Catalytic Conversion of Carbon Dioxide To Methanol

REVIEW
published: 09 February 2021

doi: 10.3389/fenrg.2020.621119
Catalytic Conversion of Carbon

Dioxide to Methanol: Current Status
and Future Perspective
Xinbao Zhang 1, Guanghui Zhang 1*, Chunshan Song 1,2* and Xinwen Guo 1*
1
State Key Laboratory of Fine Chemicals, PSU-DUT Joint Center for Energy Research, School of Chemical Engineering, Dalian
University of Technology, Dalian, China, 2Department of Chemistry, Faculty of Science, The Chinese University of Hong Kong,
Hong Kong, China
With the increasing environmental problems caused by carbon dioxide (CO2) emission and
the ultimate carbon resources needed for the development of human society, CO2
hydrogenation to methanol with H2 produced with renewable energy represents a
promising path forward. Comprehensive analysis shows that the production of
methanol by thermal catalytic CO2 hydrogenation is the most promising technology for
large-scale industrialization. This review highlights current developments and future
Edited by:
perspectives in the production of methanol from CO2, as well as the main existing
Michele Aresta, problems based on a thorough techno-economic analysis. Moreover, the utilization
IC2R srl, Italy
status and future role of methanol as a platform molecule in the energy system is
Reviewed by:
analyzed. Finally, in this review attention is paid to the development of new catalysts,
Eugenio Quaranta,
University of Bari Aldo Moro, Italy new routes and new technologies for CO2 conversion aiming to clarify the future direction.
Stefano Stendardo,
Energy and Sustainable Economic Keywords: CO2 conversion, methanol synthesis, new catalysts, new routes, new technologies
Development (ENEA), Italy
*Correspondence: INTRODUCTION
Guanghui Zhang
gzhang@dlut.edu.cn While absorbing solar radiation, the earth is also losing energy to the space, so that the energy in and
Chunshan Song
out of the earth system is basically the same (Figure 1A). However, human activities are breaking the
chunshansong@cuhk.edu.hk
Xinwen Guo
balance, and the situation is becoming more and more serious. In May 2019, CO2 concentration in
guoxw@dlut.edu.cn the atmosphere exceeded 415 ppm, about 48% higher than that before the industrial revolution. The
magnitude and rate of this increase, at least in the earth’s nearly 800,000 years of history, is
Specialty section: unprecedented (Figure 1B). The greenhouse effect caused by carbon emission has led to a series of
This article was submitted to extreme weather and is threatening the future of our living planet (Iizumi et al., 2018). Researchers
Carbon Capture, Storage, speculate that the increase of extremely severe cyclonic storms over the Arabian Sea caused by ocean
and Utilization, warming may be the ringleader of this unprecedented locust disaster in 2020 (Murakami et al., 2017).
a section of the journal Moreover, global warming will continue to increase the risk of a deadly flood outbreak due to the
Frontiers in Energy Research
collapse of an ice lake in the Himalayas (Veh et al., 2020). Related researches also pointed out that
Received: 25 October 2020 global warming is making some originally quiet volcanoes restless due to the increase of extremely
Accepted: 29 December 2020
heavy rainfall (Zhang et al., 2018; Farquharson and Amelung, 2020). Presently, slow GDP growth
Published: 09 February 2021
and rising energy prices have not stopped the rise of energy consumption, and carbon emission
Citation: exceeded ∼34,000 million tons both in 2018 and 2019, higher than the emission in recent years
Zhang X, Zhang G, Song C and Guo X
(Figure 2) (Dudley, 2019).
(2021) Catalytic Conversion of Carbon
Dioxide to Methanol: Current Status
CO2 utilization has been defined as the process of using it as a raw material for products or services
and Future Perspective. with a potential market value. The utilization includes direct approach (International Energy Agency,
Front. Energy Res. 8:621119. 2019; Ra et al., 2020), where CO2 is not chemically altered (non-conversion), and the chemical and
doi: 10.3389/fenrg.2020.621119 biological conversion of CO2 to useful products (Figure 3). Most existing commercial applications
Frontiers in Energy Research | www.frontiersin.org 1 February 2021 | Volume 8 | Article 621119

Zhang et al. Carbon Dioxide Conversion to Methanol
FIGURE 1 | (A) Schematic diagram of the energy budget of the earth: the yellow arrows are the short wave radiation reflected and absorbed by the earth; the red
arrows are the long wave radiation absorbed by greenhouse gases and released from the earth. Figure from: https://science-u.org/experiments/solar-oven-smores.
html. (B) Changes of atmospheric CO2 concentration in the past 800,000 years. Figure from: Scripps Institute of Oceanography, https://sioweb.ucsd.edu/programs/
keelingcurve/.
FIGURE 4 | Growth in global utilization and emission of CO2. Note:

Projections for future global CO2 demand are based on an average year-on-
FIGURE 2 | Global CO2 emission from the activities related to the
year growth rate of 1.7% (International Energy Agency, 2019). Projections for
combustion of oil, coal and natural gas (Dudley, 2019).
future global CO2 emission are based on an average year-on-year
growth rate of 1.4% (based on the annual average growth rate of 2009–2019)
(Dudley, 2019).
fuels (Satthawong et al., 2013), chemicals and building materials

(Jiang et al., 2015; Li et al., 2018; Liu et al., 2018a; Wang et al.,
2020a; Zhu et al., 2020). Today, around 230 million tons (Mt) of
CO2 are used each year (IEA, 2019a). However, the CO2 utilization
is less than 1% of the CO2 released (Figure 4). The largest
consumer is agriculture, where around 130 Mt of CO2 per year
is used in urea manufacturing, followed by the oil industry, with a
consumption of 70 to 80 Mt of CO2 for enhanced oil recovery
(IEA, 2019b). More than two-thirds of current global demand for
FIGURE 3 | Simple classification of CO2 utilization pathways. CO2 come from North America (33%), China (21%) and Europe
(16%), and the demand for existing uses is expected to grow
steadily year-on-year (IEA, 2019a). Until now, the process of CO2
involve direct utilization, including the production of food and conversion to chemicals is limited by the market scale. Therefore,
beverages, metals fabrication, dry cleaning, healthcare, fire the development of target product methanol, which can be used as
suppression, and the petroleum industry. Although still under fuels and chemicals (Sakakura et al., 2007; Yu et al., 2010; Cokoja
development, the chemical and biological utilization has drawn et al., 2011; Peters et al., 2011), is of great significance for achieving
much attention in recent years, including developing CO2-derived a large-scale application.

