Journal of CO2 Utilization 65 (2022) 102239

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Journal of CO2 Utilization

journal homepage: www.elsevier.com/locate/jcou

Review article

Review of carbon dioxide utilization technologies and their potential for

industrial application
Changsoo Kim a, Chun-Jae Yoo a, Hyung-Suk Oh a, b, Byoung Koun Min a, c, Ung Lee a, b, c, *
a
Clean Energy Research Center, Korea Institute of Science and Technology, Hwarang-ro 14-gil 5, Seoul 02792, Republic of Korea
b
Division of Energy and Environmental Technology, KIST School, Korea University of Science and Technology (UST), Hwarang-ro 14-gil 5, Seoul 02792, Republic of
Korea
c
Green School, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul 02841, Republic of Korea

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

Keywords: With the evermore increasing interest in climate change world-wide, various studies are being conducted with
Carbon dioxide utilization the aim of reducing CO2 emissions. The Paris Agreement vows a decrease of carbon emissions by 32 % until
Level of development 2050, and thus strategic pathways have to be set to achieve this immense goal. Carbon dioxide utilization (CDU)
Industrial application
technologies are deemed as one of the most practical methods to achieve large amounts of CO2 reduction, but
careful analysis and application plans are required to obtain the maximum efficiency regarding CO2 emissions
reduction. In this paper, various CDU technologies are reviewed in terms of efficiency, maturity, and cost. First
the various CDU technologies are sorted according to their application status and the CO2 utilization capacity of
the technology. Then each of the technologies are reviewed in detail, then their current maturity and potential
for long-term usage are reviewed regarding the various studies conducted world-wide. Finally, insight is pro­
vided on how the various methods can be integrated to practically achieve the CO2 emission reduction goal. The
purpose of this review is to provide an overview of the current CDU status, and to possibly give insight into the
practical applications and future strategies for achieving a net-zero environment.

1. Introduction Among the various options for CO2 mitigation, carbon dioxide uti­
lization (CDU) is considered as a readily-applicable option in the short to
Controlling the amount of greenhouse gas emissions and conse­ mid-term. The idea of CDU is to convert the captured CO2 into valuable
quently mitigating global warming and related climate problems is products such as fuels, chemicals, and minerals, or utilize them for
deemed as a global task. CO2 is the main contributor to global warming business applications such as enhanced oil recovery (EOR). While
and climate change, of which the global emissions from energy com­ various studies suggest a bright future for the different CDU applica­
bustion and industrial processes added up to 36.3 Gt in 2021 [81]. The tions, not many of the options qualify for the three important aspects of
United Nations Framework Convention on Climate Change (UNFCCC) CDU: long-term carbon fixation, economic feasibility, and large-scale
proposed a treaty to limit global warming to below 2 ∘C, preferably to application. Often is the case where seemingly sustainable CDU appli­
1.5 ∘C, namely the Paris Agreement in 2015 [170]. The consequences of cations fail to achieve sufficient profitability, or is not suitable for large-
global temperature increase larger than 1.5∘C are serious and extensive, scale CO2 reductions in the scale of millions of tonnes per year. To
as provided in the recent report from the Intergovernmental Panel on effectively choose mitigation options and commercialize processes in
Climate Change (IPCC) [83]. While immediate and intense actions are association with the industrial sector, it is important to acknowledge the
required to achieve the goal set by the Paris Agreement, practical ap­ development stages of the different CDU options, and their potential for
plications which are capable of reducing CO2 on a large scale are far industrial application.
from realizable, and many countries are still conducting research and Along with the technological aspects, it is essential to discuss CDU
searching for the right option to delve into as the main strategy for applications in accordance with the related market and policy trends.
tackling the climate crisis. Since CDU applications tend to be operated at a national scale, the

* Corresponding author at: Clean Energy Research Center, Korea Institute of Science and Technology, Hwarang-ro 14-gil 5, Seoul 02792, Republic of Korea.
E-mail addresses: [email protected] (C. Kim), [email protected] (C.-J. Yoo), [email protected] (H.-S. Oh), [email protected] (B.K. Min), [email protected].
kr (U. Lee).

https://doi.org/10.1016/j.jcou.2022.102239
Received 29 July 2022; Received in revised form 9 September 2022; Accepted 19 September 2022
Available online 30 September 2022
2212-9820/© 2022 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

policies regarding the organization of a greener economy, such as car­ methane reforming (SMR) reaction, where methane is reacted with
bon credits, carbon tax, and government subsidies to the industries, are water to generate a mixture of CO and H2, or syngas. Eqs. 2 and 3 shows
essential for motivating the projects. Formation of CDU product markets the methanol production via hydrogenation of CO and CO2, respec­
are also greatly affected by these policies, since additional taxation of tively. Eq. 4 shows the reverse water-gas shift (RWGS) reaction, which is
non-CDU products can invertly promote the profitability of CDU prod­ a competing reaction of Eq. 3. Most of the conventional methanol is
ucts. Overall, to determine specific CDU projects of interest and to focus produced by sequentially reacting Eq. 1 and then Eqs. 2 and 3, where a
on selected technologies for development, it is essential to understand small amount of CO2 is added to the syngas produced from Eq. 1, to
the market and policy trends related to CDU, along with the techno­ increase the reaction rate.
logical development of the separate technologies. For CDU methanol, the main reaction is Eq. 3, where CO2 is directly
In this review, CDU technologies regarding the production of reacted with 3 moles of H2 to produce methanol and water. However,
chemicals and fuels, are reviewed based on their stage of development since the enthalpy change is larger negatively compared to the CDU
and industrial application potential. Also, the market and policy trends pathway, the conventional pathway is preferred from a thermodynamic
of leading countries in the development of CDU technologies are pre­ point of view. Thus the equilibrium yield of methanol production via Eq.
sented, to provide insight into the global association of CDU develop­ 2 is over 80 % at 200 ∘C, while equilibrium yield of the Eq. 3 only shows
ment. Details of each technology are provided in comparison with the 40 %. Additionally, at higher temperatures, the reverse water-gas shift
conventional methods, usually incorporating petrochemical products, reaction (Eq. 4) is promoted, resulting in lower methanol selectivity.
along with their carbon mitigation capacity and trends within the
CH4 + H2 O→CO + 3H2 , ΔH298K = − 206.2kJ∕mol (1)
academia and the industrial sector. The various CDU technologies are
divided into three categories: technologies in the demonstration phase,
CO + 2H2 →CH3 OH, ΔH298K = − 90.5kJ∕mol (2)
technologies in the development stage having potential for large-scale
applications, and technologies in the development stage having poten­ CO2 + 3H2 →CH3 OH + H2 O, ΔH298K = − 49.3kJ∕mol (3)
tial for small-scale applications. In Section 2, CDU options in the
demonstration phase are introduced, including specific projects CO2 + H2 →CO + H2 O, ΔH298K = 41.2kJ∕mol (4)
regarding the actual pilot plant under operation. In Section 3, CDU
options in the development phase, such as carbon monoxide (CO) or Due to these limitations, the main focus of development for
fuels, having the potential of large scale application, are introduced. In increasing the yield of direct CO2 hydrogenation are the development of
Section 4, CDU technologies in the development phase with small novel catalysts and design of new process configurations for efficient
markets are introduced. These options are introduced because although energy usage.
the current market size is comparably small, it has the potential for CDU methanol is produced by incorporating the commercialized Cu/
exponential growth in the future, due to development of related tech­ ZnO/Al2O3 catalyst developed by the Imperial Chemical Industries (ICI)
nologies and changes in government policies. In Section 5, the market [36,176]. The operating conditions of the reaction are in the tempera­
and policy trend is considered for the CDU technologies, and related ture range of 230–300 ∘C, and a pressure range of 50–100 bar. However,
projects are reviewed. In Section 6 the future perspectives of CDU the Cu/ZnO/Al2O3 catalyst has numerous limitations, mainly where
technologies are provided, and the paper is finalized with conclusions in water produced as a byproduct significantly deactivates the catalytic
section 7. performance [112]. Thus various studies have conducted research on
improving the Cu/ZnO/Al2O3 catalyst, by identifying the active sites of
the catalyst and providing variations to enhance performance. Behrens
2. CDU technologies in the demonstration phase
et al. [39] identified the catalyst active sites using a combination of
experiments, imaging methods, and density functional theory (DFT)
2.1. Methanol synthesis
calculations. They showed that the active sites consist of Cu steps with
Zn atoms, and that they are stabilized by bulk defects and surface spe­
2.1.1. Overview of technology
cies. Kuld et al. [105] have presented results on quantifying the per­
Methanol is one of the most widely used chemicals throughout the
formance enhancement effect provided by ZnO during catalyst
world, with annual demand of 98 Mt in 2019 and global production
reactions. By combining experiments with DFT calculations, they
capacity of 150 Mt [84]. Methanol is mainly used as a raw material for
showed that the Zn coverage on the Cu surface is essential for methanol
synthesizing hydrocarbon compounds such as formaldehyde, ethylene,
productivity, showing a monotonic increase up to the level of 0.5. Wu
and propylene, via the methanol-to-olefins (MTO) reaction. Also, it is
et al. [183] proposed the use of inverse ZrO2/Cu catalysts with tunable
incorporated as fuel by itself, or as a blend with gasoline or diesel
Zr/Cu ratios for CO2 hydrogenation to methanol. The prepared catalyst
components. As mentioned in the work by Olah [132], methanol has the
consisting of 10 % ZrO2 supported over 90 % of Cu showed a methanol
potential to become a base chemical for the economy, serving as raw
formation rate 3.3 times higher than a conventional Cu/ZrO2 catalyst.
material for chemical compounds and as a fuel. There is also a growing
Schematic description and the performance of the inverse catalyst is
market for direct methanol fuel cells (DMFCs), or the use of methanol as
shown in Fig. 1 (a) and (b), respectively.
a hydrogen carrier, in preparation for the hydrogen economy. Accord­
Additional studies have been conducted to revise process configu­
ingly, the methanol market has large potential for growth and, despite
rations capable of maximizing energy efficiency. Such studies include
the technical barriers that need to be overcome, such as low conversion
efficient removal of heat emitted during methanol production [201],
and selectivity during synthesis, methanol is currently one of the most
and increasing the equilibrium yield by selectively removing water from
probable candidates for large-scale CDU application.
the product via membrane reactors [54].
Mainly two strategies exist for CDU-based methanol production: (1)
The second strategy for CDU methanol production, to first produce
direct hydrogenation of captured CO2 to produce methanol, and (2)
syngas using CO2, and then to convert the produced syngas to methanol,
producing CO by utilizing CO2, via either electrochemical reduction or
is being studied from various viewpoints as well. Joo et al.[90] devel­
the reverse water-gas shift reaction, and reacting it with H2 obtained via
oped the Carbon Dioxide Hydrogenation to Methanol via RWSG
an environmental pathway, such as water electrolysis.
(CAMERE) process, which sequentially produces CO via Eq. 4, and then
produces methanol by adding H2. The developed process was built as a
2.1.2. Current stage of development and research trends
pilot plant with 66 % methanol yield, producing 75 kg/d of methanol
Currently most of the conventional methanol production rely on coal
[137]. Another example is the complex reforming of methane-H2O-CO2.
gasification and natural gas reforming processes. The related equations
Since the methane-H2O reforming and methane-CO2 reforming
for methanol production are presented in Eqs. 1-4. Eq. 1 shows the steam

