Cu - ZnO-Bases Catalysts

REVIEW
published: 29 September 2020

doi: 10.3389/fenrg.2020.545431
Improving the Cu/ZnO-Based

Catalysts for Carbon Dioxide
Hydrogenation to Methanol, and the
Use of Methanol As a Renewable
Energy Storage Media
Ubong J. Etim 1, Yibing Song 2 and Ziyi Zhong 1,3*
1
Guangdong Technion Israel Institute of Technology (GTIIT), Shantou, Guangdong, China, 2Department of Chemistry, Shantou
University, Shantou, China, 3Technion-Israel Institute of Technology (IIT), Haifa, Israel
Heterogeneous catalytic hydrogenation of carbon dioxide (CO2) to methanol is a practical

approach to mitigating its greenhouse effect in the environment while generating good
economic profits. Though applicable on the industrial scale through the syngas route, the
catalyst of Cu/ZnO/Al2O3 suffers from a series of technical problems when converting CO2
to methanol directly, which include low single-pass conversion, low methanol selectivity,
Edited by:
James George Highfield, requiring high pressure and fast deactivation by the reverse water gas shift reaction. Over
Independent Researcher, Singapore the years, intensive research efforts have been devoted to proffering solutions to these
Reviewed by: problems by modifying the existing catalyst or developing new active catalysts. However,
Andreas Borgschulte,
Swiss Federal Laboratories for
the open question is if this type of widely used industrial catalyst still promising for CO2
Materials Science and Technology, methanolizing reaction or not? This paper reviews the history of the methanol production in
Switzerland
industry, the impact of CO2 emission on the environment, and analyzes the possibility of
Blaž Likozar,
National Institute of Chemistry, the Cu/ZnO-based catalysts for the direct hydrogenation of CO2 to methanol. We not only
Slovenia address the theoretical and technical aspects but also provide insightful views on catalyst
*Correspondence: development.
Ziyi Zhong
ziyi.zyong@gtiit.edu.cn Keywords: carbon dioxide, hydrogenation, methanol, Cu/ZnO catalyst, microstructure
Specialty section:
This article was submitted to Hydrogen INTRODUCTION
Storage and Production,
a section of the journal Carbon dioxide (CO2) is a greenhouse gas emitted into the atmosphere via the combustion of fossil
Frontiers in Energy Research fuels (oil, coal, natural gas) in vehicles and power plants, from many industrial processes, and
Received: 25 March 2020 household operations, etc. (Karl and Trenberth, 2003; Hansen et al., 2006; Lim, 2015). On receiving
Accepted: 25 August 2020 the CO2 from these sources, the earth heats up, resulting in global warming. A recent report shows
Published: 29 September 2020 that as of 2017, the global average concentration of CO2 in the atmosphere was 405 ppm, and it is
Citation: expected to reach 410 ppm by 2020, which shows a clear increasing level in the atmosphere.
Etim UJ, Song Y and Zhong Z (2020) Therefore, it is urgent to develop and establish practical and reliable emission reduction technologies
Improving the Cu/ZnO-Based and CO2 control approaches. In recent times, this has been one of the reasons why discussion of CO2
Catalysts for Carbon Dioxide
emission reduction tops agenda in most environmental pollution control submits, globally.
Hydrogenation to Methanol, and the
Use of Methanol As a Renewable
The reduction of CO2 to economically relevant products represents an eco-friendly and green
Energy Storage Media. route toward value-added CO2 emissions mitigation for environmental sustainability. For example,
8:545431. converting CO2 to liquid fuels and chemicals is essential to cushion the shortage of fossil fuels and to
doi: 10.3389/fenrg.2020.545431 provide cheap availability of chemical feedstock (Kattel et al., 2017a). This kind of conversions can be
Frontiers in Energy Research | www.frontiersin.org 1 September 2020 | Volume 8 | Article 545431

Etim et al. CO2 Reduction to Methanol for Renewable Energy Storage
FIGURE 1 | Diverse products from thermochemical CO2 conversion and methanol.
successfully implemented by heterogeneous catalytic processes equilibrium conversion of CO2 to methanol at high
using cheaply available hydrogen, e.g., H2 from natural gas and temperatures, the development of efficient catalysts to break
shale gas, or renewable sources of energy (Dang et al., 2018; Ouda the thermodynamics barriers is of extreme importance. Thus,
et al., 2019). The catalytic reduction of CO2 can produce carbon a selective catalyst is required to optimize methanol synthesis.
monoxide (CO), methanol, or hydrocarbons. CO is a feedstock in Although new catalysts have been developed in the last five
the Fischer–Tropsch process, while the applications of methanol years, the conventional Cu-based catalysts for CO2
and hydrocarbon are diversified. hydrogenation to methanol are still extensively investigated for
Methanol is an essential industrial commodity chemical, with further improvements. Considering the significant progress
a global production capacity higher than 100 MTY (Bertau et al., achieved in this area, we will discuss and focus on the recent
2014; Jadhav et al., 2014; Wang et al., 2014; Sehested, 2019). In advancements in the application of Cu/ZnO-based catalysts for
2018, the demand for methanol was approximately 80–90 million the direct synthesis of methanol from CO2, i.e., using CO2 as the
tons and will exceed 110 MTY by 2023. Methanol can be directly sole feed. We will also retrospect and review the history of the
used as a clean-burning biodegradable fuel in combustion engines methanol production in industry, the reaction thermodynamics,
and fuel cells, and can be transformed by various chemical mechanism, and kinetics, as well as the catalyst structures and
processes into a wide range of useful chemicals (Figure 1). suitable conditions for surpassing the equilibrium catalyst
The latter can be subsequently applied to produce a broad activity.
range of daily products—fuel additives, resins, plastics, paints,
polyester, and building materials (Goeppert et al., 2014; Sehested,
2019). With the increasing use of these products, more methanol THERMODYNAMICS AND REACTION
is required to meet the large-scale precursor chemical production MECHANISM
and other applications. Hence, the catalytic conversion of CO2 to
methanol is highly desirable to meet the high demand and to Thermodynamics
ensure a cleaner environment by reducing the burden of global In the hydrogenation of CO2 feedstock to a desirable product, the
warming caused by CO2 emission, with associated potential performance of a catalyst will be determined by the
economic benefits. thermodynamics of the reaction. Thus, the maximum
Generally, conversion to methanol and other value-added conversion of CO2 at a given pressure and temperature is
products is an effective strategy for CO2 valorization. Some defined by the thermodynamic equilibrium conversion under
literature reports in the past have reviewed the CO2 reduction the given reaction conditions (Mutschler et al., 2018). The
with hydrogen over heterogeneous catalysts focusing on the transformation of CO2 to methanol is an exothermic reaction
different aspect of the field, including the CO2 reduction to (Eq. 1), and therefore, favored at low reaction temperature and
CO, methanol and hydrocarbons, their challenges and high pressure. Consequently, elevated pressure and reduced
prospects (Porosoff et al., 2016; Yang H. et al., 2017; Whang temperature favor an increased methanol yield. However,
et al., 2019; Zhou et al., 2019). According to the thermodynamics, considering the reaction kinetics and the inert nature of CO2,
the most stable reaction path for CO2 hydrogenation yields a high reaction temperature greater than 240°C is often applied
methane as the product. The pathway to a particular reaction (Ma et al., 2009). In addition, this reaction often accompanies the
can be selectively controlled by selecting appropriate catalysts and reverse water gas shift (RWGS) reaction, that is endothermically
reaction conditions (Porosoff et al., 2016). Owning to a low (Eq. 2) favorable at high temperatures and low pressures,

generating CO, which lowers the selectivity to methanol, and Reaction Mechanism
H2O that deactivates the catalyst. These factors reduce catalyst Knowledge of the mechanistic details is a decisive catalyst design
activity and increase the difficulty in process design (Grabow and criterion for CO2 hydrogenation catalysts. Generally, two
Mavrikakis, 2011; Graciani et al., 2014; Hartadi et al., 2015). Thus, mechanistic pathways have been proposed from many studies
the overall process is limited by the thermodynamic equilibrium, for CO2 hydrogenation to methanol over Cu-based catalysts, as
and the equilibrium-shift chemistry plays out to control the shown in Figure 3 (Kattel et al., 2016; Huš et al., 2017a; Huš et al.,
conversion and selectivity of the products. 2017b; Yang B. et al., 2017; Karelovic et al., 2019). The first
pathway features the CO intermediate, which is produced from
CO2 + 3H2 ↔ CH3 OH + H2 O, ΔH298 K −49.5 kJ mol−1 (1)
RWGS: CO2 + H2 → CO + H2O reaction via carboxyl (*HOCO)
CO2 + H2 ↔ CO + H2 O, ΔH298 K 41.2 kJ mol−1 (2) species and is further hydrogenated to methanol; the other
pathway is associated with the formate (*HCOO) intermediate
Breaking the thermodynamics/kinetics limitation by formed by CO2 hydrogenation which eventually produces
increasing one-pass CO2 conversion (CO2 conversion at a methanol via the C–O bond cleavage and *HCO or *H2CO
single step) can tune the selectivity away from CO and intermediates (Liu and Liu, 2015). According to the density
toward methanol (Stangeland et al., 2018). One way to functional theory (DFT) calculations, CO2 hydrogenation
actualize this is by applying high pressure. The high-pressure prefers the formate pathway on ZnCu(211) via *HCOOH,
approach using a conventional Cu/ZnO/Al2O3 methanol *H2COOH, and *CH3O intermediates over the RWGS + CO-
synthesis catalyst was applied to CO2 hydrogenation to hydro pathway for methanol synthesis (Kattel et al., 2017b). On
methanol (Figure 2). Under the specified reaction conditions, the same ZnCu(211) surface, hydrogenation of CO2 can proceed
methanol selectivity, and productivity were remarkably boosted through the Eley–Rideal mechanism, as with pure Cu catalysts, as
at high pressure by increasing H2 partial pressure to enhance the a result of the unfavorable CO2 binding at the Zn–Cu interfacial
reaction rate and thermodynamically favor high CO2 conversion site. CO is the main product along the RWGS pathway, and only a
and methanol selectivity (Bansode and Urakawa, 2014). As relatively small proportion of *HCO could further be
reported by Stangeland et al. (2018), both temperature and hydrogenated to *CH3OH. The direct dissociation of *CO2 to
pressure have considerable effects on the equilibrium *CO and *O was also evident, and the strong oxygen affinity for
conversion. The methanol synthesis reaction becomes less Zn sites kinetically favored the formation of *O more than
favored, and the RWGS reaction more favored as the hydrogenation to *HOCO. On unsupported or unalloyed Cu
temperature is increased. On the other hand, increasing the catalysts, *HCOO species act as spectators for methanol synthesis
pressure strongly enhances the CO2 conversion at low (Yang et al., 2015; Kattel et al., 2017b). The addition of Zn or ZnO
temperatures. Moreover, lowering the concentration of CO2 stabilized the *HCOOH intermediates via direct Zn–O
in the feed stream can increase the CO2 conversion, and this interaction and by activating *HCOO via hydrogenation.
can be achieved by using excess H2 to shift the equilibrium to the Chances to suppress the undesired CO formation for an
products side. Thus, a high H2/CO2 ratio leads to high methanol increased methanol yield are high, and different strategies can
and low CO selectivity. The selection of the appropriate H2/CO2 be applied if the two reactions are known to proceed
ratio, therefore, depends on the requirements of the methanol independently via parallel pathways (and on various surface
synthesis system. For example, if high conversions are targeted, it sites). In turn, it will be a hard task to suppress CO formation
is preferable to work at high H2 concentrations (Stangeland et al., for a catalyst that produces methanol by a mechanism that shares
2018). Irrespective of the pressure, increasing the H2/CO2 ratio a common intermediate with CO formation or even uses CO as a
will lead to an increase in the CO2 conversion to methanol owing reactant (Kunkes et al., 2015). For the industrial Cu/ZnO/Al2O3
to the sensitivity of H2 partial pressure to the methanol synthesis catalyst, the Fourier-transform infrared spectroscopy analysis has
(Jia et al., 2016; Stangeland et al., 2018). It was demonstrated that shown that the hydrogenation of both formate and methoxy
product condensation could be utilized to circumvent species is the rate-determining step in the methanol synthesis
thermodynamic restrictions on the product yield. Thus, over Cu-based catalysts (Ojelade and Zaman, 2019). Formates are
significant improvements in CO2 conversion can be achieved the dominant species when CO2 is used as the feed, whereas
by operating at conditions favorable for product condensation methoxy species would result in the case with CO as the main
(Stangeland et al., 2018). Also, the thermodynamic limitation reactant.
can be overcome with reactors, which can recycle the waste CO2 Theoretical studies deciphered that the WGS reaction followed
from methanol combustion, and this can increase the conversion the carboxyl mediated mechanism, and the methanol synthesis
to almost 100% (Goeppert et al., 2014; Huš et al., 2017a). Thus, followed both CO and CO2 hydrogenation pathways (Grabow
performing multiple separation/recycling loops can produce and Mavrikakis, 2011). Under conditions typical of the industrial
high conversion under practical temperature and pressure. methanol synthesis, CO2 hydrogenation was responsible for
The use of microstructured catalytic reactors with transverse about 65% of the methanol produced from the intermediates
diameter channels on a millimeter-scale has advantages over *HCOO, *HCOOH, *CH3O2, *CH2O, and *CH3O (Grabow and
larger systems of better heat management, more efficient use of Mavrikakis, 2011; Kattel et al., 2016). The formation of *HCOO
catalysts and controlled operation at high pressure (Renken and species from *CO2 and *H on Cu(111) involved no intermediate
Kiwi-Minsker, 2010). carbonate species and the hydrogenation of *HCOO led to

