Journal of CO2 Utilization 65 (2022) 102239

Contents lists available at ScienceDirect

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
Controlling the amount of greenhouse gas emissions and conse­
quently mitigating global warming and related climate problems is
deemed as a global task. CO2 is the main contributor to global warming
and climate change, of which the global emissions from energy com­
bustion and industrial processes added up to 36.3 Gt in 2021 [81]. The
United Nations Framework Convention on Climate Change (UNFCCC)
proposed a treaty to limit global warming to below 2 ∘C, preferably to
1.5 ∘C, namely the Paris Agreement in 2015 [170]. The consequences of
global temperature increase larger than 1.5∘C are serious and extensive,
as provided in the recent report from the Intergovernmental Panel on
Climate Change (IPCC) [83]. While immediate and intense actions are
required to achieve the goal set by the Paris Agreement, practical ap­
plications which are capable of reducing CO2 on a large scale are far
from realizable, and many countries are still conducting research and
searching for the right option to delve into as the main strategy for
tackling the climate crisis.
Among the various options for CO2 mitigation, carbon dioxide uti­
lization (CDU) is considered as a readily-applicable option in the short to
mid-term. The idea of CDU is to convert the captured CO2 into valuable
products such as fuels, chemicals, and minerals, or utilize them for
business applications such as enhanced oil recovery (EOR). While
various studies suggest a bright future for the different CDU applica­
tions, not many of the options qualify for the three important aspects of
CDU: long-term carbon fixation, economic feasibility, and large-scale
application. Often is the case where seemingly sustainable CDU appli­
cations fail to achieve sufficient profitability, or is not suitable for large-
scale CO2 reductions in the scale of millions of tonnes per year. To
effectively choose mitigation options and commercialize processes in
association with the industrial sector, it is important to acknowledge the
development stages of the different CDU options, and their potential for
industrial application.
Along with the technological aspects, it is essential to discuss CDU
applications in accordance with the related market and policy trends.
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: changs90.kim@kist.re.kr (C. Kim), cjyoo@kist.re.kr (C.-J. Yoo), hyung-suk.oh@kist.re.kr (H.-S. Oh), bkmin@kist.re.kr (B.K. Min), ulee@kist.re.
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.
policies regarding the organization of a greener economy, such as car­
bon credits, carbon tax, and government subsidies to the industries, are
essential for motivating the projects. Formation of CDU product markets
are also greatly affected by these policies, since additional taxation of
non-CDU products can invertly promote the profitability of CDU prod­
ucts. Overall, to determine specific CDU projects of interest and to focus
on selected technologies for development, it is essential to understand
the market and policy trends related to CDU, along with the techno­
logical development of the separate technologies.
In this review, CDU technologies regarding the production of
chemicals and fuels, are reviewed based on their stage of development
and industrial application potential. Also, the market and policy trends
of leading countries in the development of CDU technologies are pre­
sented, to provide insight into the global association of CDU develop­
ment. Details of each technology are provided in comparison with the
conventional methods, usually incorporating petrochemical products,
along with their carbon mitigation capacity and trends within the
academia and the industrial sector. The various CDU technologies are
divided into three categories: technologies in the demonstration phase,
technologies in the development stage having potential for large-scale
applications, and technologies in the development stage having poten­
tial for small-scale applications. In Section 2, CDU options in the
demonstration phase are introduced, including specific projects
regarding the actual pilot plant under operation. In Section 3, CDU
options in the development phase, such as carbon monoxide (CO) or
fuels, having the potential of large scale application, are introduced. In
Section 4, CDU technologies in the development phase with small
markets are introduced. These options are introduced because although
the current market size is comparably small, it has the potential for
exponential growth in the future, due to development of related tech­
nologies and changes in government policies. In Section 5, the market
and policy trend is considered for the CDU technologies, and related
projects are reviewed. In Section 6 the future perspectives of CDU
technologies are provided, and the paper is finalized with conclusions in
section 7.
2. CDU technologies in the demonstration phase
2.1. Methanol synthesis
2.1.1. Overview of technology
Methanol is one of the most widely used chemicals throughout the
world, with annual demand of 98 Mt in 2019 and global production
capacity of 150 Mt [84]. Methanol is mainly used as a raw material for
synthesizing hydrocarbon compounds such as formaldehyde, ethylene,
and propylene, via the methanol-to-olefins (MTO) reaction. Also, it is
incorporated as fuel by itself, or as a blend with gasoline or diesel
components. As mentioned in the work by Olah [132], methanol has the
potential to become a base chemical for the economy, serving as raw
material for chemical compounds and as a fuel. There is also a growing
market for direct methanol fuel cells (DMFCs), or the use of methanol as
a hydrogen carrier, in preparation for the hydrogen economy. Accord­
ingly, the methanol market has large potential for growth and, despite
the technical barriers that need to be overcome, such as low conversion
and selectivity during synthesis, methanol is currently one of the most
probable candidates for large-scale CDU application.