Methanol can be integrated into the current energy system and

used as 1) a convenient energy-storage material, 2) a fuel, and 3) a
feedstock to synthesize hydrocarbons, and an all-around substitute
for petroleum (Olah, 2005; He et al., 2013; Araya et al., 2020). Indian
government has been promoting clean transportation and the
application of fuel-cell vehicles (Reddy et al., 2018). Dor Group
began pilot testing in 2012 after the government of Israel
determined one of the most favorable way to reduce the reliance
on conventional fuels which is the use of methanol as the gasoline
replacement, or gasoline-blending component, in internal
combustion engines (Dor Group, 2019). China is also speeding
up the layout of methanol fuel market. Eight departments including
the Ministry of Industry and Information technology of China
jointly issued the Guidance on the Application of Methanol FIGURE 5 | The simplified carbon cycle with methanol as platform
Vehicles in Some Regions (2019). Shanxi, Shaanxi, Guizhou, molecule in the future.
Gansu and other regions are accelerating the application of
M100 methanol vehicle and realizing the diversification of
vehicle fuel to ensure energy safety, for they have good resource demand, scale of CO2 emission source, and H2 availability (Roh
endowment conditions and methanol vehicle operation experience et al., 2019). Therefore, target products that can be used as fuels
(Ministry of Industry and Information Technology of the People’s and chemicals are of great significance for the large-scale
Republic of China, 2019). Compared with the top-down emission reduction. Moreover, small-molecule products have
development mode of natural gas, ethanol and other clean irreplaceable advantages compared with large-molecule
energy (policy in front, promotion and application in the back), products, due to the high selectivity, simple process, low
that of methanol is bottom-up, and after long-term exploration, energy consumption, etc. As a fuel and an important chemical
practice and verification, the above policy documents are in place. feedstock, methanol is used on a large scale, and has been used as
Comprehensive reviews were presented about the recent a feedstock for the synthesis of chemicals and fuels (Olsbye et al.,
significant advances in CO2 hydrogenation to methanol, 2012). The hydrogenation of CO2 to methanol has attracted
focusing on development of catalysts including metals, metal much attention as a promising way (Behrens et al., 2012;
oxides, and bimetallic catalysts, as well as the structure-activity Kattel et al., 2017a; Wang et al., 2017; Lam et al., 2018; Dang
relationship, in situ characterizations on identifying key et al., 2019b; Wang et al., 2019b; Li and Chen 2019). Next, we will
descriptors and understanding reaction mechanisms (Jiang discuss the role of methanol in the future energy system, technical
et al., 2020; Zhong et al., 2020). Researchers also provided an feasibility and techno-economic analysis for methanol synthesis
in-depth assessment of core-shell materials for the catalytic from CO2. By analyzing the research status and development
conversion of CO2 into chemicals and fuels (Das et al., 2020). potential of CO2 hydrogenation to methanol, we aim to find out
ZrO2-containing catalysts are also systematically reviewed to the existing problems and point out the direction for future
offer insights into the modification of surface properties and research.
bulk structure of catalysts driven by the supports and the resulting
effects on the performance for CO2 hydrogenation to methanol
(Li and Chen, 2019). Based on the summary of the research status The Importance of Methanol in the Field of
of the catalytic materials in published reviews, this review is Energy
organized toward the future development prospects, with an In the future we will phase out fossil fuels and switch to
emphasis on the role of methanol in the energy system in the sustainable energy, especially hydroelectricity, wind and
future and technical feasibility. By analyzing the current status of photovoltaic energy. However, due to the variable nature of
thermocatalytic conversion of CO2 into methanol, the review the latter sources which depend on time of day, and season of
highlights the development of catalysts regarding precise the year, we need to store such energy at peak production times
preparation, large-scale production, high efficiency and low cost. for use in times of low production. Converting such energy into
chemical energy and storing it in methanol molecules is regarded
as one of the promising methods. Methanol is considered as one
ANALYSIS OF THE WHOLE PROCESS OF of the potential platform molecules because of its available
THERMAL CATALYSIS OF CO2 TO applications in the fields of fuels and chemicals in the future
(Figure 5) (Su et al., 2013). At present, methanol-based
METHANOL technologies include methanol synthesis, methanol to olefins,
CO2 life cycle assessment is helpful to pick out the main problems chemicals (formaldehyde, acetic acid, methylamines, glycol, etc.),
existing in the process of CO2 conversion. Researchers have gasoline, biodiesel, direct combustion and so on (Figure 6). The
introduced a mathematical formulation to select the promising methanol economy through chemical recycling of CO2 will
CO2 capture and utilization (CCU) paths. The results indicate eventually free human from dependence on fossil fuels
that the optimal solution is greatly influenced by the market (Tountas et al., 2019). In recent years, China has developed a