FIGURE 2 | Effects of (A) CO2/H2 feed ratio and (B) temperature on conversion of CO2 (XCO2 ), conversion of H2 (XH2 ) and selectivity to CO (SCO), and methanol
(SMeOH) in CO2 hydrogenation over the Cu/ZnO/Al2O3 catalyst. Reaction conditions: T 260°C, P 360 bar, GHSV 10,471 h−1 and CO2/H2 1:10 (Bansode and
Urakawa, 2014). Reproduced with permission from Elsevier.
*HCOOH instead of *H2CO2 (Grabow and Mavrikakis, 2011). methanol synthesis are limited by the formation of *CH3O at low
However, the direct hydrogenation of formate over Cu(111) is not CO2/(CO + CO2) ratios and by its hydrogenation in CO2-rich
a feasible pathway for methanol production under dry hydrogen feeds. Thus, the *CH3O hydrogenation is a slow step during
conditions (Zhao et al., 2011). Thus, the presence of small amounts methanol synthesis from both the CO and CO2 routes. Factors
of water is essential in methanol synthesis from CO2 such as their rate-determining steps, feed composition, and
hydrogenation on Cu-based catalysts (Yang et al., 2013). It is reaction conditions influence the relative contribution of each
shown that direct formate hydrogenation does not lead to route (Grabow and Mavrikakis, 2011).
methanol due to the high hydrogenation barriers of HCOO and
H2COO. Formate, formaldehyde, and methoxy radicals are
unlikely to be reaction intermediates for methanol synthesis. METHANOL SYNTHESIS CATALYSTS
CO is also hydrogenated in significant amounts to *HCO,
*CH2O, *CH3O, and *CH3OH, and plays a promotional role in Historical Development of the Industrial
methanol synthesis, which include two possibilities: a) removal of Catalysts for CO2 Conversion to Methanol
*OH via *COOH to form CO2 and hydrogen via WGS, and b) The use of Cu-based catalysts for methanol synthesis via the CO2
assisted hydrogenation of various surface intermediates (Grabow dehydrogenation route is as old as the process itself. In 1921, the
and Mavrikakis, 2011). Route a) also contributes to methanol first patent for methanol synthesis on Cu-based catalyst was filed
production, although its effect is minute compared with the by Patart (1922), but the catalyst failed to get attention for
direct hydrogenation of CO to methanol. However, the rates of commercial use due to its susceptibility to sulfur poisoning.
FIGURE 3 | Pathways for the CO2(g) hydrogenation to CH3OH(g) over the surface of Cu-based catalysts.

The Imperial Chemical Industries developed the Cu/ZnO catalyst

in the late 1960s, which was operative at pressure and
temperature of 50–100 bar and 200–300°C, respectively, and
using syngas (CO + H2) as feedstock (Din et al., 2019).
Following the successful industrialization of the process and
development of gas purification system, which freed the
syngas produced from coal, natural gas and crude oil from
poisoning by sulfur (Supp, 1973), interest in Cu-based
catalysts revived with a ternary Cu-based catalyst—copper
oxide, zinc oxide, and chromium oxide (synthesized by in situ
reductions) (Davies and Snowdon, 1967). Subsequent studies
found that replacing chromium oxide with alumina prolonged
the catalyst life. The copper–zinc–alumina catalysts were
prepared by co-precipitation of soluble zinc and copper salts
(usually the nitrates) with an alkali carbonate solution. The
resulting mixture of carbonates was heated to form a mixture
of oxides, which were then mixed with aluminum oxide (Casey
and Chapman, 1974).
To improve the activity, selectivity, thermal stability, and
resistance to poisoning, the Raney copper catalysts consisting
of 50% aluminum and 50% copper–zinc mixture by precipitation
with NaOH (Marsden et al., 1980). These catalysts were active for
methanol production comparable to that of the commercial
copper-based methanol synthesis catalyst, but selective to
small amounts of dimethyl ether (DME) by-product.
As early as 1930, the possibility of synthesizing methanol
from CO2 as the sole feedstock was known. As then known,
methanol catalysts produced CO2 or H2O or both along with
methanol. It was proposed that the formation of methanol
from CO and hydrogen may not be direct, especially when
approaching a steady state. Smith and Hirst (1930) observed
that hydrogen and CO2 formed CO and H2O over methanol FIGURE 4 | Evolution of Cu-based catalysts for conversion of CO2 to
catalysts at atmospheric pressure. In the like manner, CO and methanol (CO2 as the sole carbon source).
H2O react over the Cu-based catalysts to form CO2 and

hydrogen, and equilibrium could be closely approached in
the water-gas shift reaction. In 1932, the reaction was Ren et al. provided the evidence than Cu species promoted by
confirmed in addition to the regular methanol formation Zn were essential for the hydrogenation of CO2 in the CO2
over the unsupported zinc–copper–aluminum catalyst under promoted CO–H2 gas system. They observed that CO2
a certain pressure at high temperatures (Boomer and Morris, inhibited the CO hydrogenation over Pd/Al2O3, and
1932). Although the catalyst was not particularly active, it ZnO–Cr2O3 catalysts, but promoted it over Cu–ZnO/A12O3,
indicated the course of the reaction. In 1945, it was found that at their respective optimum temperatures and under pressures
methanol from CO2 could be produced over copper–alumina that ensured low conversions (Ren et al., 1989).
catalysts in the temperature range of 282–487°C and the Intensive research on the methanol synthesis from CO2 and
pressure range of 117–410 atm. Catalysts consisting of Cu the active catalysts started growing in the 1980s. Currently, the
or Al2O3 alone had no catalytic activity. The most active ternary copper-based catalyst (Cu/ZnO/A12O3) is still used for
catalyst had a Cu content of 8–25% and gave a conversion the industrial synthesis of methanol from CO2 in the gas phase
of 94% under 410 atm at a temperature of 285°C. With CO as from a mixture of syngas and CO2 under the operations
the carbon source, similar experiments gave 39–43% conditions: temperature and pressure of 220–300°C and
conversions, with about 15 and 41% of the CO charge 50–100 bar, respectively (Din et al., 2019; Sehested, 2019).
converted to methane and DME, respectively (Ipatieff and In this process, methanol formation is believed to originate
Monroe, 1945). In the reaction gas mixture (CO/CO2/H2) with mainly from CO2, whereas CO acts as a scavenger of surface
CO:CO2 of 3.1:1, the methanol conversion was 64%, and the oxygen. Due to the availability of CO2 in large volumes from
formation of DME reduced to about 1%. The results led to the emissions into the atmosphere and the need for environmental
postulation that the formation of methanol from CO2 and cleaning to reduce the incidence of global warming and
hydrogen under pressure may proceed along two paths. The demand for clean fuel, research efforts are devoted to the
developmental milestone of the Cu-based catalysts for the use of CO2 as the sole reactant gas which is challenged by the
direct CO2 to methanol conversion is presented in Figure 4. unavailability of efficient catalysts (Din et al., 2019).

The Present Commercial Catalyst et al., 2014; Mota et al., 2018). Al2O3 incorporation into the
(Cu–Zn–Al) catalyst is necessary to enhance catalyst stability and resistance to
At the commercial scale, methanol is synthesized over Cu/ZnO/ thermal sintering of the Cu crystallites. In addition, studies
Al2O3 catalyst at a pressure of 50–100 bar and temperature of suggest that alumina also acts as a promoter, though there is
220–300°C. This catalyst contains 50–70 atomic% CuO, 20–50% evidence of Al3+ doping into ZnO, which specifically tailors the
ZnO, and 5–20% of the Al2O3 promoter. These combinations reduction properties of the latter. Also, Al2O3 surface acidity
allow the formation of stabilized Zn-incorporated Cu surfaces, affects the byproducts’ selectivity (Xiao K. et al., 2017). Table 1
which are highly defective, and enable the maximization or summaries the performance of the Cu/ZnO/Al2O3 catalysts
optimization of the density of the active sites. The resulting investigated in recent years.
oxide catalyst is activated with diluted hydrogen at 190–250°C, The catalyst must fulfill three important technical requirements
at which CuO is completely reduced to metallic crystallites (Figure 5) for high catalytic activity, which can be ensured by the
interspersed by ZnO/Al2O3 (Behrens et al., 2013). It should be nanoparticulate and porous Cu/ZnO aggregates (Zander et al., 2013).
noted that the commercial Cu/ZnO/Al2O3 catalysts for methanol Different methods have been investigated for the preparation of the
synthesis are not a “supported system” although researchers often commercial catalysts by researchers, including solid-state combustion,
mistake it as one because neither ZnO nor Al2O3 component is solid-state reaction, reduction–precipitation, reversed co-precipitation
classical porous oxide support to qualify it as such, and the active and deposition precipitation (Natesakhawat et al., 2012; Dong et al.,
phase has a high loading in the system (Behrens et al., 2013). The 2016; Dasireddy and Likozar, 2019); however, desirable properties for
Cu-rich composition of the industrial catalyst possesses a peculiar the industrial applications are more often achieved by the co-
microstructure, which is composed of spherical copper precipitation method. Initially developed by the Imperial Chemical
nanoparticles of sizes 5–15 nm and even smaller ZnO Industries in the 1960s, the method involves co-precipitation, aging of
nanoparticles arranged in a regular pattern (Lunkenbein et al., the mixed metal Cu, Zn, and (Al) hydroxyl-carbonate precursor
2015). In the catalyst, ZnO affords typical promoting functions, materials, thermal decomposition and finally activation by
partakes in active sites creation, and supports and stabilizes the reduction of Cu component to active species as shown in Figure 6
mesostructure of the Cu phase. In the Cu/ZnO/Al2O3 catalyst, (Waller et al., 1989; Fierro et al., 1996; Spencer, 1999; Whittle et al.,
there is a strong metal–support interaction layer of metastable 2002; Kniep et al., 2004; Behrens et al., 2011). During the synthesis, the
“graphitic-like” ZnO after reductive activation, which was initially formed solids from co-precipitation of Cu, Zn and Al
kinetically stabilized by interacting with the defective and Cu precursors are amorphous hydroxycarbonates, which evolve during
surface (Lunkenbein et al., 2015). The defects are crucial for the aging in contact with the mother liquor to crystalline forms with
stability of the ZnO overlayer and may lead to the presence of different composition, morphology, and structure as a result of
some ZnOx species that act as co-catalysts in the methanol Ostwald ripening dissolution/re-precipitation or agglomeration
synthesis. The overlayer growth protects the Cu from particle (Mota et al., 2018). Aging can increase the exposed Cu surface
size growth and reshaping. ZnO can also act as a spacer, avoiding area, ZnO crystallite size, the stability of ZnO, and the Cu–ZnO
the direct contact of the Cu particles with the Al2O3, enabling contacts due to the change in the structure of precipitates with a strong
dispersion of the Cu particles and preventing them from sintering influence on the microstructure of the final Cu/ZnO–Al catalysts
(Kasatkin et al., 2007). The Al2O3 component, although it can (Mota et al., 2018). Calcination influences the precursor
interact with the ZnO phase, does not generally change the decomposition and the CuO structure of the catalyst (Zhang et al.,
evolution of the Cu/ZnO binary phase. It helps to modify the 2010). The average CuO crystallite size increases with an increase in
ZnO surface, introducing defective sites by doping (Schumann calcination temperature, whereas the dispersion of Cu species
TABLE 1 | Performance of various Cu/ZnO/Al2O3 ternary industrial catalysts.
Catalyst T (°C) P (MPa) H2/CO2 WHSV (mL gcat−1 h−1) CO2 conv. (%) CH3OH sel. (%) References
JM-HiFUEL (50 wt% Cu/ZnO/Al2O3) 270 4.5 3:1 18,000 — 0.38a Li et al. (2018)
Industrial CuO/ZnO/Al2O3 220 8.0 — 3,400 L h–1 40 Lachowska and Skrzypek (2004)
Cu/ZnO/Al2O3 250 4.1 — 3,600 L h–1 18.2 27 Jiang et al. (2015)
Cu/ZnO/Al2O3 270 5.0 3:1 4,000 10.7 81.8 Xiao S. et al. (2017)
Cu/ZnO/Al2O3 240 2.0 — 3,600 L h–1 20.1 31.3 Hong et al. (2002)
Cu/ZnO/Al2O3 240 2.0 — 7,200 L h–1 17.3 32.4 Hong et al. (2002)
Cu/ZnO/Al2O3 260 36.0 — — 37 72 Bansode and Urakawa (2014)
Cu/ZnO/Al2O3 250 3.0 — 18,000 16.9 42.3 Lee et al. (2000)
Cu/ZnO/Al2O3 230 3.0 3:1 — 18.7 43.0 Li et al. (2014)
Cu/ZnO/Al2O3 170 5.0 2.8:1 — 4.3 45.1 Liu et al. (2007)
Cu/ZnO/Al2O3 270 4.5 2.2:1 — 12.3 42.3 Liao et al. (2011)
Cu/ZnO/Al2O3 270 4.5 2.2:1 — 10.9 72.7 Liao et al. (2011)
a
Space-time yield (STY) (gml–1 h–1); weight hourly space velocity (WHSV).

