil the
carrier for a greener future.[5] role of nucleophilic attack on the electrophilic carbon atom of
When it comes to formate production from CO2, the major CO2.[9] It is generally accepted that the reaction rate is governed
challenge lies in the unfavourable thermodynamics of the by the insertion of CO2 into metal-hydride bonds.[10] On the
reaction (Eq. 1),[6] as a result of the unfavourable entropic other hand, H2 can also be dissociated homolytically on metallic
contribution of converting gaseous reagents into liquid prod- nanoparticles such as Pd or Ru.[1e] However, the heterolysis
ucts. Two approaches have been used to address this problem. cleavage of H2 seems to be kinetically more favourable.[8]
First, using basic additives such as amines, hydroxides. Second, In the previous studies, two pathways have been suggested
choose a suitable reaction medium like water, alcohols, ionic for heterogeneous CO2 hydrogenation to formate (Figure 1).
liquids, etc. As can be seen in Eq. 2, due to solvation effects, the The first one is the “bicarbonate pathway” in which first H2 and
formate formation acid in an aqueous solution is thermody- bicarbonate adsorption on nanoparticles happen. Subsequently,
namically favourable, with a total free energy of 9.5 kJ/mol hydride as a nucleophile attacks at the carbon atom in
under standard thermodynamic conditions.[7] Apart from the bicarbonate and, eventually, formate is produced by losing a

Sara Mirzakhani received her master’s degree Dr. Ben Hang Yin is a senior scientist at the
in chemistry at Iran University of Science and Faculty of Engineering, Victoria University of
Technology. She is currently a PhD candidate Wellington, New Zealand. He obtained his
under the supervision of Prof. Alex Yip at the PhD in Chemical and Process Engineering
University of Canterbury in New Zealand. Her from the University of Canterbury in 2016. His
research interest focuses on catalysts design research focuses on developing porous mate-
and their applications especially in CO2 hydro- rials for membrane separation and catalysis
genation to hydrocarbons. applications.

Professor Alex Yip received his BE (Hon) in

Majid Masteri-Farahani is a Professor at the Chemical Engineering from UNSW (Australia)
Faculty of Chemistry at the Kharazmi Univer- in 2003. He obtained his Ph.D. from the Hong
sity. He obtained his PhD in Inorganic Kong University of Science and Technology
Chemistry from University of Tehran in 2006. (2009), studying heterogeneous catalysis. He
His current research interests include the is currently a Full Professor and the leader of
preparation and characterization of new hy- the Energy and Environmental Catalysis Group
brid materials and catalysts. at the University of Canterbury in New
Zealand. His research focuses on catalytic
micro/mesoporous materials and converting
biomass, syngas and CO2 to fuels.

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2.2. Catalytic systems for formate synthesis from CO2

In 1914, for the first time, Bredig and Carter reported the
heterogeneous catalytic hydrogenation of CO2 to formate via
the reduction of KHCO3 in the presence of Pd black as the
catalyst.[13] After that, further studies demonstrated the direct
CO2 hydrogenation to formate in ethanol in the presence of Ni
as the catalyst and amine as the base.[14] The early reported
catalysts, which featured large metallic particles, usually
exhibited poor activity and rapid aggregation. The synthesis
and application of nanocatalysts have subsequently produced
significant breakthroughs in heterogeneous CO2 reduction to
formate thanks to higher surface area and extraordinary nano-
scale electronic characteristics. Many studies have been con-
ducted using noble metals such as Ru, Au, Ag, and Pd through
nanostructured catalysts. The active site is usually immobilized
on basic support to increase the metal support interactions. It
can also be used directly as a colloidal catalytic system in the
liquid phase. Table 1 summarizes some of the most recent
works published and shows how catalytic activity changes as its
main components change. As can be seen, Ru and Au catalysts
showed outstanding performances, with turnover number
(TON) reaching tens of thousands. The superior performance
could be due to the strong hydrogen spillover effect which
promotes the formation of oxygen vacancies on the support.[15]
Although CO2 hydrogenation to formate has been extensively
studied, first-row transition metal catalysts in this area are still
rare. Copper catalysts are commonly used in CO2 reduction to
methanol, but using them in the catalytic CO2 reduction to
formate has not been widely reported. If first-row transition
metals-based systems were proven catalytically active, their
abundance and lower cost would make them optimal for large-
scale fuel production. It is worth noting that catalytic CO2
hydrogenation to formate in organic solvents is favourable in
Figure 1. The main mechanisms for CO2 to CHOO : a) bicarbonate pathway
(reproduced from ref. [11]; Copyright (2018), with permission from American the presence of a base from thermodynamic point of view.[16]
Chemical Society) and b) CO2 reduction pathway (reproduced from ref. [12];
Copyright (2017), with permission from Springer Nature).