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C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

Fig. 1. (a) Schematic of the reaction behavior of the inverse ZrO2/Cu catalyst proposed by Wu et al. [183], compared to the conventional Cu/ZrO2 catalyst. (b)
Catalytic performance of the inverse catalyst with respect to the change in ZrO2 composition, at reaction conditions of 220∘C, 30 bar, and CO2 to H2 ratio of 1:3.
Reprinted from Wu et al. [183].

processes both produce syngas with inappropriate ratios of CO and H2, due to variety of products. Unlike CDU-based fuels or chemicals which
the two reactions are incorporated simultaneously to produce syngas are combusted during usage, polymers are used as their end-product
products with CO:H2 ratio of 1:2. forms. Also, after the end of product life polymers may be recycled to
reproduce polymers, which prevents re-emission of CO2 back into the
2.1.3. Industrial applications atmosphere. Regarding the related markets, CDU polymers are capable
Industrially, research has been focused on using renewable energy of displacing the petrochemical-based polymer production market, and
and CO2 to produce methanol, since it has the effect of mitigating carbon also have the potential to create new markets with development of novel
emissions. An industrial scale version of such a process has been built by materials. The overall polymer market was valued at 533.6 billion USD
the Carbon Recycling International (CRI) Inc. in 2012, incorporating the in 2019, and is expected to expand with an annual growth rate of 5.1%
fluegas obtained from a nearby geothermal power plant, and the H2 from 2020 to 2030 [25], having potential as a suitable market for CDU
obtained by electrolysis of water to produce 4 Gt/y of methanol [6]. The products.
methanol plant uses the Cu/ZnO/Al2O3 catalyst [73], and the produced
methanol is mainly utilized for gasoline blending or for biodiesel pro­ 2.2.2. Current stage of development and research trends
duction [59]. A commercial-scale facility of CRI is currently under Various materials can be incorporated for polymer production via
construction in Anyang, China, with an expected capacity of 110, CO2, including the already commercialized polymer monomer pre­
000 t/y of methanol production. cursors with carboxylate, ester, lactone, carbonate, and carbonyl func­
Progress has been made in terms of catalysts as well. In 1996, the tional groups. These are all in the form of containing the molecular
Research Institute of Innovative Technology for the Earth (RITE) and the structure of carbon dioxide as it is or maintaining at least one C– –O
National Agriculture and Food Research Organization (NIRE) of Japan bond, so it is possible to reduce the complex process of converting to an
co-created a commercial catalyst by combining ZrO2 and SiO2 to the active state such as excessive hydrogenation of carbon dioxide when
widely used Cu/ZnO/Al2O3 catalyst [149]. By incorporating the devel­ producing a carbon dioxide polymer, so it is possible to secure a rela­
oped catalyst and recycling the unreacted syngas, they were able to tively economical process. A representative example of a technology for
produce methanol at 250∘C and 50 bar, with a purity of 99.9 wt%. Based converting CO2 to a monomer is the ethylene carbonate (EC)
on this accomplishment, the Mitsui Chemicals Inc. constructed a pilot manufacturing technology, which can be a raw material for poly­
plant producing 100 Mt/y of methanol in 2008. This plant consists of carbonate, and a representative example of a technology for direct
CO2 from fluegas and H2 acquired from solar energy driven electrolysis, conversion to a polymer compound is the production of polyether car­
making it a environment-friendly process [18]. bonate polyol, which is the main component of polyurethane.
In 2011, Air Liquide Inc. published a study regarding the production Since many CDU-based polymer products have been commercial­
of methanol from pure CO2 [139]. The commercial Cu/ZnO/Al2O3 ized, recent studies are focused on developing new pathways for poly­
catalyst was used, and the constructed pilot plant included a loop reactor mer precursors, to reduce energy usage and to enhance profitability and
with a methanol liquefier, showing a carbon conversion of 94–96.5%. carbon footprint of the products. Various studies have focused on
While the productivity of the proposed process was lower than con­ copolymerization of epoxides and CO2 which leads to the production of
ventional methanol production processes using syngas, compared to the polyalkylene carbonates or cyclic organic carbonates, which can be
conventional process it has the advantage of producing high purity further processed into polyether(-polycarbonate)s, or polyhydroxyur­
methanol in similiar conditions of gas hourly space velocity, tempera­ ethanes [188]. The various routes of epoxide and CO2 copolymerization,
ture, and pressure, where approximately 65% of the side products such are provided in Fig. 2. The reaction of epoxides and CO2 may follow the
as esters, hydrocarbons, ketones, and C2 + alcohols, were reduced. reaction route of (a) polyalkylene carbonates production, or (b) cyclic
organic carbonates production, depending on the catalyst type and re­
action conditions [120,126]. While polymers resulting from route a)
2.2. Polymer synthesis have found applications in biomedicine and polyurethane foams, new
applications are being investigated for the reaction route b), where
2.2.1. Overview of technology various forms of polymers can be synthesized depending on the type of
The advantages of polymer synthesis with regards to carbon emission epoxides. Representative applications of route b) are the preparation of
mitigation is that it can fix carbon as a product in longer durations than polyhydroxurethanes to produce non-isocyante polyurethanes (NIPUs),
other CDU-based products, and that the potential market size is large

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C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

Fig. 2. Various routes for CO2 polymerization to epoxides. Reprinted with permission from Yadav et al. [188] Copyright (2019) John Wiley and Sons.

which allows mitigating the use of isocyanates, which are toxic material by Asahi Kasei, where CO2 is utilized to produce polycarbonates (PC)
used for conventional production of polyurethane [40,95,156]. and high purity ethylene carbonates (EC). Their process producing CDU
PC was commercialized with a plant capacity of 150,000 t/y, and is
2.2.3. Industrial applications capable of reducing CO2 emissions (0.173 t/tPC) as well as substituting
Various economically viable CDU-based polymers have been the use of highly toxic phosgenes used in the conventional process [65].
commercialized, such as polycarbonate (PC), polyol and polyurethane A more recently developed process for producing high purity EC was
(PU) production. Covestro Inc. is one of the companies which have constructed with a capacity of 38,000 t/y EC, produced for developing
commercialized carbon-based polymer production. Their polyether- the solvent for lithium-ion batteries [1].
polycarbonate polyol product, cardyon™, is known to reduce CO2 Newlight Technologies, Inc. developed a CDU-based high perfor­
emissions by 20 % compared to the conventional polyol production mance thermoplastic, named AirCarbon®. AirCarbon®is produced by
process [140], and is used to create flexible polyurethane foams. Their re-assembling carbon, oxygen, and hydrogen, where carbon is obtained
core work was to develop a process to displace conventional polyol with by extraction from CH4 or CO2, incorporating a biocatalyst developed by
a carbon-based polyol, which was based on the development of a double Newlight Technologies [19]. The process for producing AirCarbon®was
metal cyanide catalyst. Covestro AG built a demo sized plant in 2016, commercialized in 2013, and the products are being provided to
producing 5,000 ton/y of polyol using CO2 obtained from a neighboring customer companies for use as packaging material.
chemical facility [10].
Novomer Inc. is also one of the leading companies in the production 2.3. Urea synthesis
of polyol. Their research is focused on the catalytic conversion of CO2 to
produce polycarbonate polyol, polypropylene carbonate, and poly­ 2.3.1. Overview of technology
ethylene carbonate. Development of the Salen-Co based homogeneous Urea was first obtained by Friedrich Wohler in 1828 by reacting
catalyst sparked the research on CO2 conversion, and their recent output silver cyanate with ammonium chloride. Mass production became
of polypropylene carbonate for polyurethane production (Converge®) available later on when Basarov started producing urea using ammonia
can displace the conventional petrochemical-based polyol, including up and CO2, and process development enabled economically efficient pro­
to 50 % of CO2 within their structure. Also, LCA of their polyol process duction of urea. It is mainly used as agricultural fertilizer, and is also
shows carbon emission mitigation of 67% compared to conventional utilized as a NOx reduction agent in diesel vehicles, a monomer for
polyol production processes [53]. The technology and production rights polyurethane and an additive for cosmetics. The worldwide production
of Converge®have been taken over by Saudi Aramco on 2016, and of urea was 233 Mt in 2019, and is estimated to increase to 300 Mt by
global market production is currently under development [29]. 2030 [30].
The Mg-based catalyst for efficient production of polyols, developed
by Econic Technologies, is currently in its pre-commercialization stage 2.3.2. Current stage of development and research trends
[12]. The Mg-based catalyst promotes epoxy copolymerization of Recently, studies are being conducted to increase the yield rate of
polyolefins and cyclohexene oxides, which results in the production of urea and also to produce it while reducing carbon emissions. Urea
polyols and polyurethane. A key point of their technology is that the CO2 production via ammonium carbamate (AC) decomposition is one of the
composition within polyol is increased, due to the use of a homogeneous representative methods. The related reactions are shown in Eqs. 5 and 6.
polyol catalyst.
Another application of CDU-based polymer is the process developed 2NH3 + CO2 →NH2 COONH4 (5)

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C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