FIGURE 5 | Properties, challenges and possible solutions.
decreases under the same condition (Guo et al., 2011). Usually, the (Bansode and Urakawa, 2014), obviously this pressure is too
calcination temperatures of 300–400°C are optimum for forming a high from an economic point of view.
suitable catalyst. The detailed description of the synthesis of this
catalyst can be found in the literature (Behrens and Schlögl, 2013). Active Sites
The Cu–ZnO–Al2O3 catalyst system has been optimized to a Theoretical Modeling of the Cu–ZnO Catalyst Surface
very high-performance level under relevant industrial conditions. The multiscale modeling techniques adopted for investigating the
Thus, one may rationally assume that the catalyst is highly active performance of the traditional Cu-based catalysts include the
for the direct CO2 hydrogenation to methanol. Although Cu/ZnO/ DFT, kinetic Monte Carlo (kMC), and microkinetic modeling (Li
Al2O3 exhibits promising performance (space-time yield up to et al., 2015; Huš et al., 2017b; Kopac ̌ et al., 2017; Kopač et al., 2019;
7,729 gMeOH kgcat−1 h−1) under 36 MPa and 10:1 H2:CO2 ratio Park et al., 2020). These models allow for the clarification of the
FIGURE 6 | Major steps in co-precipitation synthesis of Cu–ZnO–Al2O3 catalyst developed by ICI. Stages 1–4 refer to aging, washing/drying, calcination and
reduction, respectively (Behrens and Schlögl, 2013). Reproduced with permission from John Wiley and Sons.

exact reaction pathway, including energetics and kinetics of every the methanol synthesis over Cu/ZnO catalysts. The kinetics
reaction step, and help the analysis of catalyst performance over a further deviated on Zn-promoted Cu due to the reduced
range of operating conditions and different length and time scales activation energies of several critical reactions, leading to the
(Park et al., 2020). The DFT can compute ground-state energy improved catalytic performance of ZnCu(211).
and its associated properties using electron density, allowing for The simple pure-copper kinetic model can sufficiently
the calculation of relatively larger systems such as nanoparticles describe the catalysts with different supports after modifying
and periodic surfaces. The atomic configurations, transition the model active site concentrations (Jurković et al., 2020). Such a
states, energetics, energy barriers, and reaction mechanisms method can be useful for predicting the activity of the Cu/Al2O3
derived from first-principles calculations can be used to catalyst and for further reactor designs modeling and scale-up
predict the catalytic activities at an atomic level. The kMC applications. Applying these could guide the rational design of
showed how the catalytic surface coverages change with time multifaceted Cu catalysts for methanol synthesis by surface
and conditions on a microscopic scale, and resolve the surface defects engineering.
coverage with atomistic detail (Pavlišič et al., 2020). Microkinetic
modeling is an important continuum model with even higher Experimentally Observed Active Sites
accuracy and reliability than DFT and kMC. It is an ideal Studies have discussed the identity of the catalysts’ active sites,
framework for integrating the data generated by latter. Like with particular regard to the intermediates and precursors for
the kMC, it avails information on product distribution and methanol formation. The reported kind and nature of the active
estimates the catalyst activity in steady-state kinetics (Li et al., sites are closely linked with the synthesis method and/or the
2015). In many cases, the catalytic performance data form analytical techniques deployed for studying it (Herman et al.,
Cu-based catalysts compared qualitatively with those obtained 1979). For the Cu-based catalysts, the active sites are considered
from the experiments in the literature. For example, the results to be metallic Cu (Cu0) or Cu+, and the activity was shown to be
from these theoretical modellings were found to conform well to directly related to the Cu surface area (Baltes et al., 2008; Dong
the experiments over Cu–ZnO–Al2O3 or Cu–MgO–Al2O3. The et al., 2016; Dasireddy and Likozar, 2019). However, other studies
active sites of the catalysts Cu–ZnO or Cu–MgO were modeled by found that the catalytic activity was not certainly correlated
the DFT. Cu sites were modeled as a Cu(111) surface on top of linearly with the Cu surface area (Nakamura et al., 2003). The
which ZnO or MgO cluster was placed in the most energetically active sites and the activity relations of a reversed co-precipitated
favorable position. The methanol synthesis was investigated prepared Cu-based catalysts were investigated by various
under different temperatures and pressures. Both the characterization techniques (Natesakhawat et al., 2012). The
microkinetic and kMC modeling indicated high selectivities results revealed the presence of metallic Cu on the surface of
toward methanol at low temperatures (between 95 and 100%). fresh but reduced and spent catalysts. CuO in the catalyst reduced
Cu/Mg and Cu/Zn had different reaction pathways toward to Cu0 upon exposure to H2 at 250°C. This state was observed in
methanol production, which depended on the operating various kinds of Cu-containing catalysts with different supports/
conditions and the formate pathway was the energetically additives, size of Cu particle, and varying degrees of ZnO
most favorable over the Cu/Zn surface. crystallinity, thus it can be concluded from this study that
The DFT calculation found that, on a commercial Cu/ZnO/ additives, particles and support crystallite size do not affect the
Al2O3 catalyst, the open Cu surfaces [e.g., Cu(110) and Cu(100)] activity of Cu (Natesakhawat et al., 2012).
partially covered by oxygen are active for methanol synthesis, Tsang and co-workers observed the formation of CuZn alloy
suggesting that Cu species without the effect of support are the particles by X-ray photoelectron spectroscopy (XPS) in the Ga-
active sites for methanol synthesis (Grabow and Mavrikakis, promoted Cu/ZnO catalyst for CO2 hydrogenation to MeOH.
2011). Different surfaces and the presence or absence of They attributed the effect of incorporation of Ga3+ to the
surface defects have shown the ability to catalyze the methanol formation of the ZnGa2O4 spinel structure, which created
synthesis. The stepped Cu(533) surface was shown to enhance the electronic heterojunction with excess ZnO phase that eased the
selectivity for methanol about four orders of magnitude better reduction of Zn2+ to Zn0 to form CuZn alloy upon contact with
than a flat Cu(111) surface (Kopač et al., 2019). The defective Cu nanoparticle. They also correlated the concentration of Zn0 in
surface relative to the Cu(111) surface promoted the H2COH the CuZn alloy nanoparticle with the catalytic performance (CO2
hydrogenation pathway, resulting in higher CH3OH yields. Over conversion and methanol selectivity) and found that the latter
(ZrO2)3/Cu(110) interface, the adsorption energies of could be significantly improved by increasing the Zn0 content in
unsaturated species were observed to increase compared to a the heterojunction catalysts (Li et al., 2016). With advanced
pure Cu(110) surface. A similar observation was recorded for the characterization techniques, it is evident that Zn atoms can be
selectivity for methanol (Liu et al., 2020). A comparison between reduced on Cu nanoparticles, resulting in a detectable change in
the pure Cu(211) and the Zn-doped Cu(ZnCu(211)) surfaces the geometry and electronic structure of Cu due to Zn–Cu
showed differences in the reaction steps (Zheng et al., 2020). For bimetallic properties (Sanches et al., 2012). As a result, it is
the ZnCu(211) surface, the methanol formation pathway concluded that the Zn–Cu alloy is an active catalytic site. On
included the formation of CH3O instead of CH2OH species. the contrary, other studies found that reactions occur at the
The rate-limiting step over Cu(211) was the reaction, CO2 + H → atomic interface between ZnO and Cu. Thus, the presence of the
HCOO, whereas that over ZnCu(211) was HCOOH + H → ZnO–Cu interface and the synergy of Cu and ZnO are essential
H2COOH, which has been known as the main intermediate for for the production of methanol (Li et al., 2018).

FIGURE 7 | (A-C) Aberration-corrected HRTEM images of Cu particles in the commercially active Cu/ZnO/Al2O3 catalyst. (D) is a zoom-in of the marked area in
(C) (Behrens et al., 2012). Reproduced with permission from American Association for the Advancement of Science.
The active site of Cu catalysts can also exist in the form of Cu–Zn contact is necessary for the activity of the Cu/ZnO-based
other species. Recent studies have shown that stepped and catalysts.
ZnOx-decorated Cu surfaces are active sites of the industrial
catalysts (Studt et al., 2015). Both experimental and theoretical
investigations have found that decorated Cu stabilized by bulk Deactivation of Methanol Synthesis
defects and surface species participate in the hydrogenation of Catalysts
CO2 to methanol reaction (Behrens et al., 2012). The The deactivation of heterogeneous catalysts is a severe problem in
transmission electron microscopy study revealed the ZnO many reactions. Many studies have reported various deactivation
overlayer was formed on top of the Cu particles in the Cu/ mechanisms of the Cu-based catalyst in the literature; however,
ZnO/Al2O3 catalyst under reaction conditions that could create a the mechanism of deactivation is not entirely clear. One of the
metal oxide interface with catalytic activity (Figure 7). Evidence is major causes of catalysts deactivation is sintering. The sintering of
also available for the existence of the Zn–Cu bimetallic sites or catalytic materials particles results in a decrease in catalyst
ZnO–Cu interfacial sites (Kattel et al., 2017b). Over the ZnCu activity. Catalyst particles sinter in the early stages by a
bimetallic and ZnO/Cu model catalysts for methanol synthesis, it coalescence mechanism, which involves the migration and
was found that ZnCu surface oxidized in situ such that the surface coalescence of particles, while the Ostwald ripening
Zn transforms into ZnO, allowing ZnCu to form ZnO/Cu active mechanism is operative in the end phase of the process
surface in a synergistic interaction of Cu and ZnO. Cu–Zn alloy or (Bartholomew, 2001). The Ostwald ripening is caused by the
the Cu/ZnO interface has been proposed to generate the active surface diffusion of catalytic material and the higher
site responsible for the high methanol selectivity. Generally, as thermodynamic stability of larger particles (Fichtl et al., 2015).
summarized in this section, the active sites for the Cu–ZnO The initial and rapid deactivation is due to loss of surface area
catalysts can be grouped into the following categories: a) Cu when some of the finely dispersed Cu crystallites agglomerate
species (metallic or oxidized Cu species); b) Cu–ZnO interface; c) (Roberts et al., 1993; Twigg and Spencer, 2001). The later
defective Cu surface; d) Cu–Zn alloy; and e) ZnO decorated Cu. pathway, which is slow and approaches the steady-state, is
All these have led to the conclusion that the Cu species and/or caused by the surface coverage of some reaction products and