Table 1. The performance of catalysts reported recently for CO2 hydro-

water molecule. Figure 1a shows bicarbonate pathways over a genation to formate.
bimetallic PdAg/TiO2 catalyst investigated by Mori et al..[11] The Catalyst pH2/pCO2 (bar) Temp./°C Additive TON Ref.
second proposed mechanism route is “CO2 reduction pathway”,
CPC Ru-1 50/30 120 – 17919 [17]
as shown in Figure 1b, in which hydride attacks CO2 to produce Ru Co3O4 20.7/41.4 120 NEt3 219 [18]
formate. Then, the formic acid is produced and dissociated from MOF1/Pd 22.5/7.5 170 KOH 1500 [19]
the metal centre by transferring a proton. The proposed CO2 Ru/N-MCHS-900 40/40 120 NEt3 7550 [20]
Pd/g-C3N4 60/0 80 KHCO3 5051 [8]
reduction pathway over Au/SiO2-Schiff catalyst studied by Liu Au36(TBBT)24 22.5/7.5 120 – 935 [21]
and co-workers is also shown in Figure 1.[12] It is worth noting Au/TiO2 20/20 70 NEt3 111 [22]
that in most cases, both pathways could happen simultaneously Au/Al2O3 20/20 70 NEt3 215 [22]
Au/SiO2 NH2 50/30 90 NEt3 1026 [12]
to some degree. For a specific system, the predominant reaction Au/SiO2-Schiff 50/30 90 NEt3 14470 [12]
pathway depends on the reaction conditions and the nature of Ru/HT 30/30 60 – 11389 [23]
the catalyst. There is a striking similarity between the proposed Ru particles 50/80 80 NEt3 6351 [24]
Ru3(CO)12 40/30 70 BMMI·OAc 17000 [9a]
mechanistic cycles for immobilized metals and their homoge- RuFe 20/10 60 BMI·OAc 400 [25]
neous counterparts.[8] Pd/Mo2C 10/10 100 NaHCO3 72 [26]
Pd/NMC 60/0 60 KHCO3 1964 [27]
Pd/AC 50/30 40 – 594 [28]
Pd Al2O3@ICRM 40/0 r.t. NaHCO3 580 [29]
Pd@ICRM 40/40 40 NEt3 250 [29]
Pd@Ag/TiO2 10/10 100 NaHCO3 14839 [11]

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3. CO2 to CH3OH

Compared to other C1 compounds, methanol is an promising

product for CO2 hydrogenation due to its physical and chemical
properties that make it valuable for storage and transportation
as well as its potential to be converted into useful materials for
industry use.[30] In this process, methanol is produced through
either direct synthesis from CO2 (Eq. 5) or a route that includes
reverse water gas shift reaction (RWGS) (Eq. 6) followed by a CO
hydrogenation process (Eq. 7).[31] Despite being an optimal
solution for both economic and environmental benefits, there
are still many challenges to realizing this process.
Firstly, the synthesis of CH3OH is exothermic, producing two
moles of products compared to four moles of reagents. There-
fore, according to thermodynamics, increasing pressure and
reducing reaction temperature favour high CO2 conversion and
high methanol yield. However, low temperature leads to slow
reaction kinetic and favours the endothermic RWGS which
lower methanol yield.
Secondly, the inertness of CO2 requires intensive energy and
a high-performance catalyst to active the reaction. Although
small amount of water may have positive effects under certain
conditions,[32] excessive amount of by-product water can
significantly inhibit the activity of active metals as reported by
Inui and Takeguchi.[33] Therefore, proper reactor design and new Figure 2. The main mechanisms for CO2 to CH3OH.
development of more selective and water-resistant catalysts are
crucial for the large-scale production of methanol via CO2
hydrogenation. subsequently dissociated to COH* followed by a transformation
into HCOH* and H2COH*, and finally methanol.[4e,39]