NH2 COONH4 ⇌H2 N(C = O)NH2 + H2 O (6) These types of substitution reactions utilize Cs-based or K-based
catalysts. When an amine is deprotonated the basic condition of the
As shown in the reaction equations the overall process is a 2-step catalyst is relevant, and thus CO2 utilization in urea production is ad­
reaction. In the first step, AC is produced in an exothermic reaction, vantageous when alkylamine is the substrate. However, when the sub­
then in the second step, the AC is dehydrated to form urea in an endo­ strate is an aromatic amine, only benzylamine is available. CO
thermic reaction. While Eq. 5 reacts spontaneously with an ammonia to utilization shows higher reactivity compared to CO2 utilization, in the
CO2 ratio of 2–3 vol% in a temperature region of 180–210 ∘C and a presence of a catalyst and an operating condition of 100–120 ∘C. How­
pressure of 150 bar without a catalyst, Eq. 6 is a slow equilibrium re­ ever CO is more expensive compared to CO2 and also toxic, raising safety
action, and a commercial catalyst for intensifying the yield rate is yet to issues during process operation. A CO2 utilization process has to be
be developed. The created urea is retrieved in low pressure, then the operated at a temperature of 170–180 ∘C, to activate the thermody­
unreacted AC is recycled back into Eq. 5. Thus it is essential to enhance namically stable CO2. Also, H2O is produced as a byproduct, meaning
the process performance of the recycled NH3 and CO2, to maximize the that the catalyst has to be stable enough not to undergo hydration in
yield rate. Accordingly, recent studies are focused on enhancing Eq. 6, high temperatures. By optimizing the process, eliminating the water
by means of inorganic catalysts such as Cu(II) and Zn(II), or organic byproduct can increase the yield rate by promoting the forward reac­
catalyst such as DBU. One example is the study by Barzagli et al. [37], tion. Recent studies show that with the appropriate selection of anions,
where the production of urea at a mild condition of 100∘C and 3.7 bar even Cs-based catalysts are stable in hydration conditions, providing
was reported. Results of the study show that, using an organic catalyst high yield of over 95% and a turnover frequency (TOF) of 858h− 1.
DBU with the DMSO solute, an yield rate of 35% was achieved. Various efforts have been made on the production of disubstituted urea
Other research efforts are being made from a more eco-friendly via the production of a novel catalyst. Choi et al. [47] proposed the use
perspective, such as urea synthesis via an electrochemical reaction of of K3PO4 to catalyze the amine-CO2 carboxylation for producing 1,
N2 and CO2 in aqueous conditions. Chen et al. [45] published a study to 3-disubstituted ureas with high yields. The schematic of the reaction
electrochemically generate urea under ambient conditions, by simulta­ and the catalyst configuration is shown in Fig. 3(b) Truong et al. [167,
neously fixing N2 and CO2. A flow reactor cell was fabricated with a 168] presented the use of alkali metal azolides as catalysts for ami­
working electrode with Pd-Cu nanoparticles supported on TiO2 nano­ ne-CO2 carboxylation to disubstituted ureas. Nguyen et al. [129] pro­
sheets as catalysts, a Ni foam anode, and an electrolyte based on an posed the use of polystyrene-functionalized basic ionic liquids (PS-BILs)
aqueous KHCO3 solution. The proposed reaction mechanism is illus­ as catalysts for producing disubstituted ureas. Among the various can­
trated in Fig. 3(a). First, the N2 molecules are chemisorbed onto the didates the [bis-imidazolium]/[bis-bicarbonate] showed the highest
catalyst surface, forming activated N2 with reduced N–N bond order. activity and good recyclability of up to seven consecutive runs.
The existence of activated N2 promotes CO2 reduction to occur on
adjacent metal sites, forming CO. Then the intermediate *NCON* is 2.3.3. Industrial applications
formed, which is subsequently hydrogenated to produce urea, at a CDU-based urea production is a mature technology, where all of the
Faradaic efficiency of 8.92 % at − 0.4 V vs. reversible hydrogen elec­ urea production incorporates CO2 as raw material. The expected de­
trode (RHE). This research shows the potential for converting the con­ mand of urea is estimated to expand at a growth rate of 2.1% between
ventional process, which requires high initial investment costs and 2021 and 2026, forming a market size of 212 million USD [32]. Thus
energy input, into a low-energy, low-cost small scale process, which urea production is expected to play a significant role as a main CDU
allows localized production of urea in different parts of the world. application. The role of industries would be to develop optimized pro­
Various forms of research are being conducted to commercialize an cesses for cost efficient production of urea, such as integrating the en­
alternative route to produce urea. One of the representative research ergy loss from the ammonia production process.
results is to produce disubstituted urea, such as 1,3-dialkyl urea or 1,3-
diaryl urea, via carbonylation of CO or CO2 [75,99–101,154]. These
reactions are shown in the equations below: 2.4. Mineral carbonation
1
2RNH2 + CO + O2 →RNH(C = O)NHR + H2 O (7) 2.4.1. Overview of technology
2
Incorporating CO2 to mineral as a CDU application was first pro­
2RNH2 + CO2 →RNH(C = O)NHR + H2 O (8) posed by Seifritz [153]. Mineral carbonation technologies produce
carbon-based minerals by reacting CO2 with industrially developed

Fig. 3. Two examples of recent approaches for CDU-based urea production. (a) The use of Pd-Cu alloy nanoparticles on TiO2 nanosheets as catalyst in electro­
chemical conversion of CO2 to urea under ambient conditions. Reprinted from Chen et al. [45] Copyright (2020) Springer Nature. (b) Using K3PO4 as a catalyst for
CO2 carboxylation of amines to urea. Reprinted from Choi et al. [47] Copyright (2014) Elsevier.

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C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

inorganic byproducts. Main products of mineral carbonation include

calcium carbonate (CaCO3) and magnesium carbonate (MgCO3). Min­
eral carbonation processes can be categorized into two pathways: direct
and indirect carbonation. Direct carbonation is the process of mimicking
the natural process of mineral carbonation, where CO2 is directly
injected to minerals within the geological formations, and heat and
pressure is applied to accelerate the weathering process. The economic
feasibility of the direct carbonation process depends greatly on the
actual amount of heat and pressure required, and thus it is important to
design processes so that waste heat can be utilized.
Indirect mineral carbonation includes an extraction process, where
calcium or magnesium is extracted from minerals in acidic conditions.
Although an additional preprocess is required, indirect carbonation re­
quires milder carbonation conditions and shows higher carbonation
efficiency, compared to the direct carbonation process [116].
Mineral carbonation is considered the most effective option for long-
term carbon storage, since it has less effect on the environment
compared to geological or marine storage, has low possibility of re-
emission into the atmosphere, and the derived products are applicable
as a variety of industrial materials. To improve the economic perfor­
mance of the carbonation process, research efforts have been focused on
recovering valuable byproducts from the process, such as zeolites or
precipitated calcium carbonates (PCC). A preliminary economic analysis
provided in the studies by Chu et al. [48] and Liu et al. [115] have shown
that by selling byproducts such as NH4Al(SO4)2, economic profitability
can be achieved.
MgCO3 is mainly used as a desiccant, and also used as raw material in
various industries, such as pharmaceutical, cosmetics, and the ink in­
dustry. CaCO3 is widely used in the paper-making, paint, and concrete
industry. Also, it has low reactiveness and high absorption rate within
the body, making it a viable option as an inert filler and as a coating
agent in capsules used in the pharmaceutical industry.
Fig. 4. (a) Process flow diagram for producing NaHCO3, MgCO3, or CaCO3
2.4.2. Current stage of development and research trends from industrial caustics. The HE block represents the heat exchanger. Reprinted
Since the reaction of mineral carbonation does not require the use of from Kelly et al. [96] Copyright (2011) Elsevier. (b) Possible usages of CaCO3
catalysts or complex reaction paths, studies focus on developing path­ and MgCO3 via integration with other processes. Reprinted from Woodall
ways for incorporating various types of waste materials as sources of Ca/ et al. [182].
Mg, or integrating the obtained CaCO3 or MgCO3 with processes for
producing value-added products. Different types of wastes include blast developed process was able to produce CaCO3 with a purity of 99.0 %,
furnace slag, steel slag, waste gypsum, industrial caustics, coal fly ash, mitigating CO2 by 0.465 kg per process cycle, taking into account the
etc., and potential final product applications include cement ingredient, energy usage.
paper filler, fertilizer, etc. Typical process flow diagram of CO2 miner­ Studies focused on enhancing the economic feasibility include the
alization, and various options for converting the produced CaCO3 and approaches for recovering silica and aluminum resources from industrial
MgCO3 into other chemicals, are presented in Fig. 4(a) and (b), solid waste, while using CaO and MgO for CO2 fixation. Tong et al. [166]
respectively. developed a new process for simultaneously obtaining CaCO3, Fe, and
Ren et al. [142] employed different salt solutions to enhance the glass ceramics without wastewater, via reaction of steel slag and CO2.
direct carbonation process of blast furnace slag. Under reaction condi­ NH4Cl was used for leaching residue of the steel slag. Chu et al. [48] used
tions of 150∘C, CO2 pressure of 30 bar and using 1 mol/L NaCl solution NH4HSO4 to leach blast furnace slag, producing valuable resources such
as the reagent, the CO2 mineralization capacity of 280 kgCO2/tBFS was as ammonium alum and silica, and achieving CO2 mitigation of
obtained. It was shown that the saline solution promotes the dissolution 361 kgCO2/tBFS. Other studies focus on processes for producing
of calcium and enhances the CO2 mineralization process, by increasing precipitated calcium carbonate (PCC), which is basic raw material for
the effective acidity of the solution. Ghacham et al. [71] studied the plastics, coatings, and pesticides. Song et al. [158] studied the produc­
efficiency of steel slag carbonation, considering the effect of various tion of high-purity PCC via mineral carbonation of flue gas desulfur­
parameters such as gas pressure, liquid/solid ratio (L/S), gas/liquid ization gypsum. Analysis of operating conditions revealed that the
(G/L) ratio, and reaction time on the CO2 carbonation capacity. maximum formation efficiency for PCC was affected by the ammonia
Parameter analysis showed that the G/L and CO2 pressure have a posi­ content, and the S/L ratio. He et al. [78] proposed a novel process for
tive effect on the conversion of CO2, and by optimizing the parameters utilizing coal fly ash to produce high-purity PCC, where recyclable
the system achieved a carbonation capacity of 52 kg per tonne of slag. ammonium salt, such as NH4Cl, NH4NO3, and CH3COONH4, were used
Yu et al. [194] proposed to employ the coal fly ash carbonation process the extract calcium from coal fly ash prior to the carbonation process.
as an amine regeneration process, integrating it with a sterically hin­ Although in its early stage of development, the use of ultrasound is
dered amine-based CO2 absorption to maximize the energy efficiency. gaining attention as a process intensification method for mineral
The integrated CO2 absorption-mineralization (IAM) process was able to carbonation. Ultrasound can promote the mineral carbonation process
eliminate the need for an amine regeneration process, greatly decreasing by applying sound waves in the range of 16–100 kHz to enhance the
the overall energy usage. Park et al. [136] reported the use of waste mixing process, and accelerate the particle breakage and carbonate
concrete as the source of calcium, and the operation results of the passivation layer removal [150,152]. Several studies have provided
pilot-scale plant with a capacity of producing 20 kg/d of CaCO3. The