FIGURE 8 | (A) H2O impact on the Cu and ZnO particle size and on the Al2O3 surface. (B) Growth factor for Cu(dCu/dCu0) depending on the molar fraction of the
water and model results for 48 h (Prašnikar et al., 2019). Reproduced with permission from American Chemical Society.
intermediates, especially water, and carbonated species (Roberts of Cu, and the oxidation of the active Cu-phase (Clausen et al.,
et al., 1993). It was found that the cause of catalyst deactivation 1994; Omata et al., 2004). These can be explained by
was sintering of both Al2O3 and Cu with water due to the recrystallization and an enhanced tendency for sintering of the
decreasing Al2O3 surface, and Cu particle size with increasing Cu particles in the presence of water (Wu et al., 2001); however,
content of H2O (Prašnikar et al., 2019). this mechanism is not always true as no deactivation was
Figure 8A shows that all phases exhibit a reduction in surface observed by Omata et al. (2004) in their study in the presence
area (or increase of particle size) with an increasing amount of of water.
steam. The Cu particle growth was fitted to a coalescence model
for sintering (Figure 8B), which confirms coalescence as the Improvements to the Conventional
operating mechanism. The increased particle migration is due to Cu–ZnO–Al2O3 Catalyst
weak contact between the metal and support or increased surface Use of Promoters
diffusion of catalytic material (Prasň ikar et al., 2019). The To further increase the activity and stability of the Cu–ZnO or
structures of ZnO and Al2O3 species and metallic Cu can be Cu–ZnO–Al2O3 catalysts, modifiers such as K, Ba Zr, Ce, Mn, La,
stabilized to improve the catalyst lifetime, which can be Si, Pd, Ga, Mg, and Y were incorporated to promote the catalytic
accomplished by forming stable Cu interface with support performance (Iizuka et al., 1983; Inoue and Iizuka, 1986; Denize
material, and by stabilizing the dynamic nature of ZnO under et al., 1989; Toyir et al., 2009; Sanches et al., 2012; Zhang L. et al.,
working conditions using hydrophobic or hydrothermally stable 2012; Gao et al., 2013; Zhan et al., 2014; Gao et al., 2015; Zohour
materials. A promising approach is to confine the growth of Cu et al., 2016; Larmier et al., 2017; Xiao S. et al., 2017; Zhang F. et al.,
species in a porous oxide to stabilize and maximize Cu–support 2017; Hu et al., 2018). An effective promoter should be able to
interface (Chen et al., 2019). achieve large Cu surface area, high Cu dispersion, and to ease the
The water generated in the RWGS during CO2 reduction to reducibility of CuO to metallic Cu (Sanches et al., 2012).
methanol deactivates the catalyst, causing speciation of Cu active Modification to the basicity, methanol selectivity, CO2
phase and phase separation (Kung, 1992; Liang et al., 2019; conversion, and temperature and pressure have been
Prasň ikar et al., 2019). Sahibzada et al. observed a lower rate reportedly observed (Gao et al., 2013). A series of Cu/Zn/Al
of methanol production in the presence of water in the H2/CO2 catalysts promoted with Mn, La, Ce, Zr, and Y were synthesized
feed (Sahibzada et al., 1998). Another possible effect of water in by the co-precipitation method and tested for the CO2
the deactivation of the methanol synthesis catalyst is the hydrogenation to methanol, and effect of the promoters on the
crystallization of ZnO and Cu particles (Lunkenbein et al., physicochemical properties of the base catalysts was investigated
2016). Water produced can speed up the crystallization of (Gao et al., 2013). The results showed that the specific surface
particles, leading to deactivation observed for the Cu/ZnO/ area, Cu surface area, Cu dispersion and number of basic sites
ZrO2/Al2O3 catalyst. The inhibiting effect of water during CO2 increase in the order: Cu/Zn/Al < Cu/Zn/Al/Mn < Cu/Zn/Al/La
reduction to methanol was caused by the adsorption on and Cu/Zn/Al/Ce < Cu/Zn/Al/Zr < Cu/Zn/Al/Y, whereas the CH3OH
blocking of the active sites for CO2 hydrogenation (Liu et al., selectivity increases in the order of Cu/Zn/Al < Cu/Zn/Al/Mn <
1985). Water reacts with CO2, forming carbonate species that Cu/Zn/Al/La < Cu/Zn/Al/Ce < Cu/Zn/Al/Y < Cu/Zn/Al/Zr. The
have been proven to block the active sites for CO2 hydrogenation. Zr-modified Cu/Zn/Al catalyst exhibited the highest density and
The deactivation of Cu-based catalysts by water could also result proportion of strong basic sites. The addition of Mn, La, Ce, Zr,
from blocking of hydrogen adsorption sites, morphology changes and Y enhanced the production of methanol; however, the Y- and

Zr-modified Cu/Zn/Al catalysts exhibited the highest CO2 resulting catalysts as well as their catalytic activity in CO2
conversion and methanol selectivity, respectively (Gao et al., hydrogenation were studied. Analysis with various
2013). characterization techniques revealed modification of the
Lee et al. (2020) investigated the effect of adding Zr, Mg, and catalyst structures. A low content of SiO2 was more effective
Ga on the conventional Cu/ZnO/Al2O3. The incorporation of Zr for modifying the geometric structure. The addition of 1 wt%
enhanced the performance for methanol synthesis by improving SiO2 led to an increase in methanol synthesis activity (26%)
conversion and methanol yield, but the occurrence of intensified compared to the SiO2-free catalyst system. Phongamwong et al.
WGS reaction reduced CO2 conversion. On the other hand, the (2017) concluded that the addition of SiO2 to Cu/ZnO/ZrO2
addition of Ga and Mg further lowered catalytic performance improves methanol synthesis activity by increasing metallic Cu
(Table 2), attributed to reducibility difficulties and the increased surface area and surface basicity. Słoczyński et al. (2006) observed
crystalline size of Cu particles (Xiao et al., 2015). These catalysts an increase in the yield of methanol upon modification of Cu/
were evaluated using a feed composed of both CO and CO2. ZnO/ZrO2 catalyst with B, Ga, In, Gd, Y, Mn, and Mg oxides. The
The CuO–ZnO–Al2 catalysts modified with SiO2, TiO2, or addition of these elements also altered the textural and/or
SiO2–TiO2 exhibited better catalytic performances than the structural properties of the catalyst; Ga2O3 has been
CuO–ZnO–Al2O3 without any promoter. The conversion of particularly useful in promoting methanol yield. Saito et al.
CO2 and methanol yield increased when the promoters were (1996) developed a Cu/ZnO/ZrO2/Al2O3/SiO2 catalyst used for
added, and the maximum of CO2 conversion and methanol yield methanol synthesis operation in the bench plant. The catalyst was
were obtained over 2 wt% SiO2–TiO2/CuO–ZnO–Al2O3 catalyst very stable during long-term methanol synthesis (Saito et al.,
(Zhang et al., 2012). Both SiO2 and TiO2 eased the reduction and 1996; Toyir et al., 2009). The methanol production capacity of
dispersion of CuO, while SiO2–TiO2 made the reduction of CuO 50 kg d−1 of methanol over Cu/ZnO/ZrO2/Al2O3/SiO2 was also
slightly difficult. SiO2–TiO2 had the best performance than SiO2 successfully operated (Ushikoshi et al., 1998; Toyir et al., 2001;
or TiO2 as a result of synergistic interaction between SiO2 and Toyir et al., 2009).
TiO2, leading to a weaker acid strength and a higher acid
concentration on the surface of the catalyst. This resulted in Improvements in Catalyst Synthesis
weaker adsorption of CO2 but stronger adsorption of H2 and the A unique microstructure with a proper balance of Cu dispersion
dissociated H species (Zhang et al., 2012). The catalytic results and exposure of active Cu–ZnO interface sites at a high total Cu
revealed higher performance for the promoted CuO–ZnO–Al2O3 content is essential for achieving methanol selectivity (Behrens
catalysts. Maximum activity and methanol selectivity were and Schlögl, 2013). Thus, the synthesis method that guarantees
obtained for the catalyst promoted with SiO2–TiO2, giving the structure sensitivity of methanol synthesis over Cu surfaces is
CO2 conversion of 40.70% and methanol selectivity of 41.17% appropriate. Varying the specific activity of the active sites and/or
compared with the catalyst without a promoter (CO2 conversion the concentration of the sites can be a result of the deployed
of 15.81% and methanol selectivity of 23.31%) under similar synthesis method (Table 3). The ternary Cu-based catalysts are
reaction conditions of temperature 533 K, pressure 2.6°MPa, prepared by co-precipitation from a mixture of copper, zinc, and
H2:CO2 3:1, and space velocity 3,600 h−1. The introduction of aluminum nitrate using a carbonate as a precipitant (Behrens and
non-metallic ions (e.g., fluoride ion) can drastically promote the Schlögl, 2013; Behrens, 2015).
basicity of Cu/ZnO/Al2O3 and the adsorption of CO2 and The co-precipitation involves the simultaneous solubilization
increases the methanol selectivity (Dybbert et al., 2019). and solidification of copper and zinc precursors (usually nitrate
Although the CuO–ZnO–ZrO2 ternary catalysts have salts) in the presence of alkaline metal carbonates, forming binary
exhibited comparative activity with the commercial catalyst, precipitates under suitable conditions (Casey and Chapman,
the introduction of promoters such as SiO2, CeO2, Ga2O3, 1974; Kasatkin et al., 2007). The precipitate is aged, dried, and
TiO2 can further improve the catalytic performance (Zhang calcined in air to obtain the CuO/ZnO oxides. Finally, the catalyst
et al., 2012; Larmier et al., 2017; Phongamwong et al., 2017; is reduced under H2 atmosphere during which CuO is reduced to
Hu et al., 2018). A series of CuO–ZnO–ZrO2–SiO2 catalysts were metallic Cu. This method affords the study of hydrolysis of Cu2+
synthesized by the reverse co-precipitation of copper, zinc and and Zn2+ at different pH relevant to the catalyst preparation. Over
zirconium precursors with colloidal silica nanoparticles, and the the years, many researchers have investigated the synthesis
influence of silica content (0–5 wt%) on the properties of the parameters of the co-precipitation route, and have achieved a
TABLE 2 | Comparison of methanol synthesis performance between CZA and promoted CZA.
Catalyst Conversion (%) Selectivity (%) MeOH yield (%) CO:CO2 conversion ratio
CO CO2 CH4 DME (10−3) MeOH
CZA 17.9 7.0 1.51 0.13 98.49 16.0 2.57

CZA–Mg 9.2 2.8 0.73 1.54 99.27 8.2 3.24
CZA–Zr 20.9 2.3 0.21 3.90 99.79 18.1 8.98
CZA–Ga 14.7 4.5 0.43 3.22 99.57 13.1 3.27
Reaction conditions: 240°C and 30 bar; space velocity of 6,000 L/kgcat. h.