3.1. Reaction mechanism

3.2. Heterogeneous catalytic systems for methanol synthesis
Despite ongoing heated debates about the reaction mecha- from CO2
nism, there are three main reaction pathways for CO2 hydro-
genation to methanol that have been widely accepted, which The copper-based catalysts are most used for CO2 hydro-
are formate pathway, CO pathway, and trans -COOH pathway, genation to methanol. These catalysts are usually modified with
as shown in Figure 2.[34] The formate pathway involves the various promoters and modifiers like Zr, Ga, etc. for enhancing
reaction of CO2 with surface atomic hydrogen to form *HCOO. the catalytic performance.[40] Studies have shown that copper-
This intermediate *HCOO undergoes two hydrogenation steps containing catalytic systems are the most effective for this
to form *H2COOH, which upon a cleavage, produces methoxide. reaction[41] and some have even proposed that methanol
This methoxide intermediate subsequently undergoes further synthesis via CO2 hydrogenation is impossible without
hydrogenation to produce methanol. Recently, Kattel et al.[35] copper.[42] The Cu-based catalyst, however, suffer from signifi-
highlighted a synergy bimetallic effect at the Cu and ZnO cant deactivation problems due to the formation of copper
interface that could facilitate methanol synthesis via formate carbides and copper oxides during the reaction.[43] Other metals,
intermediates. The CO pathway begins with RWGS to transform such as Pd, Ga, In, Ni, Rh, and Co have been extensively
CO2 into CO* species, followed by a series of hydrogenation investigated for this reaction.[44] In particular, noble metal-based
from CO* to HCO*, H2CO*, H3CO*, and lastly to methanol. Yang catalysts, such as Pd-based, Au-based and Ag-based catalysts,
et al.[36] investigated a Cu-based catalyst for CO2 hydrogenation which exhibit extraordinary catalytic performance for CO2
to methanol using IR spectroscopy and mass spectrometry conversion to methanol. Recently, the metal oxide and
techniques. Their findings strongly support the reaction mech- bimetallic oxides have also been demonstrated to have
anism through CO pathway. In another study by Fujita et al.,[37] excellent catalytic properties in methanol synthesis from CO2
carbonate and formate intermediates were formed on the Cu/ hydrogenation.[39a] Additionally, the selection of support can
ZnO/Al2O3 catalyst. However, the carbonates had a short-life remarkably affect the catalytic performance of the catalyst
and were converted to formate.[38] In the trans-COOH mecha- because the nature of the support decides the dispersion of the
nism, CO2 is firstly hydrogenated with a H atom provided by active metals and the surface properties of the catalyst, which
H2O to form the hydrocarboxyl (COOH*) species. The COOH* is will impact the accessibility of CO2 and adsorption capability of
furtherly hydrogenated to dihydroxycarbene COHOH*, which is H2. The most common supports utilized for methanol catalysts