stranded supplies of natural gas, such as the United States. Based

upon methanol-gasoline price ratios as of early January 2015, a
reduction of ∼20% in unit energy costs could be achieved
depending on the fluctuating cost of crude oil, as well as other
market factors (Netzer et al., 2015). Based on the current
methanol-gasoline price ratio, at least in China, it is
economically feasible to replace conventional gasoline with
methanol. Methanol is also used as internal combustion
engine fuel for large ships. Diesel methanol dual-fuel ships
have entered the marine transportation trade. The first
methanol smart industrial park is located at Jiangxi, China.
The intelligent industrial park of new energy will be the first
specialized industrial cluster in China with “methanol smart
industrial chain” as the main body, and the annual output
value is expected to reach 10 billion after it is put into
FIGURE 6 | Fuels and chemicals based on methanol. Source: Methanol operation. ZHONGSHANG GUOXIN is planning to build six
Institute, www.methanol.org. distribution centers in China, striving to gradually cover more
than 10,000 retail terminals in 3–5 years. As the world’s largest
methanol producer and consumer, Chinese methanol production
series of clean coal technologies to transform black-dirty coal into capacity accounts for more than 50% of the world’s total. As of
clean fuels and chemicals. Clean coal technologies based on 2016, the annual production capacity has reached 80 million tons,
methanol platform will play an important role in Chinese and the production capacity of methanol is still increasing (China
energy system in the future (Xu et al., 2017). Shenhua, the Energy News, 2019). Several locations in North America are also
largest coal company in China is leading the considering to convert petroleum coke into methanol. Methanol
commercialization of modern clean-coal technologies for is becoming an important part of the future energy system.
value-added chemicals and transportation fuels.
As a potential clean energy carrier, methanol has been widely Technical Feasibility
used in the transportation fields such as methanol vehicles, ships, Thermocatalytic methanol synthesis from CO2 has a solid
heavy trucks, industrial boilers, stoves and other industrial and theoretical basis. Catalysts with different metals like Cu, Zn,
civil fields. The use of methanol as transport power has begun to Ag, Cr, and Pd have been employed for CO2 hydrogenation to
take shape. There are more than 6,000 well-running methanol methanol (Kattel et al., 2017a; Dang et al., 2019b; Din et al., 2019).
vehicles and 20 methanol filling stations in Xi’an, China (China Nevertheless, Cu-based catalysts exhibit high activity and
Energy News, 2019). The pilot projects around methanol fuel are selectivity. Different promoters (ZnO, ZrO2, and LaOx, etc.)
also increasing. Methanol gasoline has the characteristics of high- have been used to improve the activity of Cu-based catalysts
octane value, clean and low energy consumption. Compared with (Ham et al., 2018; Hu et al., 2018; Chen et al., 2019a; Mureddu
gasoline and diesel, methanol can burn fully, and its application et al., 2019; Noh et al., 2019). In addition, the reaction conditions
as fuels can effectively reduce the emission of harmful gases. The (temperature, pressure, and feed gas ratio, etc.) have also been
emission of PM2.5 can be reduced by 80–85%, NOx by 60–80%, investigated systematically (Arena et al., 2013; Kobl et al., 2016;
and CO by 75–90% (Olah, 2005). According to the economic Din et al., 2019). Due to exothermic nature of the reaction, the
analysis of methanol vehicles in Xi’an pilot project, the methanol process is thermodynamically favorable at low temperature.
consumption per 100 kilometers is about RMB 35 yuan, and the According to Le Chatelier’s principle, higher pressure will
gasoline consumption is about RMB 70 yuan. The price promote the formation of methanol. Therefore, reactors must
comparison of conventional oil products is summarized in be able to work at high pressure and moderate temperature. Most
Table 1. importantly, there must be 1) an efficient method to remove the
Dor Group’s pilot tests in Israel suggest that methanol can at heat released from the reactor, and 2) a recycle facility to send
least provide a partial alternative to conventional or reformulated unreacted feedstocks back to the reactor after separating
gasoline, particularly in regions with abundant but seemingly methanol and H2O. The exotherm from the reactor will be
used elsewhere, for instance, in preheat of the feedstocks, or
distillation of the methanol (Bowker, 2019).
TABLE 1 | Comparison of oil prices. Thermal catalytic methanol production from CO2 has a
mature industrial application background (Luu et al., 2015).
Products Methanol ethanol Gasoline
As early as 1923, methanol was produced at the industrial
Price ($/kg) a
0.30 0.75 1.00 scale from syngas derived from coal, thanks to the work of
($/km)b 0.05 0.1 Alwin Mittasch and Mathias Pier at BASF (Aresta et al.,
Endurance mileage (km/kg) 6 10 2015). Today, more than 90 plants are in operation
a
Data from Wanhua Chemical’s Petrochemical Information, 20190911; worldwide, nearly 200,000 tons of methanol is used as a
b
Data from: (China Energy News, 2019). chemical feedstock or a transportation fuel every day

(Methanol Institute, 2020). George Olah’s methanol economy is of 10%, has a break-even value of 0.96 $/kg for methanol (Alsayegh
exemplified in a renewable methanol production plant in et al., 2019). The current price of H2 from natural gas and coal
Reykjavik, Iceland. This industrial facility commissioned in plants varies between 1–3 $/kg, among which the price of H2 by
2007 annually produces 4,000 metric tons of methanol from steam methane reforming is about 1.59 $/kg (Roy et al., 2018;
CO2 and H2 (Tountas et al., 2019). There is another demonstrator Esposito, 2017). The price of H2 from renewable energy sources
plant for methanol synthesis, namely the pan-European MefCO2 varies between 4.00–10.00 $/kg (Roy et al., 2018). If the cost of H2
project (MefCO2, 2020). It has been constructed very recently at from renewable energy sources can be reduced to 2.75 $/kg, CO2-
Niederaussem near Cologne, at the RWE coal-fired power station based fuel becomes cost competitive with gasoline (Smejkal et al.,
with an annual output of 500 tons of methanol. 2014). Fortunately, the cost of H2 varied from 1.60–10.40 $/kg for
the photoelectrochemical water splitting by the analysis of all
operating costs, capital expenditures for the auxiliaries
Techno-Economic Analysis for Methanol (compressors, control systems, etc.) and reactors with the
Synthesis From CO2 particle bed systems (Pinaud et al., 2013), indicating that
Techno-economic assessment for CO2 hydrogenation to commercial-scale water splitting could be cost-competitive with
methanol is helpful to guide decision-making regarding R&D fossil-based fuels. CO2 capture incurs costs from capital
investment and construction of large-scale CCU plants in the investment, energy for operating the process, cost of CO2
future. Therefore, researchers have investigated a solar-based release, sorbent losses, maintenance of equipment, CO2
system for methanol synthesis from CO2 and H2O. The entire compression and transportation. The estimated cost for flue gas
system (thermochemical reactor, water gas shift reaction system, capture is between 0.028–0.104 $/kg of CO2 depending on the
methanol synthesis reaction system, amine-based CO2 separation emission source (Rubin et al., 2015), while estimates for direct air
system and methanol purification system) is based on mature capture costs are still under debate, with reports ranging from 0.030
industrial processes, except for the thermochemical reactor to 1.000 $/kg of CO2 (Sanz-Peŕ ez et al., 2016). Moreover, the
currently under development. Thermochemical reactor is a implementation of carbon tax policy will further reduce the cost
solar chemical heat engine that allows for the thermochemical of CO2 capture. The single pass yield of CO2 hydrogenation to
splitting of CO2, which is an ultra-high temperature two-step methanol is about 15% (Ham et al., 2018; Chen et al., 2019a;
FeO/Fe3O4 cycle process. Detailed sensitivity analysis shows that Mureddu et al., 2019; Wang et al., 2019b). Several examples of
a breakeven price of methanol produced using this process would overall water splitting processes using semiconductor
be 1.22 $/kg; which is higher than current market price of photocatalysts have been reported. The maximum STH
0.24 $/kg. Importantly, the analysis here identifies that more efficiency is more than 1%, but still lower than the benchmark
than 90% of the capital investment comes from the solar STH value of 10% (Chen et al., 2018b). Analysis of the above
concentrator/reactor system (Kim et al., 2011). Life cycle parameters shows that there is still a big gap between the current
analysis shows that methanol synthesis from CO2 emitted by technical level and the requirements based on the techno-economic
coal plant exhaust is predicted to be 1.3–2.6 times higher than that analysis, and detailed parameters are shown in Table 2. However,
of its fossil-based analogue, which can be estimated to decrease the efficiency can be improved by adjusting the process route. For
significantly with a drop in electricity cost for H2 production example, H2 can be produced by electrolysis of H2O by using clean
(González-Garay et al., 2019). China will levy carbon tax after energy to generate electricity, and the STH value is expected to
2020 for enterprises whose comprehensive energy consumption is exceed 20% (silicon-perovskite solar cells: 25.2% efficiency (Service,
less than 5,000 tons of standard coal (China Energy News, 2019). 2016); Faradaic efficiency of H2 production from electrolytic water:
The implementation of carbon tax policy will further improve the 99% (Dotan et al., 2019). Recently, perovskite/Si dual-absorber cells
market competitiveness of methanol by reducing the cost of CO2 have been used for the stand-alone solar water splitting. 17.6% STH
capture. In addition, significant advances can be achieved by efficiency was achieved when a Si photocathode was paired in
improving separation, combing splitting of H2O and CO2, and tandem with a perovskite cell (Karuturi et al., 2020). Of course, we
process integration and distribution in the future. must consider its impact on methanol production costs while
Based on a comprehensive economic analysis, the best-case pursuing energy efficiency. In order to improve the yield of
scenario, where electricity price is 0.06 $/kWh with 30 years plant methanol, the production of methanol should be carried out
lifetime, 0.02 $/kg CO2 cost and solar-to-hydrogen (STH) efficiency under the conditions of low temperature and high pressure, but
TABLE 2 | Optimization parameters of techno-economic analysis and current data.
Electricity Cost of Cost of STH efficiency Methanol yield Methanol