Mainly two strategies exist for CDU-based methanol production: (1)
direct hydrogenation of captured CO2 to produce methanol, and (2)
producing CO by utilizing CO2, via either electrochemical reduction or
the reverse water-gas shift reaction, and reacting it with H2 obtained via
an environmental pathway, such as water electrolysis.
2.1.2. Current stage of development and research trends
Currently most of the conventional methanol production rely on coal
gasification and natural gas reforming processes. The related equations
for methanol production are presented in Eqs. 1-4. Eq. 1 shows the steam
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Journal of CO2 Utilization 65 (2022) 102239
methane reforming (SMR) reaction, where methane is reacted with
water to generate a mixture of CO and H2, or syngas. Eqs. 2 and 3 shows
the methanol production via hydrogenation of CO and CO2, respec­
tively. Eq. 4 shows the reverse water-gas shift (RWGS) reaction, which is
a competing reaction of Eq. 3. Most of the conventional methanol is
produced by sequentially reacting Eq. 1 and then Eqs. 2 and 3, where a
small amount of CO2 is added to the syngas produced from Eq. 1, to
increase the reaction rate.
For CDU methanol, the main reaction is Eq. 3, where CO2 is directly
reacted with 3 moles of H2 to produce methanol and water. However,
since the enthalpy change is larger negatively compared to the CDU
pathway, the conventional pathway is preferred from a thermodynamic
point of view. Thus the equilibrium yield of methanol production via Eq.
2 is over 80 % at 200 ∘C, while equilibrium yield of the Eq. 3 only shows
40 %. Additionally, at higher temperatures, the reverse water-gas shift
reaction (Eq. 4) is promoted, resulting in lower methanol selectivity.
CH4 + H2 O→CO + 3H2 , ΔH298K = − 206.2kJ∕mol (1)
CO + 2H2 →CH3 OH, ΔH298K = − 90.5kJ∕mol (2)
CO2 + 3H2 →CH3 OH + H2 O, ΔH298K = − 49.3kJ∕mol (3)
CO2 + H2 →CO + H2 O, ΔH298K = 41.2kJ∕mol (4)
Due to these limitations, the main focus of development for
increasing the yield of direct CO2 hydrogenation are the development of
novel catalysts and design of new process configurations for efficient
energy usage.
CDU methanol is produced by incorporating the commercialized Cu/
ZnO/Al2O3 catalyst developed by the Imperial Chemical Industries (ICI)
[36,176]. The operating conditions of the reaction are in the tempera­
ture range of 230–300 ∘C, and a pressure range of 50–100 bar. However,
the Cu/ZnO/Al2O3 catalyst has numerous limitations, mainly where
water produced as a byproduct significantly deactivates the catalytic
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
et al. [39] identified the catalyst active sites using a combination of
experiments, imaging methods, and density functional theory (DFT)
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
cies. Kuld et al. [105] have presented results on quantifying the per­
formance enhancement effect provided by ZnO during catalyst
reactions. By combining experiments with DFT calculations, they
showed that the Zn coverage on the Cu surface is essential for methanol
productivity, showing a monotonic increase up to the level of 0.5. Wu
et al. [183] proposed the use of inverse ZrO2/Cu catalysts with tunable
Zr/Cu ratios for CO2 hydrogenation to methanol. The prepared catalyst
consisting of 10 % ZrO2 supported over 90 % of Cu showed a methanol
formation rate 3.3 times higher than a conventional Cu/ZrO2 catalyst.
Schematic description and the performance of the inverse catalyst is
shown in Fig. 1 (a) and (b), respectively.
Additional studies have been conducted to revise process configu­
rations capable of maximizing energy efficiency. Such studies include
efficient removal of heat emitted during methanol production [201],
and increasing the equilibrium yield by selectively removing water from
the product via membrane reactors [54].
The second strategy for CDU methanol production, to first produce
syngas using CO2, and then to convert the produced syngas to methanol,
is being studied from various viewpoints as well. Joo et al.[90] devel­
oped the Carbon Dioxide Hydrogenation to Methanol via RWSG
(CAMERE) process, which sequentially produces CO via Eq. 4, and then
produces methanol by adding H2. The developed process was built as a
pilot plant with 66 % methanol yield, producing 75 kg/d of methanol
[137]. Another example is the complex reforming of methane-H2O-CO2.