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are silica, alumina, zirconia, titania, zinc oxide, carbon nano- was anticipated between the number of active sites and the
tubes, and carbon nanofibers.[45] Table 2 demonstrates how size of clusters. The synthesis of methanol from CO2 in the
catalytic activity changes as its main components change in presence of Cu3, Cu4, and Cu20 clusters on Al2O3 support was
some of the recent studies.[45a] also studied by experimental data and density functional theory
Transition metal clusters have received a lot of attention in (DFT) calculations. The results of that study show a significant
catalysis, as they provide an extraordinary opportunity to dependency of catalytic activity on cluster sizes. When the
control the size of particles that promote the desired reaction, cluster supported on Al2O3 changes from Cu4 to Cu3, the
thereby contributing to an increase in activity and selectivity.[46] methanol production rate decreases by more than 50 %.
Despite a large number of studies on CO2 reduction to fuels According to DFT calculations, this reverse activity pattern
using different metal clusters[47] and other different kinds of comes from increased oxidation of the Cu3 clusters, resulting in
catalytic systems,[48] there are only a few studies on the a low binding energy on Cu3/Al2O3 catalyst. These recent
synthesis of CH3OH from H2 and CO2 on ultra-small non- investigations indicate that the size of copper clusters is one of
precious metal clusters. the critical points which can significantly change the catalytic
Vajda et al. investigated using size-selected copper clusters performance.[50]
produced in the gas phase for CO2 hydrogenation. The In contrast to Cu-based catalyst, the nobel Pd-based
experimental results and density functional theory (DFT) catalysts exhibit exceptional stability and resistance to water
calculations showed a low activation barrier for producing sintering.[51] Pd has a strong affinity for ZnO thus readily to form
CH3OH from CO2 in the presence of Cu4 clusters. This study a Pd Zn alloys under reducing environment at high temper-
proposes that small copper clusters can be outstanding and ature. The formation of Pd Zn alloy has been reported with
effective catalysts for CO2 reduction. The unique coordina- promising catalytic activity and selectivity for CO2 hydrogena-
tion environment of copper atoms in size-selected sub- tion to methanol. Bahruji et al. reported a Pd Zn alloy catalyst
manometer clusters leads to sites with significantly higher which showed reduced CO production through RWGS with
activity than larger copper particles.[49] An inverse correlation high selectivity to methanol through CO2 hydrogenation.[52] The
Au-based catalyst with different oxide supports, such as TiO2,
ZnO, ZrO2 and Al2O3, also demonstrated catalytic activity for
Table 2. The performance of some catalysts reported recently for CO2 methanol formation. Li et al. proposed that an interface effect
hydrogenation to methanol.
between the Au and CuO phases plays a crucial rule to enhance
Catalyst Reaction Methanol activity CO2 Ref. the hydrogen spillover of an Au-CuO/SBA-15 catalyst.[53] Hartadi
conditions (g/kg.h) conversion
(°C -bar) (%) et al. reported that Au particle size have a profound impact on
the catalytic performance for the formation of methanol from
20-Cu@Z- 260–30 73 12.1 [57]
rO2-U CO2 hydrogenation, that the catalytic activity increases while
Cu/CeZrOx- 240–30 222.4 4.7 [58] selectivity decrease with a smaller Au size.[54]
M Indium oxide (In2O3) has been recognized as a highly
PdCu/ 250–50 69.7 25.5 [59]
Ce0.3Zr0.7O2 selective catalyst for CO2 hydrogenation to methanol in recent
Cu/ 250–35 393.6 13 [60] years. This is because the oxygen vacancies in the In2O3-base
CeW0.25Ox catalysts, both the pure In2O3 catalyst and In2O3 supported
Cu-ZnO/ 260–30 395 12.7 [61]
Pr2O3-NS catalyst, could effectively inhibit the RWGS that lead to a high
Cu/ZnO/ 250–30 137.6 22.5 [62] selectivity for CO2 hydrogenation to methanol. Ye et al. used a
ZrO2 periodic density functional theory calculation to prove that
Cu ZrO2 230–10 17 1.6 [63]
CuZnAlCe 250–30 213 14.2 [64] oxygen vacancy promotes the CO2 hydrogenation to produce
CuZnZr/ 250–50 100 10.7 [65] methanol while impeding RWGS.[55] In addition, the In2O3-base
CuBr2 catalysts can be modified with promoters e. g., ZrO2, to enhance
CuZnZr 290–45 280 9.5 [66]
Cu1La0.2/ 240-30 186 5.7 [67] the adsorption and activation of CO2 and H2, as well as stabilize
SBA-15 the key reaction intermediates.[56]
CuZnCe/ 260–30 291.5 23.3 [68]
TNTs
Cu/Zr@SiO2 230–25 51 < 10 [69]
Cu/Ti@SiO2 230–25 91.2 < 10 [69] 4. CO2 to C2 + species
Cu/SiO2 250–41 6 2.8 [70]
Cu Pd/SiO2 250–41 35 6.6 [70]
Cu Pd/ 250–41 21 6.2 [70] Due to the high energy barrier of carbon-carbon bonding, the
MCM-41 synthesis of C2 + is more difficult than that of C1 product. In
Cu Pd/SBA- 250–41 23 6.5 [70] addition, the competitive reactions producing C1 hydrocarbons
15
Cu Pd/ 250–41 13 5.3 [70] and having a wide range of products in the reaction mixture
MSU-F have made synthesizing these hydrocarbons a real challenge.
Cu ZnO/ 250–20 137 15 [71] However, C2 + products are more beneficial than C1 compounds
CeZrO2
Cu/ZnO 250–30 51 12 [72] regarding energy densities and economic values.[74]
Cu Zn Zr/ 250–50 140 23 [73]
Al2O3