price H2 produced CO2 captured price
Data analysis parameters Alsayegh 0.06 $/kWh 0.65 $/kg 0.02 $/kg 10% 92% 0.96 $/kg
et al. (2019)
Current data 0.14 $/kWha 1.6 $/kg Pinaud et al. 0.035 $/kg Rubin et al. 1% Chen et al. 14.5% Wang et al. 0.24 $/kgb
(2013) (2015) (2018b) (2019b)
a
Electricity price of china.
b
Data from Wanhua Chemistry (20200702).

the high pressure will inevitably increase the operating cost. oxide-zeolite catalysts; 4) exploration on new technology for
Therefore, the development of high efficiency catalysts working catalysts preparation (3D-printing, plasma and atomic layer
at low temperature and pressure for CO2 hydrogenation to deposition technologies), emphasizing surface chemistry and
methanol is an important research direction in the future. It is engineering, so as to find the direction of future research.
essential to combine in situ spectroscopy and theoretical calculation
to better understand the mechanism of CO2 conversion, and then Understanding the Active Sites
develop new catalysts and new reaction paths to improve methanol One of the main obstacles in developing rational strategies for
production efficiency. With the innovation of catalyst preparation heterogeneous catalysis is that the complexity of catalysts hinders
technology, new technologies and methods are adopted to achieve efforts to characterize their active sites. Deeper insights aid in the
precise construction and modification of the active sites, thereby to design of next-generation catalysts in an optimal manner, which
achieve efficient production of methanol. will provide the opportunity to tune the catalytic performance by
optimizing the functions of the components. In recent years,
surface composition and structure of commercial Cu-ZnO-Al2O3
RESEARCH DIRECTION OF CATALYSIS for methanol synthesis have attracted wide attention from both
industry and academia. Active sites such as Zn-Cu bimetallic sites
A wide variety of heterogeneous catalysts have been evaluated in (Li et al., 2016), ZnO-Cu interfacial sites (Kattel et al., 2017b) and
CO2 hydrogenation to methanol (Figure 7) (Jiang et al., 2015; Cu steps decorated with Zn atoms have been reported (Figures
Dang et al., 2019b; Nie et al., 2019; Das et al., 2020; Jiang et al., 8A,B) (Behrens et al., 2012; Kuld et al., 2016). Experimental and
2020; Zhong et al., 2020). The development of high-activity theoretical investigation show that ZnCu alloy undergoes surface
catalysts is conducive to reducing operating pressure and oxidation under the reaction conditions, which converts surface
production costs. Simultaneously, the development of Zn into ZnO and allows ZnCu to reach the activity of ZnO/Cu
multifunctional catalysts to produce value-added products can with the same Zn coverage (Kattel et al., 2017b). Moreover,
also pull the equilibrium of the reaction by consuming the researchers found the formation of metastable “graphite-like”
methanol intermediate according to the Le Chatelier’s ZnO layers during the reductive activation of Cu/ZnO/Al2O3
principle, and it can realize the coupling of multiple units (Figure 8C). Understanding this metastable layer might help to
such as the capture unit and the different conversion units. understand the synergistic effect between the components of Cu/
The new preparation technology is also a key link in catalyst ZnO/Al2O3 (Lunkenbein et al., 2015).
research and development, which aims to achieve one-step Supported Cu-based catalysts for methanol synthesis display
synthesis of catalysts from precursors to industrial shaped strong support effects. Researchers attribute the difference
catalysts. Therefore, the following four aspects will be between oxides to variation in the initial activation of CO2
discussed: 1) the research progress on active sites for methanol (Reichenbach et al., 2018). Through DFT (density functional
synthesis; 2) development of new catalysts; 3) exploration on new theory) calculations and spectroscopic characterizations,
routes, mainly including CO2 capture-transformation and metal researchers found that the ZrO2-Cu interface is crucial for the
conversion of formate to methanol (Larmier et al., 2017). It was
also pointed that the beneficial role of the Zn ensemble in the Cu-
vacant site of the stepped Cu (211) surface can enhance the
reactivity and durability of catalysts for methanol production.
The increased activity in the Zn-associated stepped sites is related
to the enhancement of the surface affinity toward the adsorbate
with the oxygen moiety (especially, HCOO) (Jo et al., 2019). The
pre-assembled Zr6(μ3-O)4(μ3-OH)4 and bpy sites in UiO-bpy
metal-organic frameworks were used to anchor ultrasmall Cu/
ZnOx nanoparticles, thus preventing the agglomeration of Cu
nanoparticles and phase separation of Cu/ZnOx nanoparticles
(Figure 9A). The Cu/ZnOx@MOF shows high activity with a
space-time yield of up to 2.59 gMeOH kgCu−1h−1, 100% methanol
selectivity and high stability over 100 hours (An et al., 2017). A
CuZnCeOx catalyst with excellent activity, selectivity and stability
was prepared by a parallel flow coprecipitation method.
Characterization results show that a significant synergistic
effect between Cu and metal oxides was observed at the
composite catalysts (Hu et al., 2018). CuZnZr catalysts were
treated by vapor-phase-treatment (VPT) method. This VPT
method with TPABr promotes the formation of the rod-like
structure, Zr and Zn enrichments on surface and the presence of
FIGURE 7 | Heterogeneous catalysts for methanol synthesis from CO2
more oxygen vacancies. The CuZnZr-TPABr-3 days shows a
hydrogenation.
methanol selectivity above 90% and no significant deactivation