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promising results regarding mineral carbonation using ultrasound. Said 3.1. Carbon monoxide
et al. [148] showed the enhanced performance of calcium extraction
from steel slag using ultrasound. Their results showed that ultrasound 3.1.1. Overview of technology
can remove the porous layer which forms after calcium is liberated from Carbon monoxide (CO) is obtainable from CO2 reduction, and has
the slag, extracting 96 % of the Ca in the smallest particles of the slag. high industrial value while retaining large CO2 mitigation potential.
Santos et al. [151] presented results on the improved performance of Stoichiometrically, 1 mol of converted CO2 produces 1 mol of CO, which
mineral carbonation to produce aragonite, with the use of ultrasound. means that 1.57 tCO2 can be consumed by producing 1 tonne of CO.
The use of ultrasound reduced the required concentration of Mg, as well Upon mixing with H2 to obtain syngas, the widely utilized Fisher-
as decreasing the reaction temperature to 24–70 ∘C. A recent study by Tropsch process allows the conversion of syngas to a variety of hydro­
Wang et al. [173] presented the conversion of gypsum to CaCO3 via carbons and other value-added chemicals, making CO an attractive
ultrasonic carbonation, where pure vaterite was obtained by applying option for commercial CDU application. Also, syngas can be processed to
50 % ultrasonic amplitude for 30 min. While scale-up of the produce methanol, which is a valuable chemical on its own, and can also
ultrasound-integrated process is yet to be realized, and current limita­ be further processed to produce olefins via the MTO reaction, as intro­
tions such as large amounts of electricity usage [133] must be dealt with, duced in Section 2.1. Furthermore, 99 % of the CO produced within the
ultrasound may prove to be an effective mineral carbonation route in the steel industry is collected and reused within the facility or used to create
near future. electricity in power plants, providing diverse applications for large scale
CO2 mitigation.
2.4.3. Industrial applications CO can be obtained from CO2 through various pathways, such as
The carbonated mineral market consisting of products produced electrochemical, catalytic, photochemical, and plasma conversion.
from conventional processes is estimated to be 10–60 billion USD/y, and Electrochemical conversion of CO2 can be considered a green process if
is expected to increase to 550 billion USD/y in 2030. Due to this large the electricity produced from renewable energy sources, such as solar or
market potential, various construction companies are investing on the wind power, can be utilized. Photochemical conversion processes
CDU mineral carbonation process, such as Blue Planet, Calera, Skyonic, directly incorporate solar energy, and allows production of chemicals
Carbicrete, Carbon Capture Machine, and Carbon8 Systems. The Calera with minimal CO2 emissions given the appropriate light source and
Corp has published over 250 patents on the mineral carbonation pro­ catalyst. Plasma conversion allows rapid heating required for the
cess, in which electrolysis is used to separate Ca and Mg used for methane reforming process, by adjusting the frequency of plasma gen­
carbonation. eration. While the carbon abatement potential of these technologies are
The Sleipner project injects CO2 into the Utsira saline formation of clear, additional research is required for large scale demonstration of
the North Sea [38]. It is estimated that 30 million tonnes of CO2 will be these technologies to take part in the CO2 mitigation objectives.
stored in the Utsira saline formation over the project life time of 30
years. 3.1.2. Current stage of development and research trends
CarbonCure Technologies developed a CO2 curing process to pro­ Electrochemical CO2 reduction technologies producing CO can be
duce concrete, where liquid CO2 is injected into a pressurized tank categorized according to the operating temperature. Low temperature
where wet concrete is being mixed. The efficiency of CO2 absorption into electrochemical conversion is processed at temperatures below 100∘C,
the concrete is known to be approximately 50–80 % [124]. The process and make use of polymer membranes and acidic or basic aqueous
can be retrofitted into existing concrete plants, and is currently being electrolytes. Water is first decomposed into O2 and hydrogen ions at the
widely applied in ready-mix concrete plants in North America [8]. anode, then the produced hydrogen ion is transferred through the
Carbon8 Systems developed the Accelerated Carbonization Tech­ membrane to participate in reduction reactions with CO2, producing
nology (ACT), which utilizes CO2 to mineralize various thermal wastes, valuable chemicals such as CO, formic acid, methane, and alcohols [64].
including steel slags, incinerator ash, etc. [7] The first ACT plant was The specific products obtained from electrochemical systems differ ac­
built in 2012, which produces more than 65,000 t/y of carbonated cording to the catalyst and membrane type. Among the different cata­
products, namely CircaBuild®, and CircaGrow® [203]. lysts, Au, Ag, and Zn catalysts are known to provide the highest
Carbonfree Chemicals developed a CO2-mineralization process for selectivity for CO production [79]. High temperature electrochemical
manufacturing inorganic products, such as NaHCO3, baking soda, conversion systems operate at approximately 800∘C, and incorporate
caustic soda, etc. The process, namely the SkyMine®process, in­ solid oxides as electrodes and the electrolyte. Upon operation, the
corporates an electrochemical method to produce low-concentration electrical energy provided decomposes the CO2 provided to the cathode
NaOH from salt and water [172]. This solution is used to capture CO2 into CO and oxygen ion. Then the oxygen ion is transferred to the anode
to produce high-purity NaHCO3. The first SkyMine®plant was con­ through the electrolyte to produce oxygen gas by reaction with elec­
structed in 2015, utilizing CO2 at a capacity of 83,000 t/y [9]. trons. High temperature electrochemical conversion incorporate the
Carbfix, which is a carbon fixation frim in Iceland, injects CO2 into cermet family of cathodes such as Ni and Yttria Stabilized Zirconia
basaltic rock, after mixing CO2 with water. Carbfix recently partnered (YSZ), and tend to have a higher conversion rate of CO2 compared to the
up with Climeworks, which is a direct air capture (DAC) firm, to capture low temperature electrolyzers [200], regardless of the type of electrode
4000 tonnes of CO2 per year out of air, and to inject it into basaltic used. Recent research regarding electrochemical CO production focus on
formations in Iceland [3]. Currently an accumulated amount of 81,165 the development and tuning of catalysts to enhance conversion and
tonnes of CO2 have been injected by this process [4]. selectivity, the design of electrolyzers [109], and the design of processes
integrated with the capture process to maximize energy efficiency and
3. CDU in the development phase – Technologies with potential improve profitability. Chung et al. [49] reported the development of a
for large scale reduction catalyst for decomposing CO2 at low temperatures, which is produced by
sputtering of a liquid polymer and shows high stability and produc­
In this section, various technologies that retain potential for large ibility, and also high conversion rate from CO2 to CO. Nguyen et al.
scale CO2 reduction, but with less technological maturity compared to [128] proposed a method for increasing the Faradaic efficiency of CO
technologies in the demonstration phase, are introduced. While these production by adjusting the coverage of reduced graphene oxide layers
technologies are still in the development phase and various hurdles need on porous Zn electrocatalysts. Park et al. [138] recently developed a
to be overcome for commericialization, the large market available for metal-ceramic complex cathodic catalyst which operates at high tem­
these technologies are attracting many corporations and research peratures and shows stable performance even with certain amounts of
groups. impurities included. Characterization images of the developed catalyst

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are shown in Fig. 5. Rosen et al. [146] reported that the CO conversion system is the Re-carbonyl system, where it was reported to selectively
rate is extremely enhanced when ionic liquid is applied to the low produce CO when used in the form of a single component molecular
temperature electrolysis system. catalyst, acting both as a photosensitizer for absorbing light and as a
Catalytic conversion technologies include a wide range of technol­ photocatalyst for accelerating the reaction [77]. Recently, Liu et al.
ogies that utilize catalysts and a reducing agent for converting CO2 to [117] proposed the use of a CuII complex molecular catalyst for reduc­
CO. Dry methane reforming and CO2 hydrogenation reactions are tion of CO2 to CO. Using [Ru(phen)3](PF6)2) as the photosensitizer, the
representative techniques. Dry methane reforming makes use of reaction was carried out with visible light, and the developed catalyst
methane as the reducing agent to convert CO2 to syngas, which has the showed a high TON of 9900 and a CO selectivity of 98 %. Zhang et al.
effect of mitigating two different types of greenhouse gases [85], [197] developed a method for deriving single-atom catalyst from the
methane and CO2. Typical catalyst selections include transition metals metal-organic framework. Using Co as the base metal, pyrolysis of the
such as Ni, Ru, Rh, Pd, Ir, and Pt, which all show high activity when used ultrathin Co metal-organic layers during g-C3N4 formation resulted in
for methane reforming reactions. Among these candidates, Ni shows the the anchoring of single Co(II) sites. The produced photocatalyst showed
highest cost efficiency and is widely studied for commercialization of the a CO evolution rate of 464.1 μmol/gh, which was three times faster than
process. CO2 hydrogenation is the process of employing H2 as the the bulky Co-MOF catalyst. Nguyen et al. [127] developed a novel
reducing agent to reduce CO2 to CO, and different chemicals may be catalyst, Ag-decorated reduced TiO2/WO3 hybrid nanoparticles, for
obtained according to the type of catalyst used. During CO2 hydroge­ converting CO2 to oxygen and CO when exposed to visual rays. The
nation two reactions occur competitively, the reverse water-gas shift catalyst performance was shown to have an apparent quantum yield of
reaction (Eq. 4) and the methanol synthesis reaction (Eq. 3). The 34.8 %, with maximum selectivity of 100 % CO. Won et al. [181] greatly
selectivity of the reaction products are determined by the type of cata­ enhanced the efficiency and life time of a photocatalytic system by
lyst used. CuO-ZnO/TiO2, Cu/ZnO/Cr2O3, and Cu/ZnO/Al2O3 all show applying porphyrin dye.
high selectivity of over 70% towards the production of CO [162]. Song Plasma conversion of CO2 is the process of using non-thermal plasma
et al. [159] recently published a study on the development of the to split CO2 to CO and O2, or via the dry reforming of methane (DRM)
NiMoCat catalyst, which is prepared by placing Ni-Mo alloy nano­ process, where CO2 and methane are converted to CO and H2. Plasma
particles on the magnesium oxide support. The NiMoCat catalyst is re­ conversion has the advantage over catalytic conversions that carbon
ported to have a long life time when used for dry methane reforming, adsorption on catalysts are prevented [157], which is a critical factor of
and shows no sign of coking or sintering. The synthesizing process and catalyst deactivation. Aerts et al. [34] presented the experiments and
images related to catalyst production is shown in Fig. 6. Joo et al. [91] computational analysis results of CO2 splitting via dielectric barrier
implemented the atomic layer deposition (ALD) method to produce a discharge (DBD) plasma. Investigation of the operating conditions
catalyst for dry methane reforming, showing high conversion rate of showed that the discharge gap and the specific energy input (SEI) has a
methane and improved life-time. significant effect on the conversion and energy efficiency. For DRM,
Photochemical conversion is the process of converting CO2 using the recent studies focus on the hybrid application of plasma and catalysts to
excited state electron obtained by solar energy, and various products can maximize the process efficiency. Chu et al. [48] presented the use of
be obtained according to the number of electrons and photons incor­ microwave plasma coupled with a catalytic reactor to convert CO2 and
porated in the reactions. A schematic of the photocatalytic CO2 reduc­ CH4 to syngas under atmospheric pressure. The hybrid system showed
tion process is shown in Fig. 7 Typically for CO production, a approximately twice as high conversion levels for both CO2 and CH4,
homogeneous reaction system based on a transition metal complex is compared to the system using only the microwave plasma.
used. Various options of sensitizers, dopants, radiation sources are Martin-del-Campo et al. [42] proposed the integrated use of the rotating
considered for new catalyst development. An early example of such a gliding arc plasma and Ni-supported catalysts in a spouted bed reactor

Fig. 5. SEM image of the catalyst developed by Park et al. [138]. Reprinted from Choi et al. [47] Copyright (2014) Elsevier. (a) Image of the La0.6Sr0.4Co0.5
Ni0.2Mn0.3O3(LSCNM) and (b) the CoNi-R.P.LSCM catalyst obtained by reducing LSCNM. (c) The TEM and EDS mappings of each of the elements consisting the
CoNi-R.P.LSCM powder.

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Fig. 6. Preparation of the NiMoCat proposed in Song et al. [159]. (a) Synthesizing sequence of NiMoCat. MgO is obtained from combustion synthesis of Mg chips and
CO2, then the MgO nanopowder is dispersed into a Ni and Mo containing salt solution, which is then reduced with hydrazine. Images on the right show TEM and SEM
images of (b) MgO cubes, (c) freshly created NiMoCat, and (d) NiMoCat after reaction. Reprinted from Song et al. [159] Copyright (2020) The American Association
for the Advancement of Science.

Fig. 7. Schematic figure showing the photocatalytic CO2 reduction process.