TABLE 3 | Catalytic activities of recently studied Cu-catalysts for methanol synthesis from CO2 hydrogenation in fixed bed reactors.
Catalyst Preparation T (°C) P (MPa) H2/CO2 WHSV CO2 CH3OH sel. STY gml−1 h−1 References
method (ml gcat−1 h−1) conv. (%)
(%)
CuO-ZnO-ZrO2 PR 503–543 5 3:1 4,600 h−1 23 66.8 0.21 Dong et al. (2016)
Cu/ZnO/Al2O3/ZrO2 CP 190 5.0 3:1 4,000 h−1 10.7 81.8 0.087 Xiao S. et al. (2017)
CuO-ZnO-ZrO2- CP 240 3.0 3:1 2,400 5.6 64.0 — Wang et al. (2018)
WO3
Cu-LaOx/SBA-15 IP 240 3.0 3:1 12,000 6.0 81.2 0.244 Chen et al. (2019)
Cu-In-Zr-O CP 250 25 — 18,000 1.48 79.7 0.087 Yao et al. (2019)
LDH30-Ga (33.5) CP 297 4.5 — 18,000 — 49 0.60 Li et al. (2018)
Cu-ZnO-ZrO2/LDH US-CP 250 3 3:1 2,000 h−1 4.9 78.3 0.365 Fang et al. (2019)
Cu/AlCeO CP 260 3 3:1 14,400 ∼17 85 11.9a Li et al. (2020)
ZnCuCe RCP 240 3 3:1 8.8 N L g−1 h−1 — — 0.69a Bonura et al. (2011)
CuCeTiOx CP 235 3 3:1 2,000 — — 0.47a Chang et al. (2017)
1Pd-10Cu/CeO2 IP 273 3 3:1 — 17.8 23.7 0.9a Choi et al. (2017)
10Cu/CeO2 IP 273 3 3:1 — 6.4 42.8 — Choi et al. (2017)
15 wt% CuCu/Al2O3 IP 200–280 4 3:1 6,000 16.4 59 — Li et al. (2019)
15 wt% CuCu/ IP 200–280 4 3:1 6,000 22.5 94 — Li et al. (2019)
AlCeO
Cu/La2O2CO3-R DP 280 3.0 3:1 12,000 ml 5.6 92.5 110.2b Chen et al. (2018)
Cu/ZrO2 IWP 493–553 3 3:1 — 13 76.4 — Witoon et al. (2016)
CuZn@UiO-bpy DSM 523 4 — — 17.4 85.6 — An et al. (2017)
CP, co-precipitation; IP, impregnation; RCP, reversed co-precipitation; DP, deposition precipitation; DSM, double solvent method; PR, precipitation reduction; US-CP, ultrasonic assisted
co-precipitation. “a” is in mmol h−1 g−1, “b” is in molmolCu−1 h−1.
high degree of optimization, usually by empirically adjusting the a reducing agent is added, and the resulting slurry is further aged
synthesis conditions (Li and Inui, 1996; Baltes et al., 2008; at a specific temperature for sufficient time, followed by filtration
Behrens et al., 2011). Even so, further improvement of this and washing, drying, and calcination. Compared with the
catalyst is still needed. The best catalyst is usually obtained by conventional co-precipitation method, catalysts with smaller
co-precipitation with Na2CO3 solution at a constant pH 6 or 7 Cu particles are much more easily obtained by using the
and at temperatures ranging from 60–70°C (Li and Inui, 1996; precipitation–reduction method. By this method, the viewpoint
Baltes et al., 2008). The initial precipitate, which is made of that both Cu+ and Cu0 species contributed to the activity of CO2
hydroxycarbonates (Mota et al., 2018; Ghosh et al., 2019), is aged hydrogenation to methanol is accepted (Dong et al., 2016).
for around 30 min to a few hours (Li and Inui, 1996; Kniep et al., The sol–gel (SG) method is another way to prepare mixed
2004; Behrens et al., 2011) followed by washing, drying, and oxides, especially for M–CeTiOx systems (Chen et al., 2014;
calcination at temperatures around 600–700 K to form Matějová et al., 2014; Bo et al., 2016). In a study utilizing
CuO–ZnO species with some carbonate residues, responsible CuCeTiOx as the catalyst, Ce and Ti ions were hydrolyzed to
for the porous microstructure and surface area. The following form the framework at low pH during the sol–gel transformation.
further reduction of the obtained phases yields the active catalyst Then the Cu species were solidified through evaporation of the
phase—usually metallic Cu nanoparticles, although other species solvents. These steps can lead to elemental distribution that
of Cu, including Cu+, ZnO decorated Cu, or partially reduced differs between the bulk and surface, resulting in catalysts with
ZnOx, have been reported (Schumann et al., 2016; Mota et al., varying composition in CuCeTiOx on their catalytic properties.
2018). The conditions during the precipitation and aging stages, By this method, a catalyst composite (CuCeTiOx–SG) with the
as well as residual Na+ ions in the system and elemental composition (30%CuO35%CeO235%TiO2) was prepared and
composition (Cu:Zn—65:25), are crucial for the properties of compared with the co-precipitation method derived catalyst
the final catalyst (Zhao et al., 2011; Behrens, 2016; Kondrat et al., (CuCeTiOx–CP). The preparation methods show an important
2017; Mota et al., 2018; Ghosh et al., 2019; Guil-López et al., influence on catalytic performance (Figure 9). The
2019b). CuCeTiOx–CP catalyst showed a higher CO2 conversion than
To further improve the microstructural and porous properties CuCeTiOx–SG. However, the CuCeTiOx–SG catalyst showed a
of the methanol synthesis catalysts, other synthesis methods have higher selectivity to methanol than CuCeTiOx–CP at the same
also been studied (Guo et al., 2009; Natesakhawat et al., 2012; CO2 conversion (Chang et al., 2017). Also, Cu/ZnO catalysts were
Dong et al., 2016; Dasireddy and Likozar, 2019). The prepared using three different methods (co-precipitation,
precipitation–reduction method involves first the co- sequential precipitation, and homogeneous precipitation). The
precipitation step, followed by a reduction in the second step studied preparation methods influenced the surface area of the
by a reducing agent such as NaBH4. Typically, a solution of metal Cu-based catalysts, which directly impact their catalytic activities.
nitrates and a solution of Na2CO3 or NaOH precipitant are added The different preparation methods resulted in various structural
dropwise to deionized water simultaneously under stirring at a changes in the aurichalcite precursors that were transformed into
temperature and a constant pH (∼7.0) during precipitation. Then the final catalyst. From the catalytic evaluation results, it was

support (Liu et al., 2003). It can also alter the surface properties,
such as the basicity/acidity and adsorption characteristics of the
catalyst. Over the years, various support materials (Figure 10) for
the Cu-based catalysts have been studied (Weigel et al., 1996;
Tang et al., 2009; Halder et al., 2018; Lin et al., 2019; Yang B. et al.,
2019). Metal oxides are the most common supports for the
methanol synthesis catalysts, and their properties greatly affect
the catalyst activity in several ways. The non-metallic supports,
including metal organic frameworks (MOFs), porous silica
materials, layered double hydroxides (LDHs), carbon materials,
metal carbides, graphene, and porous polymers, have also been
investigated (Rodriguez et al., 2015; Wang et al., 2015; Díez-
Ramírez et al., 2016; Fan and Wu, 2016; Liu et al., 2016; Din et al.,
2018; Sun et al., 2018; Witoon et al., 2018; Mureddu et al., 2019).
We discuss the supported Cu-catalysts in a different light from
the above discussed ternary catalysts, noting that the commercial
methanol synthesis (Cu/ZnO/Al2O3) catalyst, for example, is not
a “supported catalyst.” Supported catalysts are generally prepared
by the incipient or wet impregnation methods. Of the metal oxide
FIGURE 9 | Selectivity-conversion relationships of CuCeTiOx–SG and supports investigated in the literature for Cu catalysts, ZnO,
CuCeTiOx–CP (Chang et al., 2017). Reproduced with permission from ZrO2, Al2O3, Ga2O3, SiO2, and CeO2 have drawn the most
Elsevier.
attention in methanol synthesis. These metal oxides have also
been explored as promoters to the Cu-based methanol synthesis
catalysts (Toyir et al., 2009; Zhan et al., 2014; Hu et al., 2018).
concluded that the preparation methods had noticeable effects on
the dispersion of Cu particles and the catalyst structure. These Cu/ZnO Catalysts—ZnO as a Support and Co-Catalyst
effects were more pronounced for the catalysts prepared by The Cu/ZnO-based catalysts for the production of methanol from
homogeneous precipitation and co-precipitation (Sanches CO or CO2 or a mixture of both have been in existence and
et al., 2012). The hydrogenation of CO2 was conducted over a applied for nearly six decades. Before the standardization of the
series of Cu/ZnO/Al2O3 catalysts prepared by different synthesis ternary Cu/ZnO/Al2O3 catalyst, Cu/ZnO was used as an active
methods (co-precipitation, ultrasound-assisted, sol–gel, and catalyst for the hydrogenation of CO. The Cu/ZnO catalyst is
solid-state). The characterization and catalytic performance typically prepared by the impregnation or co-precipitation
showed that the preparation strategy had a strong influence on method (Lei et al., 2015; Lunkenbein et al., 2015).
them (Dasireddy and Likozar, 2019). The ultrasonic synthesis In the Cu/ZnO catalyst, ZnO plays several important roles.
route provided catalysts with increased basic active sites and The presence of ZnO improves the dispersion and stability of Cu
significant methanol selectivity in comparison with that prepared (Bonura et al., 2011); also, the lattice oxygen vacancies and the
from the conventional co-precipitation route. This method also electron pairs in ZnO are active for methanol synthesis. These
improved the dispersion of metallic Cu particles, which altered functions lead to a more active Cu phase and larger surface area,
the intrinsic reactivity of CuO–ZnO. Since the methanol thus preventing agglomeration of Cu particles (Arena et al.,
production rate was proportional to the ratio of Cu+/Cu0, it 2007). The active Cu surface area of Cu/ZnO catalysts
was concluded that the presence of high levels of Cu+ species is correlated with the degree of Zn incorporated into the
essential for high and low selectivity to methanol and CO, precursor phase. The metallic copper surface areas in the
respectively (Dasireddy and Likozar, 2019). reduced catalysts could be determined by the N2O titration
technique (Guo et al., 2009; Guo et al., 2011).
Synergism between Cu and ZnO reportedly exists upon the
OTHER Cu-CONTAINING CATALYSTS incorporation of ZnO into the Cu based catalysts (Kanai et al.,
1996; Chen et al., 1999), and this resulted in the electronic
Supported and Promoted Cu Catalysts interaction between Cu and Zn(2−δ)+ which created active sites
Until the present, Cu-based catalysts present the most desirable like Cu+–O–Zn (Kanai et al., 1996). The catalytic activity of a Zn-
properties for the direct CO2 hydrogenation to methanol at the doped Cu(111) surface was much higher than that of the pure
industrial scale, thus proper to refer it as the methanol synthesis Cu(111) as a result that ZnO modified the electronic properties of
catalyst. However, the low conversion of CO2 below equilibrium Cu sites by an electron exchange and interaction with Cu particles
and poor selectivity to methanol have necessitated further (Twigg and Spencer, 2001; Koitaya et al., 2019). The role of ZnO
improvement of these catalysts. Although the methanol in the reduction of Cu by H2 was studied by Fierro et al. (1996).
synthesis catalyst is not a classical supported catalyst, suitable The temperature programmed reduction investigation of the
support not only provides a proper catalyst configuration but CuO–ZnO catalyst synthesized by the co-precipitation method
modify the interactions between the active component and the revealed ZnO promoted the reducibility of CuO. It is believed that

FIGURE 10 | Classification of supports for Cu-based methanol synthesis catalysts.
ZnO acts as a reservoir of atomic hydrogen and provides it for the Cu/ZrO2 and Cu/ZnO/ZrO2
CO2 hydrogenation on the Cu surface, or as a binding site ZrO2 is a good support due to its hydrophobicity, and surface
facilitating the adsorption of H2 species and CO2 via a basicity. Besides, its high thermal stability is superior to Al2O3
spillover (Chen et al., 1999). The atomic hydrogen then under reducing and oxidizing atmospheres (Li and Chen, 2019).
transfers from the Cu onto the ZnO surface and gradually The catalytic activity of ZrO2 as a support is superior to that of
hydrogenates the adsorbed CO2 to methanol (Sun et al., 2003; Al2O3, SiO2, or ZnO (Li and Chen, 2019). The addition of ZrO2
Dang et al., 2018). has been reported to improve the surface area of Cu species and
ZnO, as a support, is also suggested to be an active can alter the Cu+/Cu0 ratio in the surface (Fisher et al., 1997;
component in the methanol synthesis catalyst (Fujitani and Słoczyński et al., 2003). CuO can be uniformly dispersed on the
Nakamura, 2000; Choi et al., 2001). In a physical mixture of ZrO2 surface, forming an interface favorable for the methanol
Cu/SiO2 and ZnO/SiO2, it was found that Zn species could synthesis reaction (Li and Chen, 2019).
migrate to the Cu surface upon reduction with H2, creating ZrO2 exists in different crystal structural phases
Cu–Zn active sites on the Cu surface (Choi et al., 2001). The (polymorphs)–amorphous (a)-ZrO2 and tetragonal (t)-ZrO2
formate species were firstly formed on both Cu and ZnO and monoclinic (m)-ZrO2 (Figures 11A–C). The a-ZrO2 and
phases, and secondly, they were further hydrogenated to t-ZrO2 transform to m-ZrO2 at high temperatures. The
form methoxides located on the ZnO (Lei et al., 2015). calcination of Zr(OH)4 at temperatures greater than 400°C
Thus, ZnO is actively involved in the synthesis of methanol transforms it mainly to m-ZrO2, so Cu species are easily
by creating more stable reaction intermediates, which readily incorporated into a-ZrO2 (Tada et al., 2018). The effects of
convert to methanol on further hydrogenation (Chen et al., ZrO2 polymorphs, including -a, -t and -m phases on the
1999). The absorption strength of reaction intermediates like structure of Cu, Cu–ZrO2 interaction and
HCO, H2CO, and H3CO can be enhanced by the incorporation adsorption–desorption of H2 and CO2 were systematically
of ZnO, thus decreasing the energy barriers. Consequently, the investigated, and the catalytic performance of the catalysts,
formation rate of methanol is increased (Behrens et al., 2012). Cu/a-ZrO2, Cu/t-ZrO2, and Cu/m-ZrO2 catalysts explored
Sulfur and chlorine species are considered poisons for Cu-based (Witoon et al., 2016). By a variety of analytical techniques, the
methanol synthesis catalysts, and the addition of ZnO to the catalyst Cu surface area followed the trend: Cu/a-ZrO2 > Cu/t-ZrO2 > Cu/
irreversibly scavenges sulfur or chlorine as ZnS or ZnCl2, m-ZrO2. The increase in the yield of methanol is correlated with
respectively, militating against deactivation of the catalyst. On the the increase in Cu surface area, thus the Cu/a-ZrO2 exhibited the
negative, ZnO is a basic oxide that can neutralize the acidity of Al2O3 highest methanol yield. However, the methanol turn over
in the commercial catalyst, preventing the transformation of CO2 to frequency (TOFMethanol) of Cu/t-ZrO2 was higher than those
methanol and promoting the agglomeration of active Cu particles of Cu/a-ZrO2 and Cu/m-ZrO2. In general, the high
(Twigg and Spencer, 2001). TOFMethanol is due to a strong Cu–ZrO2 interaction and a high