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4.1. Reaction mechanism

CO2 reduction to C2 + hydrocarbons may occur through

methanol-mediated or CO2-modified Fischer–Tropsch
mechanism.[75] The process of carbon dioxide conversion to C2 +
products via a methanol-mediated mechanism can be consid-
ered as two successive reactions over a bifunctional catalyst,
during which the conversion of CO2 and H2 to methanol occurs
first through the formate or CO formation mechanism. Then,
the produced methanol is converted to C2 + hydrocarbons
Figure 3. The mechanisms for CO2 to C2 + .
(MTH) by losing water or coupling over alumina or zeolites.
Therefore, these hybrid or bifunctional catalysts contain a
catalyst for methanol production and another for methanol
dehydration/coupling, which are effective for both reactions in explain product distribution. The ASF distribution cannot lead
the same conditions. (Eqs. 8–11).[74e] to high selectivity towards a single specific type of product. For
As discussed previously, CH3OH formation happens via a example, the selectivity of C2–C4 products is approximately
formate intermediate or CO-intermediated route. The DFT 38 %, while it is 53 % for C5 + hydrocarbons simultaneously.
calculations show that the CO2 activation during conversion to Therefore, breaking ASF distribution is pivotal in increasing
CH3OH determines the reaction rate.[76] Therefore, an effective target product selectivity. The combined use of Co- or Fe-based
catalytic system for CH3OH formation is favourable for the catalysts with solid acids, such as zeolites, have been widely
following production of C2 + hydrocarbons like dimethyl ether studied to further upgrade the products via acid-catalyzed
(DME), gasoline, and light olefins. As mentioned earlier, bifunc- oligomerization, aromatization and isomerization. The micro-
tional catalytic systems contain methanol formation dehydra- porous channels of the zeolite offer unique reactant, product
tion catalysts. However, it is important to determine whether and transition-state selectivity to the upgraded products.[82]
the mechanism of these catalytic systems is the result of the On the other hand, the low activity of C C coupling is a big
simple summation of two individual catalytic processes. A study challenge that further impedes the production of desired C2 +
conducted by Li et al. proved that these two individual catalysts hydrocarbons. Consequently, light hydrocarbons, mainly
significantly affect each other in hybrid catalytic system in terms methane, are usually the majority of products generated in CO2
of synergistic effects. Therefore, more investigation is required hydrogenation. To solve this problem and tune the selectivity,
in this field.[77] many studies have focused on manipulating catalysts through
On the other hand, CO2 can be converted to CO via the different methods.[74c–e,83] For example, a high yield of light
reverse water gas shift reaction (RWGS) and hydrogenated olefins can be achieved by bifunctional catalysts, such as
further to C2 + products via Fisher–Tropsch synthesis (FTS) ZnZrO,[77] ZnGaO,[84] and CuZnZr[85] mixed with zeolites, like
mechanism. The effective catalyst in this process must be active SAPO-34 or HZSM-5. In another study, 78.6 % selectivity of C5 +
for both reactions under the same conditions (Eqs. 12–14). hydrocarbons, with only 1 % CH4 selectivity, was obtained from
Because CO2 is reduced to CO by RWGS, understanding the the In2O3/HZSM-5 catalyst.[86] These results were a significant
desired reaction conditions for the RWGS reaction is crucial. For breakthrough in this field.[87] A summary of previous studies in
instance, high temperatures are required to achieve good this field has been provided in Tables 3 and 4. The bi-functional
conversion in RWGS (Eq. 13). catalysts that catalyzed the reaction through methanol medi-
According to the RWGS mechanism, *CO can be produced ated mechanism include Cu-, In-, Zr-, and Ga-based materials
by either decomposition of *HOCO or direct CO bond for CO2 hydrogenation. In contrast, the commonly used
cleavage.[78] Ko et al. proclaimed that CO2 could be converted to catalysts for the MTH process are zeolites. On the other hand,
CO2δ due to transferring charge from the surface.[79] During the the catalysts for C2 + hydrocarbon production based on CO2-
FTS process, *CO is chemically adsorbed on active sites, and modified FTS mechanism are usually Fe-and Co-based
then hydrogen inserts to form *CHx, which can initiate the chain systems.[64,67,72]
growth (Figure 3). The FTS limits the reaction rate in this Reports focused on the production of the higher alcohols
mechanism due to the lower reaction rate.[80] Pour et al. (C2 + OH) are less prominent in the literature compared to the
suggested that the reaction between CO and H2 producing studies on methanol and other C2 + species produced in CO2
*HCO limits the FTS reaction during the CO2 hydrogenation.[81] hydrogenation. Higher alcohol formation is a simultaneous
reaction that competes with hydrocarbon formation during the
FTS process, resulting in much lower C2 + alcohol selectivity. In
4.2. Heterogeneous catalytic systems for hydrogenation of addition, heavy alcohols are difficult to produce as their
CO2 to C2 + species synthesis involves C C coupling and C-OH formation. However,
as seen in Table 4, some recent studies could achieve good
Regarding CO2 hydrogenation to C2 + products, a wide range of results in producing C2 + alcohols.
hydrocarbons can be found in the reaction mixture. In most
cases, Anderson–Schulz–Flory (ASF) model can be used to