Reprinted from Wu et al. [184].

for DRM. The reactor image and performance of the proposed system is
given in Fig. 8. Upon experimenting with two different catalysts, Ni
Fig. 8. Reactor image and performance of the system proposed by Martin-del-
supported on Al2O3 or SiO2, maximum selectivity of 96.7 % was ob­ Campo et al. [42]. By integrating the rotating gliding arc plasma with
tained for CO using a combination of plasma and passivated 30 wt% Ni-supported catalysts CO is produced with high selectivity. Reprinted from
Ni/SiO2, and maximum selectivity of 84.9% for H2 was obtained using Martin-del-Campo et al. [42] Copyright (2021) Elsevier.
plasma and fresh 15 wt% NiO/SiO2.
plant [17]. The Nordic Blue Crude is currently constructing a pilot
3.1.3. Industrial applications plant for producing blue crude at a capacity of 10 million liters by 2025.
Progress in CO2 conversion to CO in the industry has been intense The syngas which is used as material for blue crude production is ob­
over the last few years. Considering electrocatalytic conversion, the tained by reacting CO2 with H2 in a RWGS reaction, where the H2 is
Sunfire GmbH integrated the CO conversion process to a fuel production produced by alkaline electrolysis [20].
process, where syngas is produced by co-electrolysis of CO2 and water in Regarding photochemical CO2 conversion, the Sandia National
a high-temperature electrochemical system, then the produced syngas is Laboratory (SNL) of the U.S. Department of Energy (DOE) have
converted to a synthetic fuel named “the blue crude.” Efforts are being demonstrated a Sunshine to Petro (S2P) reactor, which incorporates
made to upscale the process for industrial commercialization [31]. solar energy to produce syngas from CO2 and water [121]. The ther­
Studies on catalytic conversion of CO2 are being conducted mainly mochemical heat engine, i.e., the Counter-Rotating Ring Receiver
by corporations in Germany and Norway. Linde developed a green Reactor Recuperator (CR5), produces CO with input of CO2, and H2 with
process for dry methane reforming, and received funding from the input of H2. Thus syngas can be produced with adjusting the ratio of the
German government for the construction and operation of a pilot-scale operations. However, the current system is incapable of achieving

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efficiencies high enough to compete with other CO producing technol­ catalyst performance by enhancing H2 adsorption, and that the Na
ogies, and further improvements are required for commercialization of promoter increases the CO2 adsorption and inhibits hydrogenation of
the process [122]. olefin, increasing selectivity. Witoon et al. [180] implemented the
ReCarbon Inc. made progress on converting methane-CO2 to syngas Fe/Co/K/Al oxides catalyst for CO2 hydrogenation to olefins, with
via plasma conversion at a foodwaste site, and is recently working on the alternating preparation methods to alter CO2 and H2 adsorption. The
construction of a commercialized power plant based on these results. results showed that by preparing catalysts by precipitation with NH4OH
The Emission Blade, a microwave plasma generation device, conducts as the reducing agent, followed by reduction using NaBH4 as the
DRM to produce syngas in a Plasma Carbon Conversion Unit (PCCU) reducing agent, showed the highest olefin yield of 16.58 % at 350 ∘C and
[26]. 20 bar.
Kolesnichenko et al. [104] studied the conversion of methanol and
DME to olefins using zeolite catalysts modified with Rh compounds.
3.2. Light olefins Their results show that the implementation of Rh centers increases the
selectivity of lower olefins synthesis. Hanaoka et al. [76] studied the
3.2.1. Overview of technology performance of zeolite catalysts for the DEM-to-olefins reaction. The
Light olefins are carbon-based chemicals that compose the building results showed that ferrierite zeolite with NH+ 4 showed the highest
blocks for various polymers. Light olefins include ethylene, propylene, n-butene yield.
and butadiene, and are conventionally obtained by the naphtha cracking Another significant pathway for converting CO2 to olefins is the use
process, ethane cracking process, and coal-to-olefin process from natural of electrochemical reactions, where CO2 is reduced to produce olefins of
gas, coal, and crude oil. The basic conversion equations of this process various carbon numbers, depending on the catalyst used.
are shown in Eqs. 9 and 10. Tomboc et al. [165] proposed the electrochemical conversion
mechanism of CO2 to ethylene, using Cu-based electrocatalysts. They
CO2 + H2 ⇄CO + H2 O (9)
categorized the Cu-based electrocatalysts into four groups, namely
CO2 + H2 ⇄(− CH2 − )n + H2 O (10) metallic Cu, Cu alloys, Cu compounds, and supported Cu-based cata­
lysts, and identified the detailed mechanisms for selective CO2 reduction
Olefins can be obtained from CO2 via thermochemical and electro­ reaction for each of the different types of catalysts. Kim et al. [102]
chemical pathways. For the thermochemical pathway, direct and indi­ synthesized a monodisperse nanoparticle of CoFe2O4 to produce
rect hydrogenation are available options. For direct hydrogenation, Na-promoted CoFe2O4 catalysts supported on carbon nanotubes, which
multi-functional catalysts are used to produce C2-C3 olefins. As for in­ showed high CO2 conversion of 34% and light olefin selectivity of 39 %.
direct hydrogenation, CO2 is first converted to CO, then proceeds with Jeong et al. [86] proposed the method of controlling the spacing be­
the FT reaction, or is further converted to methanol to undergo the MTO tween Cu facets within the atomic-scale to maximize binding energies of
reaction. A summary of the thermochemical reaction routes from CO2 to CO2 reduction intermediates, enhancing the selectivity of C2 + products
olefins is provided in Fig. 9. For the electrochemical pathway, Cu-based during CO2 electrochemical reduction. Yang et al. [191] showed that
catalysts are incorporated to directly produce light olefins by CO2 olefin production from CO and CO2 is possible using Na- and K-pro­
reduction. moted Fe-Zn catalyst. They found that the use of Na- and K-promoters
alters the balance between iron oxides and iron carbides in the catalyst,
3.2.2. Current stage of development and research trends affecting the CO and CO2 conversion. Gao et al. [67] proposed the use of
Since the reactions related to thermochemical conversion of CO2 to bifunctional catalyst composed of indium-zirconium composite oxide
olefins is mature, most of the recently published studies focus on the and SAPO-34 zeolite, with the former composite responsible for CO2
development of catalysts to improve the overall performance. activation and the latter composite responsible for selective C-C
Dorner et al. [56,57] developed catalysts based on Fe, Mn, and K for coupling. The results showed high olefin selectivity as high as 80% at
CO2 hydrogenation to C2-C5 + olefins. The developed catalyst combines CO2 conversions higher than 30 %. Yuan et al. [195] made use of
the RWGS and FT chain growth reactions, and the Fe/Mn/K catalyst acts CoFe2O4 as a catalyst precursor for CO2 precursor, which showed high
as a bifunctional catalyst. Sai Prasad et al. [147] studied the FT reaction selectivity for C2 + hydrocarbons. Analysis of the results showed that
of CO/CO2/H2 bio-syngas with Fe-based catalysts. At reaction condi­ high dispersion of Fe and Co helped inhibit the formation of methane,
tions of 300 ∘C and 10 bar, they obtained 39.19 % distribution of C2-C4 and consequently promoted the formation of longer chain products.
products, with an olefin selectivity of 77.23 % within the C2-C4 prod­
ucts, using a Fe/Cu/Al/K catalyst. Zhang et al. [199] developed the Na 3.2.3. Industrial applications
and Zn promoted Fe catalyst to achieve C2-C12 olefin selectivity of 80 % While various corporations produce olefins via the MTO reaction,
at 39 % CO2 conversion. Analysis showed that using Zn enhances the Fe currently none of the processes are integrated with CDU. This is due to
the fact that overall processes need to be retrofitted and revised to
implement CDU-based applications of olefin production, and that
currently it is not economical to produce olefins as the end-product of an
entire plant. Future developments should be focused on integrating the
existing MTO processes with the CDU-based methanol processes.

3.3. Aromatic compounds

3.3.1. Overview of technology

While the current level of research compared to previously reviewed
technologies is at a novice stage, the conversion of CO2 to aromatic
compounds, such as benzene, toluene and xylene (BTX), is gaining
considerable attention. Two main pathways exist for producing BTXs
from CO2: the Fischer-Tropsch (FT) synthesis pathway, where CO2 is
Fig. 9. Various routes for producing light olefins from CO2 and H2 obtained first converted to C2 + hydrocarbons, then transformed into aromatic
with renewable energy. Reprinted with permission from Centi et al. [43] compounds on zeolites, and the methanol pathway, where methanol is
Copyright (2013) Royal Society of Chemistry. first synthesized from CO2, converted to olefins on zeolites, then finally

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converted to aromatic compounds. 5, CR2O3/HZSM-5, ZnAlOx/HZSM-5, and ZnCrOx/HZSM-5, typically

The FT pathway first produces CO from RWGS reactions, then the CO show low conversion of 10–20 %. Also, since conventional catalysts
is converted to C2 + compounds. The most widely used catalysts are Fe show low selectivity towards aromatic compounds, various studies are
and Co-based, but has the limitation in terms of selectivity, where the focused on compositing HZSM-5 to increase the selectivity of BTX. For
selectivity towards C2 + compounds are limited by the Anderson- the methanol pathway, the conversion tends to be low (9–22 %) and
Schulz-Flory (ASF) distribution limitation[62,63]. The typical selec­ selectivity high (56–74 %), whereas for the FT pathway, CO2 conversion
tivity value of the FT pathway to C2 + hydrocarbons is below 60%. is higher (27–34 %) compared to the methanol pathway but the selec­
The methanol pathway is free from the ASF distribution limitation, tivity is lower (20–53 %).
and typically shows higher selectivity compared to the FT pathway. The Regarding the methanol pathway, the Liu group of Dalian Institute of
C2 + compounds produced via both the FT and methanol pathway un­ Chemical Physics (DICP) conducted various studies on incorporating the
dergo C-C coupling reactions, ring formation and dehydration reactions spinel type ZnAlOx&HZSM-5 catalyst. When the catalyst was used to
on the surface of the zeolite to produce aromatic compounds. react H2:CO2:Ar with a ratio of 3:1:0.2 at 30 bar and 320 ∘C, the con­
version of the reaction was 9 %, and showed an aromatic compound
3.3.2. Current stage of development and research trends selectivity of 76% [130]. The Tsubaki group conducted studies on the
Catalytic conversion of CO2 directly to aromatic compounds is at its subject as well, where reaction of H2:CO2 ratio of 3:1 at 30 bar and
very early stage of development. A majority of the studies conducted on 350∘C, using a Cr2O3/HZSM-5 catalyst showed 34 % of CO2 conversion
the subject focus on the development of effective catalysts. Conventional and 76% aromatic compound selectivity [35]. In another study by the
catalysts of CO2-to-methanol, such as ZnCrOx/HZSM-5, ZnZrO2/HZSM- Tsubaki group using Cr2O3/Zn-doped HZSM-5 @SiO2 catalyst, 22 %

Fig. 10. Schematic illustrations and representative performances of the direct CO2 hydrogenation and CO-mediated pathways for BTX production. (a) Reaction
mechanism of CO2 hydrogenation on the ZnZrO/ZSM-5 tandem catalyst proposed by Li et al. [111], and (b) the performance of the variations of the catalyst, in terms
of product hydrocarbon distribution. (c) Schematic flow diagram of the CO-mediated production of BTX. (d) Performance of the Na/Fe and HZSM-5 catalyst proposed
by Xu et al. [187] in terms of the aromatic distributions according to temperature change, and (e) time-dependent stability test of the developed catalyst. (a) and (b)
reprinted from Li et al. [111] Copyright (2019) Elsevier. (c) and (d) reprinted from Xu et al. [187] Copyright (2019) Royal Society of Chemistry.