within 100 h (Chen et al., 2019b). In short, the conversion of CO2

can also be achieved at the interfacial sites by taking advantage of
the synergy between the metals (Au, Cu, Ag, Pt, Pd, etc.) and
oxides.
The study on metal-oxide interface provides a better
understanding of the complex reaction network to identify the
key descriptors of the activity and tune reaction performance
(Kattel et al., 2017a). Surface organometallic chemistry has been
used to tailor active components and oxide supports to
understand the structure-activity relationship of catalysts. Cu/
Al2O3 catalysts prepared by surface organometallic chemistry
display higher activity toward CO2 hydrogenation compared to
Cu/SiO2. Researchers found that methanol formation involves
formate intermediates and that the increase of rate originates
from the metal-oxide interface (Lam et al., 2019). Moreover, Cu
nanoparticles supported on isolated Zr(IV) sites modified SiO2
exhibit high methanol selectivity and activity compared to those
loaded on SiO2 (Lam et al., 2018). SiO2 decorated with isolated
Ti(IV) sites also show significantly improved methanol selectivity
and CO2 hydrogenation activity. These isolated Ti(IV) sites
stabilize intermediates at the interface between the support
and Cu nanoparticles (Noh et al., 2019). However, researchers
found that the surface organometallic chemistry approach does
not affect the rate of CO formation. Here, further exploration is
needed to understand the differences of active sites and reaction
paths for methanol and CO formation.
In the study on the support effect of Cu-based catalysts, we
need to understand the difference between oxide supports with
and without oxygen vacancies. Moreover, the exact structure and
composition of the active sites need to be further identified under
the reaction conditions, especially for the Cu-ZnO-Al2O3
catalysts. This also requires us to rethink the role of supports
in industrial Cu-based catalysts, which is an active component
and participating in the construction of interfacial active sites for
CO2 and H2 activation or is mainly used to disperse active metals.
New Catalyst Development

Metal oxide (indium-, zinc-based oxide, etc.) catalysts have
drawn increasing attention, due to their excellent catalytic
performance in the CO2 hydrogenation reaction (Wang et al.,
2020a). High activity and stability for 1,000 h on stream of In2O3/
ZrO2 has been achieved. Characterization points that the oxygen
vacancies are active sites for methanol synthesis (Martin et al.,
2016). Pd is applied to enhance the performance of indium-based
catalysts. Pd atoms replacing indium atoms in the active In3O5
attract additional Pd atoms to form low-nuclearity clusters, which
promotes H2 activation (Frei et al., 2019). Methanol synthesis on
the defective In2O3(110) surface was investigated by DFT
calculations. The calculation results indicate that the
FIGURE 8 | (A) Aberration-corrected HRTEM images of Cu particles in
hydrogenation of H2CO* to H3CO* is the rate-limiting step
the conventionally prepared, most-active Cu/ZnO/Al2O3 catalyst (Behrens for methanol formation (Ye et al., 2013). A binary metal
et al., 2012). (B) Promoting effect of ZnO on Cu catalysts for methanol oxide, ZnO-ZrO2 solid solution catalyst, can achieve high
synthesis (Kuld et al., 2016). (C) Formation of a ZnO overlayer in methanol selectivity, high CO2 single-pass conversion and high
industrial Cu/ZnO/Al2O3 catalysts induced by strong metal-support
stability for at least 500 hours. Moreover, no deactivation was
interactions (Lunkenbein et al., 2015).
observed in the presence of SO2 or H2S in the reactants (Wang

FIGURE 9 | (A) CuZn@UiO-bpy for selective methanol synthesis from CO2 hydrogenation (An et al., 2017). (B) CO2 hydrogenation to methanol over ZrO2-
containing catalysts (Li and Chen, 2019). (C) Hydroxyl groups of SiC surface boosting catalytic activity in CO2 hydrogenation into methanol (Peng et al., 2018).
et al., 2017). ZrO2 support always plays important roles such as Researchers reported that supported Pt nanoparticles on
dispersants of active components, promoter and even active MoOx/TiO2 promote selective hydrogenation of CO2 to
component. The interaction between ZrO2 and metals (or methanol under mild conditions (Toyao et al., 2019). Another
oxides) affects the adsorption and activation of CO2 and H2, kind of catalyst (NiaInbAl/SiO2) for methanol synthesis at
and changes the reaction pathways and/or the binding of key ambient pressure was prepared by a phyllosilicate precursor,
intermediates (Figure 9B) (Li and Chen, 2019). which can form well-dispersed metallic particles. The
Exploring how surface properties regulate catalytic activity is also performances of NiaInbAl/SiO2 is better than that of
very important to deepen the mechanistic understanding. A conventional Cu/ZnO/Al2O3 catalyst at ambient pressure
molybdenum phosphide catalyst for methanol synthesis can (Richard and Fan, 2017). A Ni-Ga catalyst can reduce CO2 to
improve the activity and stability of the catalyst in a wide range methanol at ambient pressure. Ni5Ga3 is particularly active and
of CO/CO2/H2 feeds through weakening the interaction with formate selective among a series of tested catalysts (Studt et al., 2014).
(Duyar et al., 2018). Manganese-cobalt catalysts are also promising Moreover, SiO2, acting as a ligand and support, can also modify
for methanol synthesis. A significant improvement in cobalt species via Co-O-Si linkages, which favors the reactivity of
methanol selectivity was observed due to a synergistic effect *CH3O intermediates and hydrogenation to methanol rather than
between cobalt and manganese as well as an increase in surface the C-O dissociation to produce methane (Wang et al., 2020b).
basicity (Stangeland et al., 2019). Hydrophilic SiC quantum At present, the harsh operation conditions of industrial
dots (QDs) exhibited higher activity than commercial SiC for process restrict the development of the methanol industry, and
CO2 hydrogenation to methanol (Figure 9C). Mechanistic also bring large energy consumption. In the future, the research
studies show that the surface hydroxyl species directly and development of new catalysts should proceed toward mild
participate in CO2 hydrogenation through the addition of H operating conditions, with the purpose of reducing energy
atoms in hydroxyl groups into CO2 to form HCOO* consumption. Simultaneously, if H2 production is
intermediate (Peng et al., 2018). Understanding the decentralized, small-scale CO2 reduction devices that can be
interactions among different components (active metals, operated at low pressures and low temperature are required.
oxide supports and doped ions) and surface properties Moreover, the development of catalysts with high activity at low
should help elucidate the governing principles for designing temperature is also conducive to coupling the active components
high-performance catalysts with multiple active components. of CO2 capture, and realizing the integrated operation of CO2