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Table 3. Examples of efficient catalysts reported for CO2 hydrogenation to C2 + products.

Catalysts Temp. P CO2 con. Hydrocarbon distribution (%) Ref.
(°C) (bar) (%) C2-C4
CH4 Paraffins Olefins C5 +

FeZn Na 320 30 37.5 15 6.8 36.9 41.3 [89]

FeZnNa/MWNTs 320 20 36.5 20.7 6.2 34.9 37.2 [90]
Na Zn Fe 340 25 39 12 4.7 43 40.5 [91]
ZnFe2O4 320 25 42.1 11.4 4.2 28.1 56.3 [92]
CoFe2O4/CNT 340 30 25.2 55.3 24.7 12.8 7.1 [93]
FeZnK–NC 320 30 34.6 24.2 7.1 40.6 28.1 [94]
10Fe0.8 K0.53Co 300 25 54.6 19.3 7.8 24.9 48.0 [95]
Fe Co/K Al2O3 320 30 41.4 21.7 6.3 45.0 27.0 [96]
C Fe Zn/K 320 20 54.8 23.1 8.5 57.4 11.0 [97]
Fe Cu K La/TiO2 300 11 23.1 19.4 – – 67.2 [98]
Na ZnFe2O4 340 10 34.0 9.7 – – 58.5 [99]
K Fe 300 15 43.9 12.2 – – 56.6 [100]
10Fe4.8 K 300 25 35.2 8.1 4.3 16.4 71.2 [95]
CuFeO2 24 300 10 16.7 2.4 – – 64.9 [101]
Na CoCu/TiO2 250 50 18.4 26.1 – – 42.1 [102]
Co/MIL-53(Al) 260 30 25.3 35.2 – – 35.0 [103]
In2O3/SAPO-34 380 30 15.3 2.7 13.7 81.9 1.7 [104]
In2O3 ZrO2/SAPO-34 380 30 26.2 2.0 21.5 74.5 2.0 [104]
In2O3/HZSM-5 340 30 13.1 1.0 – – 78.6 [86]
Cr2O3/HZSM-5 350 30 33.6 3.0 15.7 3.1 78.2 [105]
ZnAlOx and HZSM-5 320 30 9.1 0.5 6.7 10.7 80.3 [106]
ZnZrO/HZSM-5 320 40 14.1 0.3 14.5 4.9 80.3 [76a]