FIGURE 11 | TEM of (A) Cu/a-ZrO2, (B) Cu/t-ZrO2 and (C) Cu/m-ZrO2 catalysts (Witoon et al., 2016). (D) The selectivity to methanol as a function CO2 conversion
over FSP-made CuO/ZrO2 and commercial CuO/ZnO/Al2O3 at different contact times. (E) The selectivity to CO as a function CO2 conversion over FSP-made CuO/ZrO2
and commercial CuO/ZnO/Al2O3 at different contact times. The contact time of commercial CuO/ZnO/Al2O3 and CuO/ZrO2 prepared at P 1–10 ml min−1 were
60–1,500 gcat s LSTP−1 and 600–1,500 gcat s LSTP−1 , respectively. For CuO/ZrO2 prepared at P 3 ml min−1, the contact time at 200–500 gcat s LSTP−1 was also
examined (Fujiwara et al., 2019). Reproduced with permission from John Wiley and Sons.
surface concentration of atomic hydrogen to CO2 (Witoon et al., surface to stabilize small Cu particles and formed interfacial
2016). A highly loaded CuO (65.2 wt%) on ZrO2 support Cu-ZrO2 active sites. The crystallite size and crystallinity of
prepared by flame spray pyrolysis (FSP), showed a good t-ZrO2 could be controlled by varying the precursor feed rate
catalyst activity compared with a commercial catalyst (Fujiwara et al., 2019).
(Figure 11D). The production rate of methanol by CO2 Cu/ZnO/ZrO2 catalyst is more resistant to water deactivation
hydrogenation and the selectivity to methanol over FSP-made due to the hydrophobic nature of ZrO2 (Li and Chen, 2019). The
CuO/ZrO2 catalysts were obviously higher compared with those Cu/ZnO/ZrO2 catalyst contains ZrO2 instead of Al2O3 and
of commercial CuO/ZnO/Al2O3 (Fujiwara et al., 2019). For all exhibits high performance in methanol synthesis from CO2
catalysts, the CO2 conversion increased, with increasing contact hydrogenation. Compared with Al2O3, the impressive
time, while the selectivity to methanol decreased, but the performance is linked with the possibility of interactions
selectivity to CO increased (Figure 11E). The activity and between Cu-species and ZnO–ZrO2 oxides (Li and Chen,
selectivity of the prepared catalysts depended on the spray 2019). Moreover, ZrO2 exhibits a weaker hydrophilic character
pyrolysis rate. They were higher at low feed rates than either Al2O3 or CeO2, which promotes the desorption of
(2–3 ml min−1) than those of the catalysts prepared at higher formed water, and benefits the formation of methanol (Arena
feed rates (5–10 ml min−1). The former feed rate led to the et al., 2007). The presence of ZrO2 in the Cu/ZnO catalysts could
formation of smaller ZrO2 particles, which provided more lower the Cu coordination with oxygen and increase the Cu–O

distance, as studied by the extended X-ray absorption fine method. Characterization results revealed CuO–ZnO–ZrO2
structure. This indicates the presence of defective Cu nanoparticles were uniformly dispersed and attached to the
structures resulting from the strong Cu–support interaction surface of the LDH, which improved the specific surface area
(Yang et al., 2006). Consequently, the Cu/ZnO catalyst and Cu dispersion compared with a reference catalyst without the
containing ZrO2 exhibited much higher activity and selectivity support. The catalyst showed a high methanol selectivity of 78.3%
toward methanol production than the Cu/ZnO catalyst. While it at 250°C under a pressure of 3.0 MPa, which is about 50% higher
is a proven fact that the impressive performance of the Cu/ZnO/ than conventional Cu-based catalysts reported in the literature.
ZrO2 catalyst arises from the structural and surface modifications Raising the temperature of the CuO-ZnO–ZrO2–LDH catalyst
of the Cu/ZnO by ZrO2, it is important also to note that the slightly decreased the conversion. Very promising is that the
crystallinity of ZrO2 strongly affects the Cu–ZrO2 interaction activity of the can be recovered by reduction with H2 (Fang et al.,
(Baiker et al., 1993). Thus, the co-presence of amorphous ZrO2 2019).
and crystalline Cu/ZnO enhances the synergistic effect of Cu/
ZnO/ZrO2, facilitating the dissociative adsorption of CO2 and the Cu/CeO2 and Cu/ZnO/CeO2
selective conversion of CO2 to methanol (Słoczyński et al., 2004). CeO2 has also been studied as a support or co-support for the
Both experiments and DFT calculations using Cu–ZnO–ZrO2 methanol synthesis catalysts via the CO2 hydrogenation route
have provided evidence on the separate functions of the Cu (Hu et al., 1991; Wang et al., 2016; Chang et al., 2017; Li et al.,
species and ZnO–ZrO2 interface in the catalytic conversion of 2019). It has a strong adsorption affinity for CO2 due to its strong
CO2 to methanol by hydrogenation (Wang Y. et al., 2019). The basicity and oxygen vacancies. The latter can improve the
catalytic evaluation at 220°C under 3.0 MPa showed very high dispersion of Cu particles and promote the spillover of atomic
activity (CO2 conversion of 18.2% and selectivity to methanol of hydrogen, which benefits the production of methanol (Chang
80.2%). The binary oxides of ZnO–ZrO2 showed a higher ability et al., 2017; Li et al., 2020); also, a negative influence on the surface
for CO2 adsorption and the hydrogenation of carbonate species to area of catalysts with ceria was observed (Bonura et al., 2011). In
formate and methoxy intermediates than the Cu–ZnO or 2014, Rodriguez and co-workers published a study that
Cu–ZrO2 systems. Cu/ZrO2 and Cu/ZnO catalysts synthesized demonstrated the combination of Cu metal and oxide sites in
by various methods show different catalytic performance. While the Cu–CeO2 interface affords favorable reaction pathways for
Cu/ZrO2 is more effective for the selective formation of methanol the conversion of CO2 to methanol (Graciani et al., 2014). By
from CO2, higher activity for CO2 conversion is associated with theoretical methods, the CO2 hydrogenation over a CeOx/
Cu/ZnO (Li and Chen, 2019). Cu(111) surface was demonstrated. The complementary
So far, efforts have been made to enhance the catalytic surface analysis with XPS indicated Ce2O3/Cu(111) as the
performance of CuO–ZnO–ZrO2 catalysts further. active phase of the catalyst (Figure 12A). This inverse catalyst
Modification of CuO–ZnO–ZrO2 catalysts with various was much better for methanol synthesis than either Cu(111) or
additives is a feasible option to alter the physicochemical Cu/ZnO(0001) (Figure 12B). It was also found that the catalytic
properties of the catalysts, improving the methanol synthesis activity of CeOx/Cu(111) was of an order higher than those of
activity and preventing the Cu sintering. The CuO–ZnO–ZrO2 Cu(111) or ZnO/Cu(111) (Senanayake et al., 2016). The
catalysts supported on graphene oxide (GO) gave a higher STY in activation energy for the conversion of CO2 to methanol
comparison with the GO-free catalyst due to the increased active decreased from 25 kcal/mol on Cu(111) to 16 and 13 kcal/mol
sites for the adsorption of CO2 and H2. The methanol selectivity on ZnO/Cu(111) and CeOx/Cu(111), respectively. The analysis of
of GO supported catalysts was above that of the unsupported the surface of the CeOx–Cu(111) interface by ambient
catalyst. Specifically, the highest methanol selectivity of 75.88% pressure—XPS and ambient pressure infrared reflection
was obtained over the CuO–ZnO–ZrO2 catalyst prepared with absorption spectroscopy revealed the formation of formates
1 wt% GO (CZZ-1GO) at 200°C and 20 bars. This performance and carboxylates (CO2δ−) during the reaction. These results
was attributed to a promoting effect of GO nanosheet serving as a demonstrate CeOx–Cu as an active catalyst riched in Ce3+
bridge between metal oxides, which enhanced a hydrogen sites, which stabilized the CO2δ− species, an essential
spillover from the Cu surface to the carbon-containing species intermediate for the production of methanol (Graciani et al.,
adsorbed on the metal oxide particles (Witoon et al., 2018). The 2014).
mixed oxides of Cr, Mo, or W and CuO–ZnO–ZrO2 prepared by In ceria-containing Cu–ZnO oxide catalysts, the presence of
the co-precipitation method showed better activity for methanol CeO2 promoted the surface activity of the Cu–ZnO system,
synthesis. The results indicated an improved methanol selectivity although negatively influenced the catalyst texture and metal
and yield of the CuO–ZnO–ZrO2 catalyst upon addition of MoO3 surface area in comparison to ZrO2 (Bonura et al., 2011). As
or WO3 but slightly dropped when doped with Cr2O3. The discussed earlier, CeOx can improve the dispersion of Cu particles
improved methanol yield over these catalysts can be attributed and promote the spillover of atomic hydrogen. On the other
to the differences in their Brunauer-Emmett-Teller surface areas hand, ZnO can improve the dispersion of the CeOx nanoparticles.
and adsorption capacities for CO2. It was also found that the ratio Thus, the ternary CuZnCeOx exhibited higher performance than
of surface Zn to Cu, as well as the fraction of strong basic sites, the binary CuZnOx catalyst (Shi et al., 2019); but had relatively
improved the methanol selectivity (Wang G. et al., 2019). A very high selectivity toward CO (Hu et al., 2018). A CuZnCeOx
layered double hydroxide (Mg-Al LDH) was used as a carrier for catalyst prepared by a parallel flow co-precipitation technique
Cu–ZnO–ZrO2 catalyst synthesized by the co-precipitation was evaluated in the hydrogenation of CO2 to methanol and CO.