capture and conversion. Transition metals (Ni, Co, etc.) often has shown high selectivity to gasoline (78.6%) with a very low
have high hydrogenation activity. How to realize the synthesis of methane selectivity (1%) (Gao et al., 2017). Moreover, the
methanol with high selectivity by transition metal catalysts is a catalysts exhibit a better performance during an industry-
fascinating research direction in the future. relevant test, which indicates promising prospects of its
industrial application.
New Route Exploration Metal oxide-zeolite bifunctional catalysts can also catalyze
Integrative CO2 Capture and Conversion CO2 to lower olefins with high selectivity. For example, a
The integration of CO2 capture and conversion can simplify the series of bifunctional catalysts containing In2O3-based or ZnO-
CO2 cycle process and reduce energy consumption. An air-stable based oxides and various SAPO (Silicoaluminophosphate)
and well-defined Mn-PNP pincer complex catalyzed one-pot zeolites with different crystal sizes, pore structures and amount
homogeneous CO2 hydrogenation to methanol is demonstrated. of acid sites were developed for the production of lower olefins by
The hydrogenation consists of two steps, N-formylation of an CO2 hydrogenation (Dang et al., 2019a; Tan et al., 2019). It can
amine utilizing CO2 and H2, and subsequent formamide remarkably realize highly selective synthesis of lower olefins and
reduction to methanol, regenerating the amine. Methanol yields inhibit the formation of methane. In-Zr oxide and SAPO-34
up to 71% and 84% (w.r.t amine) were obtained, when morpholine bifunctional catalyst exhibits an excellent C2-C4 selectivity of
and benzylamine were used, respectively; and a TON (turn over up to 80% at more than 35% CO2 conversion, and no significant
number) of 36 was observed (Kar et al., 2017). CO2 can also be deactivation was observed within 150 h (Gao et al., 2017). ZnZrO/
captured in amine aqueous solution and then hydrogenated to SAPO tandem catalyst fabricated with ZnO-ZrO2 solid solution
methanol (>90% yield) in a biphasic 2-Methyltetrahydrofuran/ and Zn-modified SAPO-34 zeolite can also achieve a selectivity
water system, which allows for easy separation and recycling of for C2-C4 as high as 80–90% among hydrocarbons through
the amine. CO2 from air can also be converted to methanol using CO2 hydrogenation (Li et al., 2017). Similarly, a ZnGa2O4 and
this route (Kar et al., 2018). Amines were also immobilized onto SAPO-34 bifunctional catalyst can also catalyze the direct
silica support and employed for tandem CO2 capture and methanol conversion of CO2 to C2-C4 with a selectivity of 86% (Liu
synthesis. Covalently attached amine functionalities on solid et al., 2018b).
supports displayed high recycling potential with almost no Researchers have also developed metal oxide-zeolite
leaching under the reaction conditions (Kar et al., 2019). CZA- bifunctional catalysts to convert CO2 to aromatics in a single
HT catalyst was prepared by physically mixing copper-based path with methanol and other oxygenates as the intermediates. A
catalyst for methanol synthesis with hydrotalcite for high composite catalyst of ZnAlOx and H-ZSM-5 has high aromatics
temperature CO2 adsorption. The catalytic performance of the selectivity (73.9%) with low CH4 selectivity (0.4%) among
CZA-HT catalyst was clearly promoted by CO2 adsorption on hydrocarbons. Furthermore, The selectivity of p-xylene in
hydrotalcite. The sample containing 40 wt% hydrotalcite and 60 wt xylenes is 58.1% on the composite catalyst containing Si-H-
% CZA shows the highest methanol selectivity of 73.4% (Fang et al., ZSM-5 (Ni et al., 2018). Cr2O3/H-ZSM-5 bifunctional catalyst
2019). can also realize the one-step conversion of CO2 to aromatics. Due
In the current demonstration project, CO2 capture and to the synergistic effect between the two components, aromatics
conversion are two independent operation units, which may selectivity of ∼76% was achieved, and there was no deactivation
also involve CO2 transportation, storage and different after 100 h on stream (Wang et al., 2019). ZnO/ZrO2-ZSM-5
downstream conversion processes. We postulate that tandem tandem catalyst was prepared for direct CO2 conversion to
CO2 capture and hydrogenation to methanol system presented aromatics with a selectivity of 70%, and the selectivity of CH4
here could be an important step toward the implementation of is greatly suppressed to lower than 1% (Figure 10B) (Zhang et al.,
the carbon neutral and methanol economy concept, which can 2019). Similarly, CO2 is converted into aromatics with selectivity
reduce the energy consumption and simplify the production up to 73% over ZnZrO/ZSM-5 tandem catalyst (Figure 10C). The
process. However, matching the working conditions of CO2 presence of H2O and CO2 suppresses the formation of polycyclic
conversion and capture is a key issue that must be solved, and aromatics and enhances the stability of the catalyst (Li et al.,
the adsorbent also faces the problems of decomposition and 2019). Moreover, the conversion of CO2 into para-xylene was also
poisoning of nitrogen oxides and sulfur oxides. Although this reported, in one-pass by combining Zn-ZSM-5@SiO2 and Cr2O3.
process is still in the embryonic stage of research and facing many Through regulation of the acidity of Zn-ZSM-5@SiO2, high
problems, it has an attractive prospect. p-xylene selectivity (38.7% in the total products) at a CO2
conversion of 22.1% was achieved (Wang et al., 2019a).
Metal Oxide-zeolite Catalysts In brief, the direct transformation of CO2 into high value-
To improve the efficiency of CO2 conversion, researchers are added hydrocarbons (i.e., olefins and aromatics) has obtained
trying to transform the methanol and other intermediates into important fruits (Ye et al., 2019). The development of
fuels and chemicals in situ (Wang et al., 2018a; Ye et al., 2019). multifunctional catalysts can often achieve high-value and
Therefore, metal oxide-zeolite bifunctional catalysts have been complex chemicals synthesis. Moreover, the multifunctional
developed, which can catalyze CO2 to gasoline. Metal oxide is catalyst has become a research direction favored by the
responsible for CO2 hydrogenation to oxygenates, and zeolite industry due to its simple operation and low energy
accounts for the subsequent C-C coupling reaction (Figure 10A). consumption. However, there is a lack of in-depth
A bifunctional catalyst composed of reducible In2O3 and ZSM-5 understanding of its reaction paths, intermediate species, and