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CO2 conversion and 39 % paraxylene selectivity was achieved, when requires high process temperatures above 800∘C, where as FT synthesis
reacting H2/CO2 with a ratio of 3:1 at 30 bar and 350 ∘C [175]. Li et al. operates at relatively lower temperatures of 250 ∘C, but requires higher
[111] used the ZnZrO/HZSM-5 tandem catalyst to react H2:CO2 = 3:1 operating pressures. Due to the difference in operating conditions of the
gas at 50 bar and 320 ∘C, showing 14 % CO2 conversion and 73 % aro­ two processes, a significant amount of energy loss is inevitable when
matic compound selectivity. The reaction pathway via the tandem sequentially connecting the two processes. Thus to maximize the energy
catalyst, and the overall performance is provided in Fig. 10(a) and (b), efficiency and product yield, it is essential to optimize the process
respectively. Tan et al. [196] used ZnCrOx/HZSM-5 catalyst for reacting configuration, and to develop catalysts most suitable for an integrated
H2:CO2 = 3:1 at 30 bar and 340 ∘C, showing 20 % conversion of CO2 and configuration. To avoid overlap with the previous sections, the
56 % aromatic selectivity. Zhang et al. [198] used ZnO/ZrO2/HZSM-5 methanol-to-fuel and syngas-to-fuel reactions are the main focus of this
catalyst to react H2:CO2 = 3:1 at 30 bar and 340 ∘C to obtain 9 % CO2 section.
conversion and 60 % aromatic selectivity. When producing hydrocarbons via hydrogenation of CO2, the num­
Regarding the FT pathway, Xu et al. [187] developed the ber of hydrocarbons follow the Anderson-Schulz-Flory (ASF) distribu­
Na/Fe/HZMS-5 catalyst to react H2:CO2 = 3:1 at 10 bar and 340∘C, tion [62,63], which shows the distribution of hydrocarbon formation
achieving 27 % CO2 conversion and 53 % aromatic selectivity. The based on the chain-growth probability (α). Thus, while it is not possible
overall mechanism and performance of the catalyst is shown in Fig. 10 to specifically determine the types of hydrocarbons to be produced, it is
(c) and (d)/(e), respectively. Sun et al. [177] used Na-Fe3O4/HZSM-5 possible to manipulate the dominant hydrocarbon among the products,
catalyst to react H2:CO2 = 3:1 at 30 bar, 320 ∘C, and achieved 30 % by altering the α value with different catalysts. Conventional studies
CO2 conversion and 20 % aromatic selectivity. have shown that Co-based catalysts retain α values of 0.8–0.9, and
Fe-based catalysts retain values of 0.7–0.8. Accordingly, using Co-based
3.3.3. Industrial applications catalysts increases the portion of n-paraffin within the final product, and
Since the production of aromatic compounds is still at its early stage, sequential upgrading processes can be installed to decrease the viscosity
no commercialized plant exists. or control fuel performance indices such as octane and cetane values.
Using Fe-based catalysts produces a product mixture of more than 20 %
olefins and less than 5 % oxygenates, which can further be separated to
3.4. Fuel (Power-to-liquids)
produce chemical materials.
3.4.1. Overview of technology
3.4.2. Current stage of development and research trends
The production of fuels from carbon dioxide, namely the power-to-
For both the methanol-mediated and CO-mediated pathways, the
liquids (PtL) process, can be divided into two types according to the
main focus of research is the catalyst development, since specific cata­
intermediate product, methanol or CO [193]. A schematic of the overall
lysts must be used to increase the selectivity towards desired products.
processes are given in Fig. 11. In the methanol-mediated fuel production
Regarding the methanol-mediated pathway, a catalyst produced by
pathway, CO2 is first hydrogenated to produce methanol, then catalysts
combining metal oxides with zeolites are used, and the type of catalyst
suited for converting methanol to long-chain hydrocarbons are used to
determines the confinement of the hydrocarbons, altering the final
produce fuel. The equation for CO2 to methanol is shown in Eq. 3, and
product. Gao et al. [68] presented the use of a bifunctional catalyst for
the conversion of methanol to hydrocarbons is shown in Eq.11.
directly hydrogenating CO2 to liquid hydrocarbon. By developing a
nCH3 OH + H2 →CH3 (CH2 )n− 2 CH3 + nH2 O (11) catalyst consisting of reducible indium oxides (In2O3) and zeolite
HZSM-5, C5+ products were obtained with a 78.6 % selectivity. The
As for the indirect CO2 hydrogenation as CO as the intermediate
oxygen vacancies of the In2O3 surface promote CO2 hydrogenation, and
product, the RWGS process for producing CO from CO2 and H2, and the
the high C-C coupling is overcome by the zeolite pores, enhancing
FT synthesis step are integrated, to produce long-chain hydrocarbons as
long-chain hydrocarbon production.
the final product. The chemical reaction for converting syngas to hy­
Research regarding the CO-mediated pathway has been focused on
drocarbons is shown in Eq. 12.
the single reactor process, and on the bifunctional catalyst capable of
nCO + (2n + 1)H2 →Cn H2n+2 + nH2 O (12) promoting both the RWGS and FT synthesis. Mainly, Fe-based bifunc­
tional catalysts [55] are studied. Choi et al. [46] presented the devel­
For both pathways, extensive amount of research has been conducted
opment of a new catalyst producing C5+ hydrocarbons with a 65 %
for the separate steps, but there has been less interest in the integrated
selectivity, by in-situ carburization of CuFeO2 to Hägg carbide. Wei et al.
process design to maximize efficiency. For example, considering the CO-
[177] developed a Na-Fe3O4/HZSM-5 catalyst with three types of active
mediated pathway, the RWGS step is an endothermic process, which

Fig. 11. A schematic diagram showing fuel production from CO2 via the CO-mediated pathway and the methanol-mediated pathway. Reprinted from Rego de
Vasconcelos et al. [171].

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sites. The Fe3O4, Fe5C2 and acid active sites, promote a tandem reaction Copenhagen Airports, A.P. Moller-Maersk, DSV Panalpina, DFDS, SAS,
to produce C5-C11 products with 22 % conversion and 78 % selectivity, and Ørsted [14]. The project aims at decarbonizing the transportation
at 320 ∘C and 30 bar. Jiang et al. [87] developed Fe- and FeCo-based sector, by producing renewable methanol and renewable jet-fuel to
catalysts, achieving 54.6 % conversion and 47.0 % C5+ selectivity. reduce 5 % of fossil fuel usage at Copenhagen Airport by 2027, and 30 %
Tarasov et al. [164] showed the performance of Co-based bifunctional by 2030. The core idea is to increase green H2 production using offshore
catalyst in CO2 hydrogenation to hydrocarbon. At 260∘C, the 10% wind power (1.3 GW electrolyzer by 2030), then to react the H2 with
Co/MIL-53(Al) catalyst showed 35.0% selectivity to C5+ with 25.3 % of CO2 obtained from point sources to obtain methanol and jet-fuel. The
CO2 conversion. Shi et al. [155] presented the results of applying Na as a consortium is planning to provide 250 kt/y of green fuel by 2030,
promoter to the CoCu/TiO2 catalyst, to enhance selectivity towards abating CO2 emissions by 850 kt/y [15].
longer hydrocarbons. Their results showed that the addition of the Porsche AG is cooperating with Siemens Energy on the Haru Oni
promoter increased the C5+ selectivity from 4.9 to 42.1 %, while project aiming to produce e-fuels [24]. The Chile-based plant is expected
decreasing the CH4 selectivity from 89.5 to 26.1 %. Cui et al.[50] pre­ to produce e-fuel at a capacity of 130,000 L by 2022, and is planning to
sents an approach for increasing the CO2 conversion and C5+ selectivity, construct a scaled-up plant producing 550 million liters of e-fuel by 2026
by coupling homogeneous and heterogeneous catalysts. Applying the [23]. The main reaction pathway is to first produce methanol from green
RuCl3 catalyst for RWGS and Ru0 catalyst for FT synthesis, and adding hydrogen and CO2, then to convert the produced methanol to e-fuel.
LiCl as a cocatalyst and LiI as a promoter, the overall reaction could The Spanish oil firm Repsol is planning to fund 100 million dollars
proceed at a low temperature of 180 ∘C and achieve C5+ selectivity of for constructing a zero-emission fuel production plant. In association
71.1 %. with Saudi Aramco, the they are planning to operate a e-fuel production
A few studies focus on the kinetic modeling of the CO2 to hydro­ plant via the FT reaction, with a capacity of 2100 t/y by 2024 [28].
carbons reactions, based on the developed catalysts. Ghosh et al. [72] Another large-scale e-fuel project is being in progress by the Reliance
presented results on the experimental and kinetic modeling results of the Industries, which are planning to convert all transportation energy
methanol-mediated CO2 conversion to hydrocarbons, using the sources to carbon-zero fuel by 2035 [27]. Their projects focus on cata­
In2O3/HZSM-5 bifunctional catalyst. Using a Langmuir Hinshelwood lytic and electrochemical conversion of CO2 to useful feedstock.
Hougen Watson (LHHW) reaction mechanism the model was success­ Other CO2-based fuel production projects within the industry include
fully validated with experimental data and was able to predict the hy­ the e-diesel project by Audi, and the Air to Fuels™ (A2F) by Carbon
drocarbon product distribution according to the ratio change among the Engineering. The Audi e-diesel is a project to produce diesel from green
bifunctional catalytic bed components. Brübach et al. [41] proposed a hydrogen and CO2 obtained from a biogas facility. The project is oper­
kinetic model of the CO-mediated hydrocarbon production reaction, ated in partnership with Sunfire GmbH, and has been producing e-diesel
based on the potassium-doped, alumina supported, Fe catalyst (the long-chain hydrocarbon products obtained from the process) since
(Fe/K@ γ-Al2O3). Using a LHHW-type kinetic model their model was 2015 [2]. The A2F process of Carbon Engineering combines direct air
able to reproduce the experimental results within the operating condi­ capture (DAC) with H2 obtained from water electrolysis and CO2 hy­
tions of 280–320 ∘C, 10–20 bar, and H2-to-CO2 molar ratio of 2–4. drogenation to produce liquid hydrocarbon fuels [5]. First fuel pro­
Panzone et al. [134] also developed a kinetic model for CO2 hydroge­ duction from the A2F process was achieved in 2017 and further scale-up
nation using a Fe-K/Al2O3 catalyst based on a LHHW kinetic mechanism. and commercialization studies are under research, in partnership with
Their model considers the overall reactions capable via the CO-mediated the PtL firm, Greyrock Energy [16].
pathway, including alcohols and acids production, and includes oxy­
genates formation which are a critical byproduct of the CO2 hydroge­ 4. CDU in the development phase – Technologies with potential
nation reaction. These studies are important as the consecutive step for for small scale reduction
developing the reactions to large-scale production plants.
Summarizing the mentioned studies, typical operating conditions of 4.1. Formic acid
the one-reactor conversion system is 300–350 ∘C and 15–25 bar, which
are mild conditions compared to the two-step process and is thus more 4.1.1. Overview of technology
efficient in terms of energy usage. However, additional research is Formic acid is utilized throughout various industries, such as for
required to improve the one-step process, such as increasing the CO2 leather and fiber production, and as eco-friendly snow removers and
conversion rate of 30–40 %, which is low compared to the two-step coagulants for rubber production. The amount of formic acid production
process of 80 %. In addition, process configurations need to be revised was 870 kt in 2021, and the market is estimated to grow to 1.8 billion
and validated, such as adding process units for recycle and eliminating USD by 2027. The current formic acid market is small compared to other
excessive amount of water produced during the overall process. chemicals such as ammonia, but its demand is expected to increase with
Currently only model-based studies exist on the process configuration of the development of direct formic acid fuel cell (DFAFC) technology and
one-reactor conversion system [80,103], and thus experimental vali­ with extended applications as a hydrogen carrier [52]. Production of
dation of the processes and further optimization of the configuration are formic acid via CO2 is achieved through various pathways, including
important for increasing the energy efficiency. catalytic chemical conversion and electrochemical conversion. Pre­
liminary life cycle assessment (LCA) results show that formic acid has
3.4.3. Industrial applications the highest potential for CO2 mitigation compared to the conventional
The PtL technology is widely studied in Europe, and various projects process [160]. However, the catalytic and electrochemical technologies
are being conducted to commercialize CO2-based fuel production. for converting CO2 to formic acid are still in their development stage,
Currently the largest consortium under operation is the Norsk e-fuel and further studies on the catalysts and process configuration, and
project, which consists of European energy companies such as Sunfire, experimental validation from large-scale pilot operation are required for
Climeworks, Paul Wurth, and Norsk Vind [22]. The Norsk e-fuel project commercial applications.
is planning to operate a PtL plant for producing aviation fuel with a Catalytic chemical conversion involves the hydrogenation of CO2 to
capacity of 10 million liters of liquefied hydrocarbon by 2023. A obtain liquid chemicals, and formic acid is considered one of the most
scaled-up plant producing 100 million liters of PtL fuel is planned to be valuable products of catalytic conversion, other than methanol, ethanol,
operated by 2026, which is estimated to mitigate CO2 by 250kton/y light olefins, gasoline, and diesel.
[21]. Electrochemical conversion involves the coupled conversion of CO2
The “Green Fuels for Denmark” project is a Danish consortium con­ and H2O by applying electrical energy to an electrolyzer⋅H2O is oxidized
sisting of major transportation corporations of Denmark, such as at the anode, while CO2 is reduced at the cathode by receiving the