FIGURE 12 | (A) Ce 3d XPS spectra collected before and after performing the hydrogenation of CO2 on a CeOx/Cu(111) surface. Reaction conditions: catalyst was
exposed to 0.5 atm of CO2 and 4.5 atm of H2, at 500 K, for 15 min. (B) Arrhenius plot for methanol synthesis on Cu(111); Cu/ZnO(0001), 0.2 ML of Cu; CeOx/Cu(111),
Cu(111) surface covered 20% by ceria; and Cu/CeOx/TiO2(110), 0.1 ML of Cu on a TiO2(110) surface pre-covered 15% with ceria. Reaction conditions: catalysts were
exposed to 0.5 atm of CO2 and 4.5 atm of H2 (Graciani et al., 2014). Reproduced with permission from American Association for the Advancement of Science.
The amount of CeOx in the catalyst controlled the selectivity of properties (Słoczyński et al., 2003). Zander et al. (2013) found
the products. Characterization results revealed a significant that the methanol production rate from synthesis gas by Cu/
synergistic effect between Cu and metal oxides (ZnO and/or MgO/ZnO was higher than that by Cu/ZnO, ascribed to the
CeOx) in the catalyst. Cu played a critical role in the activation of higher Cu dispersion caused by Mg addition. Recently, the
H2, and CeOx strongly adsorbed CO2, improved the dispersion of influence of Mg addition on the performance of Cu/Zn/Al/Mg
Cu nanoparticles, and promoted the spillover of atomic hydrogen methanol synthesis catalyst prepared by co-precipitation and
(Shi et al., 2019). The results of these studies suggest that CeO2 in fractional-precipitation methods was investigated. In a series
Cu–ZnO catalysts can offer a viable way to produce methanol or on Cu/Zn/Al/Mg catalysts obtained, the preparation method
CO from CO2 hydrogenation selectively. The selectivity toward was found to have a significant effect on the properties as well
the products (methanol and CO) can be regulated by changing as the catalytic performance. The co-precipitation method
the reaction conditions, catalyst formulation, or preparation resulted in catalysts with higher Brunauer-Emmett-Teller
method (Hu et al., 2018). For example, the CuZnCeTiOx surface area and Cu dispersion, but with decreased catalytic
showed significantly enhanced activity in comparison with the activity. On the other hand, the fractional precipitation
CuCeTiOx catalyst and was twice more active than the facilitated the Cu substitution by Zn in the sub-carbonate
commercial catalyst as measured by TOF values. However, the precursor, which cushioned the effect resulting from the
stability is still not good enough, with high selectivity toward CO former method, catalytically performed better than those
(Chang et al., 2019). prepared by the co-precipitation method (Zhang et al., 2017).
In these catalysts, there was the formation of Mg–Al hydrotalcite
Other Metal Oxides Employed as Promoters or unfavorable for methanol production. Moreover, the formation
Additives of CuAl2O4 and MgAl2O4 spinel phases in Cu/MgO/Al2O3
Magnesium Oxide (MgO) catalysts were observed (Dasireddy et al., 2018).
Mg-containing Cu/Zn/Al industrial catalysts for methanol
synthesis were developed in the 1990s (Bozzano and Manenti, Gallium Oxide (Ga2O3)
2016). The effect of metal oxides on the Cu/ZnO/Al2O3 catalyst Ga2O3 is reported to increase the activity per unit Cu surface area
from co-precipitation was investigated. MgO showed a negative of methanol synthesis catalyst (Toyir et al., 2009). Ga3+ can
impact on the catalytic activity, but a positive effect on the modify the hydroxycarbonate precursors during the catalyst
stability of the catalyst (Meshkini et al., 2010). It was synthesis to form the precursors with hydrotalcite structure
concluded that Mg affects the activity of the Cu/Zn/Zr catalyst (An et al., 2007). The catalysts derived from the Ga-modified
for methanol synthesis from CO2 by improving the adsorption hydrotalcite showed improvement in the dispersion of Cu

particles and the formation of active Cu–ZnOx sites, which 1995; Grandjean et al., 2011). Micro-spherical SiO2 prepared by
enhanced the efficiency of Cu–ZnGa catalyst system for CO2 the spray-drying method was investigated as support for Cu/
hydrogenation to methanol (An et al., 2007). One reason for this ZnO-based catalysts synthesized with different percentages of Cu
improvement is that the hydrotalcite derived catalysts could and ZnO by the ammonia-evaporation method (Jiang et al.,
maintain their morphology in ultrafine layers even after heat 2018). The results revealed the deposition of Cu and Zn ions
treatment at high temperatures, which transformed the phase to in the pores of the SiO2 and high distribution, which depended on
amorphous (Guil-López et al., 2019a). The amorphous phase is the metal loadings. The specific surface area of the catalysts
more accessible with better dispersed metallic Cu crystal, and increased with increasing loadings to a critical amount due to
with a large surface area decorated with a small amount of Zn the formation of the porous structure of SiO2. Beyond this
atoms. CuZnGa catalysts derived from the LDH precursor gave loading, CO2 conversion slightly reduced due to the blocking
good catalytic activity in CO2 hydrogenation to methanol. of the pores of the support. The combination of X-ray diffraction,
LDH30Ga (Cu: 33.5 wt%) yielded STY of 0.59 gml−1 h−1, higher XPS, X-ray Auger electron spectroscopy and CO-adsorption in
than the commercial JM-HiFUEL (50 wt% Cu/ZnO/Al2O3) with situ Fourier-transform infrared spectroscopy analysis
a STY of 0.38 gml−1 h−1 after 25 h on stream at 290°C and 4.5 MPa demonstrated that SiO2 facilitated the formation of both Cu+
(Li et al., 2018). However, there is an obvious requirement of high and Cu0 species on the surface of the reduced Cu/ZnO/SiO2
temperature and pressure for realizing the high activity. catalysts (Jiang et al., 2018). Other examples of the SiO2
supported catalysts for methanol synthesis can be found in the
Titanium Oxide (TiO2) literature (Studt et al., 2014; Fiordaliso et al., 2015; Phongamwong
The incorporation of titanium nanotubes (TNTs) support into et al., 2017; Jiang et al., 2018).
CuO–ZnO–CeO2 catalysts can promote CuO reducibility, Carbon materials possess a very large surface area, high
improve metallic Cu dispersion and increase the specific thermal stability, high hydrogen uptake, mechanical strength,
surface area. The CuO–ZnO–CeO2/TNTs composite catalysts and facilitate H2 dissociation. All these properties contribute to
with different TNTs contents prepared by a the increasing rate of CO2 hydrogenation to methanol at a lower
deposition–precipitation method gave high CO2 conversion temperature with high methanol selectivity than the equilibrium
and methanol selectivity. The selectivity was positively when used as supports, but unsuitable for a commercial
correlated with the number of basic sites, whereas the CO2 application due to low conversion. GO as support for the
conversion was a function of the specific surface area of Cu. Cu–ZnO catalysts was studied for the CO2 hydrogenation to
The catalyst prepared with 10 wt% TNTs (CuO–ZnO–CeO2/10 methanol. The results found that 10 wt% CuZn/rGO catalyst
TNTs) possessed high metallic Cu surface area, high CO2 exhibited a good activity for the CO2 hydrogenation, achieving
adsorption capacity and a large number of basic sites, 26 % CO2 conversion, methanol selectivity of 51%, and 424 ± 18
translating into excellent catalytic performance (methanol mgmethanol at 250°C under 15 bar after 5 h on a stream
selectivity of 59.8%, CO2 conversion of 23.3% and STY of (Deerattrakul et al., 2016). With MOF as a support or
9.33 mmolMeOH h−1 gcat−1 at 260°C, H2/CO2 of 3, gas hourly component of catalyst, very high methanol selectivity (up to
space velocity (GHSV) of 7,500 ml g−1 h−1) (Shi et al., 2019). 100%) was reported (Rungtaweevoranit et al., 2016; An et al.,
2017; Hu et al., 2019). Still, its application suffers from serious
Non-Metal Oxide Supports challenges that are undesirable for industrial applications—low
In general, SiO2 possesses large surface area and porosity, high conversion and instability at high temperatures. GO as support
thermal stability, and good dispersion capacity but weak for the Cu–ZnO catalysts was studied for the CO2 hydrogenation
interaction with metals (Nitta et al., 1994; Sugawa et al., 1995). to methanol. The results found that 10 wt% CuZn/rGO catalyst
However, the presence of steam at high temperatures weakens its exhibited a good activity for the CO2 hydrogenation, achieving
thermal stability due to its transformation to Si(OH)2. During the 26% CO2 conversion, methanol selectivity of 51%, and 424 ±
methanol synthesis from CO2, the stability of Cu/ZnO-based 18 mgmethanol at 250°C under 15 bar after 5 h on a stream
catalysts was improved by incorporating a small amount of silica, (Deerattrakul et al., 2016).
which suppressed the crystallization of ZnO in the catalysts The promotion of the Cu/Zn catalyst supported on SBA-15
(Toyir et al., 2009). Cu supported on high-purity silica was (CZ/SBA-15) with transition metals (Cr, Mn, Fe, Co, Ni) revealed
nearly inactive in methanol synthesis (Fujita et al., 1995; Gotti impressive catalytic performances of the modified catalysts. The
and Prins, 1998), and the selectivity toward methanol was low. In Mn promoted catalyst (Mn-CZ/SBA-15) was the most active due
another study, the Cu/SiO2 catalyst exhibited a low selectivity to to the presence of small copper crystallites and strong interaction
methanol (Sugawa et al., 1995). A 10 wt% Cu/SiO2 exhibited between CuO and other oxide species in the catalyst. At a reaction
higher methanol formation rate (2.1%) than 10 wt% Pd/SiO2 temperature of 180°C under 4.0 MPa, WHSV of 60 L/gcat. h and
(0.3%) (Kunkes et al., 2015). Some experimental results have H2/CO2 of 3, the catalyst presented a methanol yield of 10.4%,
reported higher activity and relatively better selectivity for CO2 conversion of 10.5% and a methanol selectivity of 98.6%
methanol over silica-based than ZnO-based catalysts, due to (Koh et al., 2019).
the higher surface area of the former (Nitta et al., 1994). SiO2
can function better as a support for Cu-catalyst for methanol Bimetallic Cu-Based Catalysts
synthesis in the presence of other metal oxides as a promoter or Bimetallic Cu-based catalysts also have good catalytic
co-support, or for the copper bimetallic catalysts (Sugawa et al., performances in the direct CO2 hydrogenation to methanol.

Noble metals such as Pd have proper properties for activating RENEWABLE ENERGY STORAGE IN AND
hydrogen, which could spread through a hydrogen spillover NEW PROCESSES FOR METHANOL
mechanism to the neighboring catalytic sites (Melián-Cabrera
et al., 2002; Ponce and Klabunde, 2005). The hydrogen spillover The chemical recycling of CO2 to renewable fuels and commodity
can result in a catalyst surface with a highly reduced state that chemicals represents an economic aspect of the CO2 mitigation.
could facilitate the hydrogenation process. In the methanol Methanol, a primary liquid product derived from the
synthesis application, Pd is reported with good catalyst hydrogenation of CO2, aside being used directly as a fuel, can
improvement roles. It is suggested that Pd enhances the be efficiently processed into other products of high societal
activity of Cu sites. Upon the addition of Pd, the Cu needs—DME, ethylene, propylene, gasoline, and other
dispersion and surface concentration on the catalyst surface products currently obtained from petroleum and natural gas.
were improved. The Cu dispersion and the surface Cu The combustion of methanol and its derivatives will release CO2,
concentration increased with an increase in the amount of loaded which can be recycled back effectively, forming a carbon loop
Pd to a certain level. It was explained that the interaction between Pd (Goeppert et al., 2014). Biomass is a form of recycled CO2 that can
and Cu decreased the Cu–Cu bond distance due to the strong electronic be converted into DME, for example. Since CO2 hydrogenation is
perturbation, resulting in well-dispersed Cu species (Kugai et al., 2016). carried out using hydrogen produced from renewable energy
In this way, the aggregation or agglomeration of Cu particles was sources—electrical, wind, hydro or solar energy (Goeppert et al.,
suppressed due to the interaction with Pd, which was highly dispersed 2014; Patterson et al., 2019), it is required to store it for use at a
on CeO2 support (Choi et al., 2017). According to the XPS results, the later time due to the obvious challenges with each of the energy
peaks for Cu 2p electrons in Pd–Cu/CeO2 catalysts appeared at sources. For example, solar and wind are seasonal, intermittent
relatively lower binding energy than those in Cu/CeO2 catalyst, and fluctuating. The storage of electricity on a large scale and
meaning that Cu sites in Pd–Cu/CeO2 catalysts were more transportation at a very long distance are still challenging. The
abundant in electrons and could donate them to Cu, enabling Cu to electrical energy can be conveniently stored in chemical
stabilize in a more reduced state (Fox et al., 2008). Thus, Pd promotion compounds such as hydrogen, methanol, methane and higher
generated more electron-rich Cu sites by electron transfer (Choi et al., hydrocarbons that can then be stored, transported and used when
2017). Pd can also improve the reducibility of CuO and enrich the needed to produce electricity or for various other applications
catalyst surface with electrons, enabling the activation of CO2 by such as heating, cooking and transportation (Olah, 2005;
interaction with the carbon atom of CO2 (Choi et al., 2017). A Goeppert et al., 2014). It has been proposed that the carbon-
strong Pd–Cu bimetallic promoting effect on the formation of based liquid fuels will continue to be important energy storage
methanol from CO2 hydrogenation was observed, which is due to media in the future because of their higher volumetric stored
the synergetic effect between Pd and Cu as a result of the Pd–Cu alloy energy density. Methanol has great merits as a storage medium
formation (Jiang et al., 2015). Pd–Cu supported on amorphous silica for renewable energy. As an energy storage medium, methanol
exhibited higher catalytic activity than monometallic Cu/SiO2 or Pd/ displays high performance as an additive or substitute for gasoline
SiO2 for CO2 hydrogenation to methanol. Some authors attribute the in internal combustion engines. The direct conversion of the
synergistic effect between Pd and Cu, which contributes to the chemical energy in methanol to electrical power at ambient
improvement of catalytic activity to the alloy formation, as temperature has been demonstrated in methanol fuel cells
evidenced by the correlation between catalyst composition, structure (McGrath et al., 2004). Methanol is also a feedstock for a
and catalytic performance (Jiang et al., 2019a; Jiang et al., 2019b). The number of chemicals such as formaldehyde and acetic acid. It
Pd–Cu bimetallic catalysts with total metal loadings (2.4–18.7 wt%) and can produce light olefins, including ethylene and propylene, used
optimal Pd/(Pd + Cu) atomic ratio exhibited a bimetallic effect on in the synthesis of various polymers, and any hydrocarbons and
promoting CH3OH synthesis at 250°C and 4.1 MPa. The improvement products currently obtained from petroleum oil through the
in catalytic performance was realized at lower metal loadings, and methanol-to-olefin process. DME produced from methanol
Pd–Cu(2.4)/SiO2 catalyst could yield approx. 1.6 times higher methanol can be easily liquefied at moderate pressure and applied as
than the commercial Cu/ZnO/Al2O3 catalyst as measured with the diesel fuel substitute with high cetane rating, producing little
metal-based STY. At high loadings, Pd–Cu alloy exhibited high or no soot emissions (Semelsberger et al., 2006; Arcoumanis et al.,
selectivity to CO (Nie et al., 2018; Jiang et al., 2019a). The amount 2008). It is a good substitute for liquefied petroleum gas in most
of alloy, as determined by quantitative X-ray diffraction, correlated with applications, such as heating and cooking.
the observed promotive synergy; and the estimated TOFs, suggesting its The CO2 hydrogenation to methanol can be processed by the
involvement in methanol synthesis (Jiang et al., 2019b). A Cu–Zn thermochemical, electrochemical and photochemical methods.
bimetallic catalyst supported on Al foam (Cu–Zn/Al foam) gave a high These processes are challenging in several aspects. The
methanol yield of 7.81 g gCu−1 h−1 at CO2 conversion of 9.9% and thermochemical process applied in the commercial methanol
methanol selectivity of 82.7% under reaction conditions of 3 MPa and synthesis from natural gas is a two-step process that transforms
250°C at a high WHSV of 20,000 ml gcat−1 h−1. It was found that the the energy and molecules in a fossil fuel (Olah, 2013). The first
support structure played a significant role in the performance of this step is the steam-methane reforming into synthesis gas, which
catalyst. Compared with the other Cu-based catalysts, the Cu–Zn/Al subsequently converts to methanol in the second step. A few
foam catalyst possesses a good heat/mass transferability, and an percent of CO2 is also produced in the first step. Methanol cannot
appropriate amount of basic sites (Liang et al., 2017). be directly generated electrochemically from CO2 with high