FIGURE 10 | (A) Schematic for CO2 conversion on metal oxide-zeolite bifunctional catalysts. (B) ZnO/ZrO2-ZSM-5 bifunctional catalyst was designed for the direct
conversion of CO2 to aromatics. (C) Highly selective conversion of CO2 to aromatics over ZnZrO/ZSM-5 (Li et al., 2019).
the synergistic effect among multiple components. The

bifunctional catalyst has shown obvious advantages in terms of
anti-carbon deposition deactivation compared with the single
methanol conversion process. The permanent deactivation of the
acid sites of the zeolite, due to the migration of metal oxides
during the reaction, restricts the regeneration and utilization of
the catalyst. At present, we still lack powerful tools to control the
distance between two components to prevent the acidic sites from
being covered by metal oxides. The development of multi-
functional catalysts also requires more efficient technology for
FIGURE 11 | 3D printing of artificial leaf with tunable hierarchical porosity
precise control of the distance between different components.
for CO2 photoreduction (Chen et al., 2018a).
Although the current understanding is limited, its excellent
performance attracts the unremitting efforts of researchers.
New Technology Exploration to the bio-ink developments in future. A 3D printing method has
3D-Printing Technology been developed for rapid, programmable, and scalable
3D-printing technology has been considered for numerous manufacturing of artificial micro-leaves with 3D architectures
research fields, ranging from medicine, mechanical ranging from nanometer to centimeter. Thus, a TiO2-based ink
engineering, and materials science to chemistry. For example, was developed to construct hierarchical 3D architectures with
3D-printing technologies pave the way for the design and high surface area (∼259 m2 g−1) (Figure 11) (Chen et al., 2018a).
manufacture of higher performing and cheaper electrochemical 3D printing has unique advantages on the modification of
devices (Ambrosi and Pumera, 2016). It is believed that some catalytic surfaces and the fabrication of catalysts (Jungst et al.,
concepts of supramolecular chemistry can be directly transferred 2016). It provides a convenient and economical way to prepare

3D architectures with well-designed patterns. With the reduction (e.g., acetic acid, methanol, ethanol, and formaldehyde) were
of operation cost in the future, 3D printing will be more widely synthesized in a one-step process from CO2 and CH4 at 30 °C and
used in the preparation of catalysts with controllable structure atmospheric pressure by using a plasma reactor with a water
and highly dispersed active components (Zhou and Liu, 2017), as electrode. The total selectivity to oxygenates was approximately
well as integration of the whole process from the design of active 50–60%, with acetic acid being the major component at 40.2%
sites to the shaping of industrial catalysts. selectivity (Wang et al., 2017). The use of plasma with the catalytic
bed enhanced the CO2 conversion (∼20 times) relative with
Plasma Technology thermal catalysis, whereas CH4 selectivity increased around
Plasma technology is increasingly attracting interest in the 5 times by introducing nickel catalyst into plasma discharge
preparation of catalysts. Nucleation and crystal growth of compared to plasma only at 150 °C (Ahmad et al., 2020). In the
materials under the influence of plasma is different from those future, plasma technology will play an important role in the
in the conventional thermal method. Plasma is also an effective preparation of catalysts and subsequent CO2 conversion.
tool for oxidation, reduction, etching, doping, coating and surface
treatment. It can operate at room temperature and allows the Atomic Layer Deposition Technology
catalyst preparation on temperature-sensitive supporting Atomic layer deposition (ALD) technology is expanding into new
materials. A method using plasma to remove template has areas and discovering other applications that benefit from its
been established for zeolites synthesis (Liu et al., 2015). In precise control capability (George, 2010). The design of catalysts
addition, transition-metal catalysts prepared by plasma for CO2 conversion requires high selectivity, activity and stability.
technology show enhanced activity at low-temperature (Yan ALD is a promising technology to address the main problems of
et al., 2015; Wang et al., 2018b). Moreover, plasma-assisted CO2 reduction, since it can construct catalysts with atomic
CO2 conversion is attracting more and more attention (Zhang precision in a highly controllable manner. Researchers have
et al., 2010; Shirazi et al., 2017). However, the process is highly been focusing on the designs of nanomaterials via ALD
complex due to the interaction between plasma and catalysts, and technology and its applications in CO2 capture and conversion
little is known about the factors leading to the observed synergy. (Chen et al., 2019c). The preparation of CaO-based sorbents
Catalytic mechanisms relevant to the specific application should assisted via ALD technology has shown high and cyclically stable
be extensively studied (Neyts et al., 2015). Plasma has been CO2 uptake (Armutlulu et al., 2017). Arrays of parallel CuO
introduced as a promising technology for modification of nanowires were surface decorated with dense ZnO islands via a
carbon materials, and modification of surface can often few pulsed cycles of ALD. A mechanism of CO2 reduction and
provide sites that can anchor active components. H2O oxidation occurred simultaneously in the active region
Hydrophobic/hydrophilic properties can also be tuned via between CuO nanowires and ZnO islands is proposed to
plasma technology (Zhang et al., 2017). The water produced elaborate the photocatalysis of CO2 into CO (Wang et al.,
in the process of CO2 hydrogenation can accelerate the sintering 2015). Pore mouth of 5 Å zeolite was decorated by depositing
of metal catalysts and occupy the active sites through competitive an ultrathin TiO2 layer on its external surface. The composite
adsorption. The stability of catalysts used for the hydrogenation sorbents show an ideal CO2/N2 adsorption selectivity, which is 4-
of CO2 to methanol can be enhanced by replacing oxide supports fold higher than uncoated zeolite sorbents, while maintaining a
(i.e., Al2O3, SiO2, TiO2, etc.) with hydrophobic carbon supports fast CO2 adsorption rate and a high capacity (Song et al., 2018).
(Furimsky, 2020). Therefore, plasma technology can further Porous TiO2 from a metal-organic framework MIL-125 was
optimize the performance of catalysts by adjusting the surface engineered using ALD method to deposit an ultrathin
hydrophobic/hydrophilic properties. Cold plasma is also used MgO layer. The CO2 photoreduction activity increased more than
to improve the dispersion of active components and enhance 4 times compared with that of the commercial P25 (Feng et al.,
metal-support interaction. Plasma reduction under room 2018). Surface atomic-layer modification technology has
temperature was developed for the reduction of metal oxides, provided an effective strategy to control the performance of
where no hazardous reducing agent or H2 were needed. This nanomaterials. In the future, development of low-temperature
provides many opportunities for the preparation of supported precursor presents unique opportunities, because it is easy to
catalysts with heat sensitive supports (high surface area carbon, perform ALD at low temperatures and it can avoid the
metal organic frameworks (MOFs), covalent organic framework aggregation of particles at high temperature (Adhikari et al.,
(COFs), peptide, proteins and others) (Liu et al., 2016). As an 2018).
example, β-Mo2C nanorods were coupled with non-thermal
plasma to catalyze CO2 reduction to CO by H2. In the absence
of additional thermal input, the turnover frequency was an order SUMMARY AND FUTURE PERSPECTIVE
of magnitude higher than that obtained during thermal catalysis
(Zhang et al., 2020). The combination of the plasma with Pt/ Capturing CO2 from flue gas and the atmosphere and its catalytic
γ-Al2O3 or Cu/γ-Al2O3 enhanced the methanol yield compared conversion to fuel and chemicals using H2 from renewable energy
to the plasma hydrogenation of CO2 without catalyst. The can lead to a sustainable future for humankind. Methanol can be
methanol selectivity of 53.7% and methanol yield of 11.3% used as fuel-substitute and raw material for hydrocarbon and
were achieved over Cu/γ-Al2O3 with a CO2 conversion of chemicals with many industrial applications. The hydrogenation
21.2% in the plasma process (Wang et al., 2018). Chemicals of CO2 to methanol not only effectively alleviates the greenhouse