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electron and hydrogen ion to produce formic acid or formate. Only 2 for include Pb, Ru-Pd, Hg, Sn, In, and Cd [119]. In, Bi, Hg, and Pb cat­
moles of electrons are required per 1 mol of CO2 reduction, and thus alysts have shown high Faradaic efficiencies of above 80% at high cur­
formic acid is considered the most economic chemical obtainable rent densities. Other metal catalysts, including Zn, Cu, and Cd promoted
through electrochemical conversion. The selectivity of the products the reduction of CO2 to formic acid, but showed low Faradaic effi­
obtained from the cathode mainly rely on the type of metal/metal oxide ciencies and current densities. Among the D-group metals, such as Pd,
catalysts used. Formic acid is the primary product when catalysts such as Rh, and Ir, Pd has been known to show the highest performance, having
Sn, In, Pb or their oxide forms are used [89]. achieved 100 % Faradaic efficiency at high current densities. Rh and Ir
Photoelectric methods incorporate solar energy to reduce CO2 to catalysts have shown low Faradaic efficiency toward formic acid, and
produce valuable products. There two types of photoelectric methods the products are dominated by CO and H2. Despite the high electro­
based on the material used for the reactions, namely photocatalytic chemical performance of some of the metal catalysts, the large over­
conversion and photoelectrochemical conversion. Photocatalytic con­ potential still imposed a problem, providing motivation for development
version reduces CO2 within a solution where the photocatalytic nano of the metal-complex catalysts. Transition metal complexes, suchs as Rh,
particles are suspended. Photocatalysts mainly consist of semiconductor Ir, and Ru complexes, have shown to lower the require overpotential
material, where electrons are emitted upon solar exposure to be deliv­ while retaining good electrochemical performance. Ishida et al. reported
ered to the CO2. While photoelectric conversion of CO2 is the most eco- large amounts of formate production using the [Ru(bpy)2(CO)2]2+. The
friendly technology to reduce CO2, since it reduces CO2 by mimicking electrochemical conversion pathways of CO2 reduction to formic acid,
the photosynthetic process of plants, its research is still in the basic and a summary of the various metals implementable as catalysts is
phase and there are many hurdles to overcome for commericialization. presented in Fig. 12.
Recent studies on the electrocatalysts of CO2 hydrogenation present
4.1.2. Current stage of development and research trends results of enhancing formic acid productivity by employing solid-state
Recent research results regarding CO2-based formic acid production electrolytes. Formate produced by CO2 reduction in aqueous condi­
is focused on the development of catalysts for thermochemical conver­ tions require additional separation processes to purify formic acid as the
sion, electrocatalyst development for reducing the required over­ final product, deteriorating the economic potential [186]. Xia et al.
potential, and studies on extracting H2 from formic acid. [185] studied the performance of a CO2 reduction cell with a
Formic acid production via CO2 hydrogenation usually occurs in three-chamber configuration, based on the use of Bi nanosheets as teh
aqueous amine conditions, since the direct reaction of CO2 and H2 is electrode. Sequentially utilizing the solid-state electrolyte (SSE), anion
thermodynamically unfavored. During early stages of research, focus exchange membrane (AEM), and the cation exchange membrane (CEM),
has been made on development of homogeneous catalysts for enhancing formic acid is produced separated from the electrolyte. The results of
CO2 hydrogenation reactivity within the aqueous amine environment. their study showed formic acid Faradaic efficiency of up to 93.1 % at
Noble metals such as Ru, Rd, and Ir, and transition metals including Ni, 3.08 V. Fan et al. [60] conducted research on the use of an all-solid-state
Cu, and Fe have been incorporated as homogeneous catalysts. Tanaka electrochemical CO2 reduction system to enhance the concentration and
et al. [163] developed a new catalyst, PNP-Ir(III) hydride complex, purity of formic acid. By combining the grain boundary-abundant Bi
where PNP is a alkylphosphine-based pincer ligand acting as an efficient nanoparticles, which originally showed high current density and Fara­
electron donor. In aqueous KOH conditions and at 120∘C and 60 bar, the daic efficiency, and the porous solid electrolyte (PSE) layer to obtain
proposed catalyst showed good performance with a TOF of 73,000 h− 1 formic acid in the form of vapors, the authors obtained high purity
for 48 h. Filonenko et al. [61] studies the Ru PNP-pincer catalyst-based formic acid solutions with concentrations of near 100 wt%.
CO2 hydrogenation and dehydrogenation system. Using 1,8-diazabicy­
clo[5.4.0]undec-7-ene (DBU) as a base promoter, the developed cata­ 4.1.3. Industrial applications
lyst showed TOF performance of 1,100,000 h− 1 for formic acid Formic acid production via CO2 hydrogenation is yet to be
production at 120∘C and 27 bar. Liu et al. [114] developed an Ir catalyst commercialized, and various research efforts are being made for formic
containing an imine-diphosphine ligand. Using a 5 M KOH as the base, acid process development, but many obstacles have to be overcome.
the developed catalyst showed performance of TOF 450,000 h− 1 at Researchers in Germany and corporations such as BASF have conducted
140 ∘C for 20 h. However, despite the good performance shown by much research on the topic, but their focus was on homogeneous cata­
previous studies, homogeneous catalysts have a critical limitation for lysts, which has the inherent problem of separating the catalyst from the
large-scale applications, due to the difficulties of catalyst separation produced formic acid, hindering commercialization.
from the final product [74]. Thus to overcome this limitation, recent Another actively studied field for formic acid production is the use of
studies have focused on the development of heterogeneous catalysts for electrochemical conversion of CO2. Formic acid or formate may be
CO2 hydrogenation. produced according to the electrolyte or catalyst system of the electro­
Su et al. [161] studied the performance of carbon-supported palla­ chemical reactor. Recent work on the topic include the electrochemical
dium nanocatalysts based on the ammonium bicarbonate/formate redox reactor and reduction electrode by Liquid Light, the anion exchange
equilibrium. They tested the performance of CO2 hydrogenation at membrane system, Sustainion, by Dioxide Materials [190], the separa­
varying operating conditions, and showed that the highest performance tion of formic acid and potassium sulfate via pH swing developed by
was obtained at 55 bar with Pd/AC (activated carbon) nanocatalyst, Seogang University, the catholyte-free CO2 reduction system [108],
showing TOF of 1103 h− 1. Umegaki et al. [169] studied the hydroge­ which overcomes the restrictions imposed by CO2 in water and mass
nation of supercritical CO2 using Ru nanoparticles as the catalyst. At transfer within the electrolyte, by KIER, and the cyclic two step elec­
operating conditions of 80 ∘C and 130 bar, the catalyst performance trolysis developed by KIST [106]. Other researchers make use of solar
showed a TOF of 2117 h− 1. Park et al. [135] developed and studied the energy to increase the energy efficiency of the electrochemical system.
performance of Ru molecular catalyst on a bpyTN-30-CTF support. The Kang et al. developed a photocatalyst based on Cu-Fe oxide, allowing
use of the bpyTN-30-CTF support increased the porosity and metal formate production with a 90% selectivity, without the application of
anchoring sites, enhancing the performance and stability of the catalyst. additional power voltage [93]. Yadav et al. developed a flexible polyer
Notably, the performance of the catalysts were validated on a contin­ film-based photocatalyst, which selectively produces formic acid upon
uous hydrogenation reactor, reaching a total TON of 524,000 during 30 exposure to solar energy [189].
days of operation. The ECFORM process developed by the DNV GL is a process for
Regarding electrochemical reduction of CO2 to produce formic acid, directly converting CO2 to formic acid and formate. By applying a Sn-
high overpotential, low product selectivity, and electrode poisoning are based alloy catalyst, the electrolysis reactor is known to have a
the main hurdles that need to be overcome. Conventional metal catalysts formate selectivity of 75 %. A bench-scale plant with a CO2 utilization

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Fig. 12. (a) Detailed pathways of CO2 reduction to formic acid, and (b) available metal catalyst options for electrochemical conversion of CO2 to formic acid.
Reprinted from Lu et al. [119] Copyright (2014) Elsevier.

capacity of 1 kg/d has been built in 2017, and further research is being 4.2.2. Current stage of development and research trends
conducted for additional scale-up of the plant. While research on CO2 conversion to acetic acid is still at an early
stage, mainly two pathways are considered for substituting conventional
4.2. Acetic acid acetic acid production: the thermochemical and electrochemical path­
ways. The first pathway is to convert CO2 using thermocatalysts,
4.2.1. Overview of technology reacting CH4 with CO2 to produce acetic acid. Early studies showed the
An active research area for catalytic conversion of CO2 is the pro­ development efforts of direct CO2 conversion to acetic acid, such as the
duction of acetic acid, which is a C2 chemical with the potential for study by Wilcox et al [179]. The authors studied the acetate formation
producing chemical products such as polymers. Acetic acid is widely via direct catalytic reaction of methane and CO2, using both 5 %
utilized as a basis material for complex chemical formation, with a Pd/carbon and 5 % Pt/alumina catalysts. At 400 ∘C operation, both
production capacity of 9.07 Mt/y in 2020 [13]. Main usages of acetic catalysts showed acetate formation, where the 5 % Pt/alumina catalyst
acid include dyes, pharmaceuticals, solvents, adhesives, and raw mate­ showed larger peaks on the diffuse reflectance Fourier transform
rials for polymers such as polyvinyl. Acetic acids are conventionally infrared spectroscopy (DRIFTS), indicating higher catalyst reactivity.
produced using CO and methanol, but recent research trends focus on However, due to the high thermodynamic barrier of the reaction and low
the utilization of CO2 as a material for acetic acid formation. Acetic acid product selectivity, recent studies have focused on the development of
has a large potential for CO2 mitigation since the weight percent of CO2 new pathways for producing acetic acid more efficiently.
within acetic acid is high. Recently, Qian et al. [141] proposed a mechanism for producing

Fig. 13. Reaction mechanisms for producing acetic acid presented in various studies. (a) Reaction mechanism for producing acetic acid through hydrocarboxylation
of methanol using a Ru-Rh bimetallic catalyst. Ru* and Rh* represent active Ru and Rh species, respectively. Reprinted from Qian et al. [141] (b) Effect on product
selectivity when using catalysts with non-thermal plasmas for producing oxygenates via CO2 reforming with CH4. Reprinted from Wang et al. [174]. (c) Stability, FE,
and acetate purity during acetate production using Cu NC catalyst, as proposed in Zhu et al. [202]. (d) Structure of the Mn-corrole catalyst presented in the work by
De et al. [51].