Table 4. Examples of efficient catalysts reported for CO2 hydrogenation to higher alcohols.
Catalysts Temp./°C P/bar CO2 con./% MeOH C2 + OH Ref.
select./% select./%

Co/La4Ga2O9 270 35 4.6 15.3 34.7 [107]

Na–Co/SiO2 300 5 18.8 12.5 87.5 [108]
RhFeLi/TiO2 250 30 15.7 2.2 31.3 [109]
Mo1Co1K0.8 320 50 28.8 70.9 10.9 [110]
1 wt.%Pt/Co3O4 200 80 – – 82.5 [111]
PdCu NPs/P25 200 32 – – 92.0 [112]

5. Catalyst synthesis methane, respectively.[114] In addition, incipient wetness impreg-

nation can be achieved by reducing the solvent-to-support
The catalyst performance in CO2 hydrogenation can be ratio. The method often allows a good control of particle size.
influenced by various structural factors, e. g., the morphology
and crystal phases of the catalyst, the active metal dispersion or
the metal-support interaction. These factors are very much 5.2. Deposition-precipitation
dependent on the catalyst synthesis method. The most
promising supported metal/metal oxide catalysts for CO2 hydro- Deposition-precipitation is achieved by using a metal precursor,
genation generally can be prepared by impregnation, deposi- typically an inorganic metal salt, to deposit the targeted
tion-precipitation and co-precipitation.[113] metal(s) onto an existing support. In this method, metal particle
growth occurs when the precursor solution is supersaturated,
leading to the formation of nuclei and the subsequent growth.
5.1. Impregnation The nucleation of the metal species is controlled by changing
the pH or temperature, through which the solubility of the
Impregnation involves mixing pre-made supports with a metal species are reduced and the formation of bulk phases in
solution of metal precursors. The metal precursor, when solution can be minimized. The presence of the support in fact
dissolved, may or may not chemically interact with the support decreases the energy barrier for nucleation, resulting in
surface. If there is a chemical interaction, excess solvent can be preferential precipitation on the support over homogeneous
removed through filtration. Alternatively, if there is no chemical growth of particles in solution. Din et al. used deposition-
interaction, the solvent can be removed by evaporation. This precipitation to synthesize zeolite based Cu Co bimetallic
method is applicable to a wide range of solid supports. For catalysts with Cu Co metals interaction that is beneficial for
example, For example, Zhang et al. synthesized coal char- catalytic conversion of CO2 into methanol.[115]
supported Ni catalysts and Popova et al. synthesized Ni/Ru-
modified ZSM-5 zeolites catalysts for CO2 hydrogenation to

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5.3. Co-precipitation Data Availability Statement

Co-precipitation is similar to deposition-precipitation that it The data that support the findings of this study are available
relies on induced nucleation and growth by a change in pH, from the corresponding author upon reasonable request.
temperature or evaporation. Co-precipitation, however, involves
dissolving both the salts of the active metal and that of the Keywords: CO2 hydrogenation · heterogeneous catalysis ·
support simultaneously. As such, the nucleation and growth of formate · methanol · C2 + hydrocarbons
a combined active metal and support are achieved in a single
step. This method is able to give a very high metal loading (up
to 70 % or higher) while maintaining small particle size that is
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