FIGURE 12 | Schematic diagram of CO2 capture and conversion process and industrialization process of catalysts assisted by new technologies.
effect, but also produces fuel and value-added chemicals. Carbon `methanol (Li et al., 2020). Moreover, nano-reactor with
capture and storage efforts are expected to reduce CO2 emissions hydrophilic/hydrophobic surfaces will act as powerful
by about 8 Gt in the IEA 2010 Energy technology perspectives by supports for metal nanoparticles, and the molecular-fence
year 2050 (Styring et al., 2015). At present, the production concept should open a promising route to more-efficient
capacity of methanol in the world is about 0.20 Gt (China catalysts for methanol synthesis (Jin et al., 2020). The
Energy News, 2019). If methanol is produced entirely from construction of multifunctional catalysts to realize the
CO2, it will consume 0.27 Gt of CO2. Therefore, the energy further conversion of product methanol to high value-added
system with methanol as the platform molecule requires chemicals can also drive the shift of thermodynamic
further expansion of methanol production scale. One of the equilibrium. What we must explore is how to achieve
main obstacles in developing rational strategies for methanol controllable coupling between different components while
synthesis is the complexity of the catalysts, which hinders avoiding cross-contamination issues. Moreover, more
characterization of the active sites. Therefore, an in-depth sensitive spectroscopy techniques should be used to
understanding of active sites and reaction mechanism is characterize key intermediate species, and combined with
significant for the rational design of high-performance kinetic simulation to explore the influence of reaction
catalysts. Furthermore, operando characterization of catalysts atmosphere and intermediates concentration on the yield of
under working conditions is highly recommended to correlate the target products. It is expected to guide the development of
the structure-activity relationship. In situ techniques with high high-performance composite catalysts based on a deep
sensitivity of surface species (e.g., in situ IR, in situ XPS) and understanding of the reaction paths.
active sites (e.g., in situ TEM, in situ X-ray absorption techniques) The research and development of catalysts will also go hand
should be widely employed. in hand in high-throughput screening mode and precision
Various strategies have been explored for thermocatalytic CO2 construction mode. Because the function of heterogeneous
hydrogenation into methanol via heterogeneous catalysis, catalysts is defined by a mixture of molecular and
spanning from new catalyst development (transition metals/ mesoscopic components, atomistic simulations cannot fully
metal oxides to main group metal/metal oxides) to new route capture this multi-length-scale complexity in present, and the
exploration (metal oxide-zeolite catalysts and integrative CO2 design of such catalyst from first principles is still rare
capture and hydrogenation). The development of new catalysts is (Woodley and Catlow, 2008). At present, the integration of
toward the direction of lower energy consumption (e.g., low- machine learning and high-throughput technology have been
pressure hydrogenation process) and higher methanol yield (e.g., emerging to improve the development of new materials and
low temperature methanol synthesis). Here, we need to take into performance of catalysts (Cole et al., 2017; Damith et al., 2018;
account the problem that highly active catalysts are more likely to Hartrampf et al., 2020). High-throughput synthesis and
be poisoned by impurities. On the other hand, the design of evaluation devices are speeding up the development of new
membrane reactor is of great practical significance for delaying catalysts. Moreover, robots will become one of researchers in the
water-induced catalyst deactivation and for the shift of future laboratory, and the heavy and repetitive work will be completed
thermodynamic equilibrium after the in situ removal of the by robots (Burger et al., 2020; Epps et al., 2020). High-throughput
water byproduct. Highly efficient in situ by-product H2O technology will also be the mainstream means of catalyst research and
removal through water-conduction membrane has led to a development in the months and years to come. With the development
drastic increase in ethanol yield in CO2 hydrogenation to of new technology (3D, Plasmas and ALD), efforts are also being made

to engineer catalytic materials with desired structure in nanoscale or AUTHOR CONTRIBUTIONS

even at the atomic level. New technologies are applied to design of
catalysts toward precise construction of active sites and environmental XZ summarized the literature and wrote the paper. GZ made the
protection in the preparation process. Moreover, the preparation of manuscript design, writing-reviewing and funding acquisition.
the catalyst and the molding technology are no longer independent, CS made the writing-reviewing, editing and supervision. XG
but the synthesis of catalyst from the precursor to the industrial made the writing-reviewing, editing, supervision and funding
catalyst is realized in one step to eliminate the current amplification acquisition. All authors contributed to the article and approved
effect of the catalyst in industrial applications. In the future, the reactor the submitted version.
integrates the functions of CO2 capture from air, methanol synthesis,
in situ by-product H2O removal and further conversion of methanol
(Figure 12). With the development of distributed wind and solar FUNDING
energy, energy generation will gradually decentralize. Fragmented
forms of energy utilization also require development of CO2 The authors acknowledge funding from the National Key Research
capture units, separation units and conversion units toward the and Development Program of China (2016YFB0600902-4), National
direction of assembly and modularization. Promoting the Natural Science Foundation of China (21902019), and the
development of CO2 conversion process toward high integration, Fundamental Research Funds for the Central Universities
green and efficient process. (DUT20RC(5)002).
photoreduction. Chem. Mater. 30, 799–806. doi:10.1021/acs.chemmater.

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Catalytic Conversion of Carbon Dioxide To Methanol

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published: 09 February 2021

Catalytic Conversion of Carbon

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FIGURE 4 | Growth in global utilization and emission of CO2. Note:

fuels (Satthawong et al., 2013), chemicals and building materials

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Methanol can be integrated into the current energy system and

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stranded supplies of natural gas, such as the United States. Based

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TABLE 2 | Optimization parameters of techno-economic analysis and current data.

Electricity Cost of Cost of STH efﬁciency Methanol yield Methanol

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within 100 h (Chen et al., 2019b). In short, the conversion of CO2

New Catalyst Development

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the synergistic effect among multiple components. The

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to engineer catalytic materials with desired structure in nanoscale or AUTHOR CONTRIBUTIONS

photoreduction. Chem. Mater. 30, 799–806. doi:10.1021/acs.chemmater.

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