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acetic acid using CO2, H2, and methanol. Using a bimetallic catalyst ion batteries. Also, conversion of CO2 to construction material such as
Ru-Rh with imidazole as the ligand, LiI as the promoter, and 1,3-dime­ CaCO3 gives them the potential to substitute conventional material such
thyl-2-imidazolidinone (DMI) as the solvent, methanol was hydro­ as steel and cement.
carboxylated to acetic acid with a yield of 70.3 %. The imidazole ligand
played an important role in enhancing the reaction via good coordina­ 4.3.2. Current stage of development and research trends
tion capability with the active center, showing TOF in acetic acid pro­ Different research groups have presented studies regarding the pro­
duction of 30.8 h− 1 at 200 ∘C. The reaction mechanism is shown in duction of various carbon materials. Wei et al. [178] reported the for­
Fig. 13(a). mation of porous carbon via the reaction of supercritical CO2 with alkali
Other studies report the use of plasma-driven catalysis for acetic acid metals, at intense operating conditions of 500 ∘C and 300 atm in an
production from CO2. Wang et al. [174] proposed the use of non-thermal autoclave. Upon analysis of the product, it was shown that graphite
plasmas with catalysts to directly produce acetic acid from CO2 and particles with relatively low graphitization, retaining Raman spectra
methane. The proposed system couples a dielectric barrier discharge relative intensity ratio values in the range of 1.02–1.11, were produced.
(DBD) reactor with a ground water electrode to allow acetic acid for­ Lou et al. [118] presented the results of producing diamonds of sizes up
mation at mild operating conditions (30 ∘C, 1 atm). Utilizing a to 250 μm by reducing CO2 at low temperatures, using pure Na to reduce
Cu/γ-Al2O3 catalyst in the DBD reactor, acetic acid selectivity of 40.2 % dense CO2 at 440 ∘C and 800 atm. Ren et al. [145] presented the results
was obtained. The performance test results of the product selectivity of producing carbon nanofibers (CNFs) by electrolytic conversion of
when using different operational modes (catalyst only, plasma only, and CO2. The electrolysis was carried out using inexpensive electrodes of Ni
combination of catalyst and plasma) are provided in Fig. 13(b). and Ir, and the structure of the CNF could be manipulated by addition of
The second pathway of CO2 utilization for acetic acid formation is trace transition metals or an initiator such as Zn. Extending from the
the direct reduction of CO2 through electrochemical conversion. Studies previous study, Ren et al. [143] proposed the method of transforming
regarding electrocatalysts have focused on the use of metal catalysts CO2 to multi-layered carbon nanotubes via molten electrolysis. This
such as Cu, Fe, and Mn. Genovese et al. [69] used Cu nanoparticles on technology incorporates electricity produced by solar energy, and pro­
carbon nanotubes as the catalyst for promoting the C-C bond formation, duces O2 as a byproduct, meaning minimal emission of pollutants during
achieving Faradaic efficiencies for acetic acid formation of 56%. With the process. A summary of the pathways for producing CNT “wool”,
the use of Fe, Genovese et al. [70] achieved Faradaic efficiencies of which is an extension of the study by Ren et al. [145] presented in
60.9%, using FeIII oxyhydroxide on N-doped carbon as the catalyst. Johnson et al. [88], is shown in Fig. 14. Kim et al. [97] proposed the
Other studies have combined the use of electrolyzer configuration with method of using boron hydride reducers to produce carbon nanotubes at
catalyst development to improve the overall performance. The mild conditions. The operating conditions of this process is very mild
three-chamber cell consisting of SSE, AEM, and CEM, which was used for compared to previous studies, operating at 1 atm, and also the
formic acid production in section 4.1.2, can be further extended for post-processed carbon nanotubes can be applied to fuel cells and super
electrocatalytic acetic acid production systems. The system proposed by capacitor electrodes.
Xia et al. [185] showed that 1.3 mM of acetic acid could be obtained at
3.45 V operation, using a Cu catalyst obtained from commercial Cu2O 4.3.3. Industrial applications
nanoparticles. Zhu et al. [202] present results for obtaining acetic acid While no commercialized application of CDU-based carbon material
via CO reduction. By optimizing the edge-to-surface ratio to obtain a Cu production exists up to date, a few start-ups are working on the
nanocube catalyst suited for the reaction, and coupling the catalyst with demonstration of large-scale application of CNT production from CO2.
the porous solid electrolyte (PSE) reactor, acetic acid was obtained at One of the leading corporations of CNT production is Carbon Corp, who
neutral pH, with Faradaic efficiency of 43% and partial current density have research experience in terms of CNT and carbon nanofiber pro­
of 200 mA ⋅ cm− 2. While the study does not directly incorporate CO2 for duction [88,144,145].
electrochemical conversion, the high selectivity of the proposed reactor
could be successfully coupled with CO2 to CO reduction for carbon 5. Overview of factors related to commercialization
mitigation. Acetate production performance using the developed cata­
lyst is presented in Fig. 13(c). De et al. [51] proposed the use of mo­ For a CDU-based product to be commercialized, various factors,
lecular manganese corrole complex as the electrocatalyst for CO2 including the chemical costs, market scale, and the technology readiness
conversion to acetic acid. Structure of the Mn-corrole catalyst is shown levels (TRLs), have to be considered. The market sizes and costs for the
in Fig. 13(d). MnIII-corrole was stabilized on carbon paper and used as chemicals considered in this study are presented in Fig. 15. It should be
the CO2 reduction catalyst in a moderate acidic medium of phosphate noted that the provided chemical prices are not values obtained by CDU-
buffer. The experimental results showed that the cell was operable at based production, but by conventional production methods. Among the
− 1.25 V vs. Ag/AgCl (1 M KCl) reference node, and a maximum FE of CDU-based chemicals considered in the review, CO, light olefins, and
63 %, and TOF of 8.25 h− 1 was obtained. The suggested mechanism is fuel were excluded from the figure since a realistic market size could not
that the MnIII bound oxalate intermediate readily forms acetate, be defined. An overall tendency is for chemical price to be inversely
increasing the selectivity of the product. proportional to market size, since prices become higher when chemicals
are produced in less quantity, and vice versa.
4.2.3. Industrial applications Considering the technology readiness level (TRL) of each technology,
Since CDU-based acetic acid production is still in its early stage, which is a factor for indicating the maturity of a technology with an
large-scale application of the processes are yet to be developed. index value from 1–9, Chauvy et al. [44] provided the TRL of various
technologies and the timeframe to actual deployment of the technology.
4.3. Carbon material While not all of the technologies considered in this review are provided,
the TRLs are in correspondence with the categorization used in this re­
4.3.1. Overview of technology view. Thus the timeframe to deployment for each technology can be
Other than producing chemicals and fuels from CO2, various at­ estimated accordingly. According to the TRL values, methanol and cal­
tempts have been made to produce carbon material from CO2. Examples cium carbonates have a high probability of commercialization in the
of these efforts include the production of diamonds, carbon nanotubes, upcoming years. Both products have a sufficiently large market, and
and carbon blacks. Carbon materials with good electrical, mechanical thus focusing on the scale-up operation of pilot plants and process
characteristics, and thermal stability allow them to be implemented for validation of the developed technologies will be a good strategy for
energy conversion equipment such as fuel cells, super capacitors, and Li- promoting the realization of a CDU technology. For technologies

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Fig. 14. Conventional and newly proposed CDU-based CNT formation pathways presented in Johnson et al. [88] The presented pathway does not require the use of
Zn coated steel in the cathode, and imlements the Monel cathodes and Nichrome anodes to produce high yields of CNT wool. Reprinted with permission from
Johnson et al. [88] Copyright (2017) Elsevier.

Fig. 15. The market sizes and price of the candidate chemicals considered in
the review. Chemical price values obtained from the commodity price database
of Intratec IC [82], and market sizes were obtained from the database of Mordor Fig. 16. TRL and timeframe to deployment for various CDU-based chemical
Intelligence [125]. Values were averaged over the year 2021, and for chemicals production technologies. Copyright (2019) Elsevier.
where prices for 2021 were not available, the most recent prices were used.
In terms of large-scale application, methanol, polymer, urea syn­
retaining TRLs of less than 6, research should be more focused on thesis and mineral carbonation technologies are leading the race. Some
fundamental development and bench-scale operations Fig. 16. common factors of these CDU technologies are: (1) they have in common
a large market, and (2) the processes are profitable, and (3) the tech­
6. Conclusion and Perspectives on CDU nologies are capable of carbon fixation for a long period of time. These
aspects have motivated governments to supply funding for development
Many countries have invested in the development of CDU technol­ of the core technologies, and have encouraged industrial partners to
ogies as a means of approaching a net-zero economy. While the final participate in verifying the validity of the technologies, after being
goal may be to achieve net-zero via total transition of the economy to­ verified at lab scale. Taking into account these three aspects, a potential
ward renewable energy, realizing the technologies to every corner of the CDU application with high possibility of large-scale applications in the
society requires a great deal of time, when immediate action is essential near future is the production of chemicals via the direct conversion of
to meet short-term CO2 mitigation goals. amine-captured CO2, including formic acid, CO, and methanol

17
C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

production. the work reported in this paper.

The concept of direct conversion of amine-captured CO2 is to convert
CO2 (or its solvated state within the amine solution) directly to the target Data availability
product, hence reducing the additional input of energy required in
conventional CDU processes for amine regeneration. Since amine Data will be made available on request.
regeneration energy is a major cost factor of the CDU process, retaining
more than 50 % of the increase in energy use required for CO2 capture Acknowledgments
[123], direct conversion of amine-captured CO2 can greatly improve the
costs required for CDU applications. The direct conversion of This work was supported by the National Research Foundation of
amine-captured CO2 can be achieved either through a thermocatalytic Korea (NRF) grant funded by the Korean government (MSIT) (no. NRF-
pathway or an electrochemical pathway. Early studies have been 2020M3H7A1098271).
focused on the thermocatalytic conversion, as presented in Yang et al.
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