selectivities or current densities (Malik et al., 2016; Yang D. et al., CONCLUSION AND OUTLOOK
2019).
Researches are continuously seeking new technologies to In this review, we have discussed the recent developments in the
recycle CO2 to liquid fuel most efficiently and economically. direct hydrogenation of carbon dioxide to methanol over the Cu/
Patterson et al. (2019) developed a new approach integrating the ZnO-based catalysts. No doubt, the Cu-based catalysts are still
existing conventional chemical catalytic process and energy very promising for the direct hydrogenation of CO2 to methanol
harvesting methods. They proposed combining solar methanol in the industry. Still, they need to be improved to overcome a
islands and human-made marine structures that use renewable series of technical problems. Many studies have been conducted
energy to harvest CO2 from seawater and catalysis to produce to understand the catalyst structures and to enhance their
methanol. This approach uses clusters of marine-based floating functionalities. From the thermodynamical aspect, both low
islands on which photovoltaic cells convert sunlight into electrical temperature and high pressure are favorable conditions for the
energy to produce H2 and extract CO2 from seawater, where it is methanol synthesis from CO2 reduction with hydrogen; however,
in equilibrium with the atmosphere. H2 and CO2 then react to low temperature is kinetically unfavorable for breaking the
form methanol. H2 is electrochemically generated and the O–C–O bonds in CO2 molecule. High temperature increases
extraction of CO2 is possible using a series of membrane cells. the rate of RWGS and other side reactions, whereas high pressure
Methanol is then synthesized using a looped gas-phase is economically infeasible. It is a challenge to obtain both a high
heterogeneous catalytic process. They suggested that a single single-pass CO2 conversion and a high methanol selectivity with
solar methanol island could output up to 15,300 tons/year of the current industrial catalyst via the direct CO2 hydrogenation.
methanol. The process is particularly of advantage compared with Consequently, developing Cu-based catalysts with high activity
the direct atmospheric CO2 capture because CO2 in seawater (high single-pass CO2 conversion and high selectivity to
(0.099 kg CO2/m3) is about 125 greater than the amount in the methanol) at lower temperatures and pressures are crucial for
atmosphere (0.00079 kg/m3) (Patterson et al., 2019). This the CO2 to methanol hydrogenation.
innovative technology for renewable fuel synthesis from the With the Cu/ZnO/Al2O3 catalysts, the sintering of the Cu
marine environment has attractive features, such as abundant particles is a crucial problem. Thus, high mechanical strength and
raw materials and large exposure to solar energy, and avoidance thermal stability are essential to maintain a long catalyst life
of local CO2 depletion. However, this technology relies on under typical industrial conditions. These may be achieved by 1)
previously demonstrated chemical and physical processes to use of confined catalysts, such as Cu or Cu/ZnO in porous
produce the solar methanol island on a significantly large materials, e.g., mesoporous SiO2 (SBA-15) and porous ZrO2;
scale. It is suggested that wind could also serve as a power 2) use of binders in the catalyst composition which can boost
source; thus, analyzing how other energy sources or energy both thermal stability and water resistance, and 3) deploying
mixture could contribute is expected to further the suitable synthesis methods and protocols, such as adding
development of the process. For a practical design of solar- promoters to the base catalyst, forming promoted or multi-
powered artificial marine-islands to recycle CO2 into methanol metallic catalysts
and other synthetic liquid fuel, some issues must be addressed. Besides the conventional methods for catalyst preparation,
These include i) how photovoltaic modules can be deployed on a several other approaches are promising for the development of
large-scale in the marine environment, and properly maintained. modified catalysts. These catalysts can be grouped into the
ii) Is combined technology such as desalination and electrolysis a following: 1) solid-solution derived catalysts, e.g., the solid
possibility to efficiently produce H2 from seawater? iii) Can solution of ZnZrOx is demonstrated to possess high selectivity
electrodialysis be deployed for large-scale CO2 extraction from and stability. Therefore, opportunities exist for even better
seawater? iv) What kind of reactor material and systems performances of some other solid solutions for methanol
engineering are required to realize a large, practical marine synthesis from CO2. Several materials acting both as support
installation? If methanol is the end product, there is the need or co-catalysts are effective as the traditional alumina in the Cu/
to look into the optimal design, including reactor looping and ZnO/Al2O3. Specifically, ZrO2 is a good substitute for Al2O3 due
heat and pressure management, for a marine-based synthetic fuel to its excellent catalytic and surface properties; 2) catalysts
reactor and separation system. These frontline questions need derived from complex metal oxide compounds, e.g.,
urgent technological answers. hydrotalcite, perovskites, spinel compounds, MOFs, zeolites,
The integration of direct CO2 air capture with CO2 and H2O as etc. The catalysts derived from these compounds can have a
electrolyzers and a traditional methanol synthesis step in a high Cu dispersion and intimate contact among various catalyst
process termed “air-to-barrel” has been proposed (Smith et al., components. For example, Cu or Cu/ZnO nanoparticles derived
2019). The process uses CO2 electrolyzers to convert atmospheric from perovskites and hydrotalcites through a proper reduction
CO2 into solar fuels using renewable electricity. This technology strategy may have high dispersion of Cu; MOFs and zeolite
has the potential of producing 10,000 tons of methanol/day. The derived catalysts may have the well-defined component
CO2 and water electrolyzers can replace the steam-methane composition and ratio, and precise location, which should be
reforming step of current methanol synthesis by producing suitable for the reaction and the clarification of the property-
CO and H2 from CO2 and H2O. Essentially, the carbon and structure relations of the catalysts, as the well-defined structures
hydrogen content of methane is replaced by CO2, H2O and solar can enable the understanding of how catalyst micro/
energy. macrostructure affects conversion and selectivity; 3) core–shell

catalysts, e.g., Cu or Cu/ZnO with ZrO2 shells. The core–shell a major liquid product of CO2 hydrogenation with hydrogen
catalysts are highly thermally stable and could form efficient from renewable energy sources, can serve as a storage medium
function-selective catalysts; 4) alloy and bi- or tri-metallic for future use of energy in various applications such as heating,
catalysts, and 5) metallic–nonmetallic hybrid systems. cooking and transportation. New processes for renewable fuel
It is believed that the CO2 reductive hydrogenation to methanol production have been developed, such as “solar methanol
commonly proceeds mainly through two mechanisms—the RWGS island” involving CO2 from the marine environment in
(via *HOCO intermediate species) and the formate (via *HCOO combination with catalysis, and “air-to-barrel” process,
intermediate species) pathways. While the former involves a CO which uses CO2 electrolyzers to convert atmospheric CO2
intermediate followed by hydrogenation, in the latter, CO2 is into solar fuels. It is not yet developed a practical design of
initially hydrogenated to the formate species, further solar-powered artificial marine-islands to recycle CO2 into
dissociating to methanol. The various active sites reported methanol and other synthetic liquid fuels. Several issues,
include metallic Cu, oxidized Cu, Zn decorated Cu, and isolated including deployment at marine environment on large-scale,
Cu–Zn interfaces. Although the active sites and reaction proper maintenance, efficient production of H2 from seawater,
mechanisms have been explored and analyzed in the literature, and the reactor requirements for practical marine installation
yet, knowledge of the detailed structure of the catalysts is still need to deal with.
lacking. Analytical approaches such as the in situ experimental
measurements should be deployed to elucidate the active sites and
reaction mechanisms. Theoretical calculations using multiscale AUTHOR CONTRIBUTIONS
modeling techniques should complement experiments to
elucidate the structures of the traditional catalysts further and to UJE wrote the manuscript. YS revised the manuscript. ZZ
improve the design of new ones. It should be kept in mind that a organized, wrote and modified the manuscript.
well-designed catalysts will catalyze the desired reaction but inhibit
the side reactions. However, the design of suitable catalysts mainly
depends on understanding the reaction mechanism and active site FUNDING
structures, and the advances in the catalyst preparation. Therefore,
a comprehensive solution combining a fundamental This work is financially supported by 2020 Li Ka Shing
understanding of catalysis with advanced catalyst preparation Foundation Cross-Disciplinary Research Grant
and process optimization is necessary. (2020LKSFG09A), Guangdong Province Key discipline fund
The recycling of CO2 to renewable fuels and platform (GTIIT), and Department of Education of Guangdong
chemicals is an important aspect of CO2 mitigation. Methanol, Province (2018KTSCX063).
Bartholomew, C. H. (2001). Mechanisms of catalyst deactivation. Appl. Catal. Gen.

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published: 29 September 2020

Improving the Cu/ZnO-Based

Heterogeneous catalytic hydrogenation of carbon dioxide (CO2) to methanol is a practical

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FIGURE 1 | Diverse products from thermochemical CO2 conversion and methanol.

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The Imperial Chemical Industries developed the Cu/ZnO catalyst

H2O react over the Cu-based catalysts to form CO2 and

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TABLE 1 | Performance of various Cu/ZnO/Al2O3 ternary industrial catalysts.

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FIGURE 5 | Properties, challenges and possible solutions.

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CZA 17.9 7.0 1.51 0.13 98.49 16.0 2.57

Reaction conditions: 240°C and 30 bar; space velocity of 6,000 L/kgcat. h.

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FIGURE 10 | Classiﬁcation of supports for Cu-based methanol synthesis catalysts.

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Bartholomew, C. H. (2001). Mechanisms of catalyst deactivation. Appl. Catal. Gen.

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