Since the methane-H2O reforming and methane-CO2 reforming
C. Kim et al.
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,
the two reactions are incorporated simultaneously to produce syngas
products with CO:H2 ratio of 1:2.
2.1.3. Industrial applications
Industrially, research has been focused on using renewable energy
and CO2 to produce methanol, since it has the effect of mitigating carbon
emissions. An industrial scale version of such a process has been built by
the Carbon Recycling International (CRI) Inc. in 2012, incorporating the
fluegas obtained from a nearby geothermal power plant, and the H2
obtained by electrolysis of water to produce 4 Gt/y of methanol [6]. The
methanol plant uses the Cu/ZnO/Al2O3 catalyst [73], and the produced
methanol is mainly utilized for gasoline blending or for biodiesel pro­
duction [59]. A commercial-scale facility of CRI is currently under
construction in Anyang, China, with an expected capacity of 110,
000 t/y of methanol production.
Progress has been made in terms of catalysts as well. In 1996, the
Research Institute of Innovative Technology for the Earth (RITE) and the
National Agriculture and Food Research Organization (NIRE) of Japan
co-created a commercial catalyst by combining ZrO2 and SiO2 to the
widely used Cu/ZnO/Al2O3 catalyst [149]. By incorporating the devel­
oped catalyst and recycling the unreacted syngas, they were able to
produce methanol at 250∘C and 50 bar, with a purity of 99.9 wt%. Based
on this accomplishment, the Mitsui Chemicals Inc. constructed a pilot
plant producing 100 Mt/y of methanol in 2008. This plant consists of
CO2 from fluegas and H2 acquired from solar energy driven electrolysis,
making it a environment-friendly process [18].
In 2011, Air Liquide Inc. published a study regarding the production
of methanol from pure CO2 [139]. The commercial Cu/ZnO/Al2O3
catalyst was used, and the constructed pilot plant included a loop reactor
with a methanol liquefier, showing a carbon conversion of 94–96.5%.
While the productivity of the proposed process was lower than con­
ventional methanol production processes using syngas, compared to the
conventional process it has the advantage of producing high purity
methanol in similiar conditions of gas hourly space velocity, tempera­
ture, and pressure, where approximately 65% of the side products such
as esters, hydrocarbons, ketones, and C2 + alcohols, were reduced.
2.2. Polymer synthesis
2.2.1. Overview of technology
The advantages of polymer synthesis with regards to carbon emission
mitigation is that it can fix carbon as a product in longer durations than
other CDU-based products, and that the potential market size is large
3
Journal of CO2 Utilization 65 (2022) 102239
due to variety of products. Unlike CDU-based fuels or chemicals which
are combusted during usage, polymers are used as their end-product
forms. Also, after the end of product life polymers may be recycled to
reproduce polymers, which prevents re-emission of CO2 back into the
atmosphere. Regarding the related markets, CDU polymers are capable
of displacing the petrochemical-based polymer production market, and
also have the potential to create new markets with development of novel
materials. The overall polymer market was valued at 533.6 billion USD
in 2019, and is expected to expand with an annual growth rate of 5.1%
from 2020 to 2030 [25], having potential as a suitable market for CDU
products.
2.2.2. Current stage of development and research trends
Various materials can be incorporated for polymer production via
CO2, including the already commercialized polymer monomer pre­
cursors with carboxylate, ester, lactone, carbonate, and carbonyl func­
tional groups. These are all in the form of containing the molecular
structure of carbon dioxide as it is or maintaining at least one C– –O
bond, so it is possible to reduce the complex process of converting to an
active state such as excessive hydrogenation of carbon dioxide when
producing a carbon dioxide polymer, so it is possible to secure a rela­
tively economical process. A representative example of a technology for
converting CO2 to a monomer is the ethylene carbonate (EC)
manufacturing technology, which can be a raw material for poly­
carbonate, and a representative example of a technology for direct
conversion to a polymer compound is the production of polyether car­
bonate polyol, which is the main component of polyurethane.
Since many CDU-based polymer products have been commercial­
ized, recent studies are focused on developing new pathways for poly­
mer precursors, to reduce energy usage and to enhance profitability and
carbon footprint of the products. Various studies have focused on
copolymerization of epoxides and CO2 which leads to the production of
polyalkylene carbonates or cyclic organic carbonates, which can be
further processed into polyether(-polycarbonate)s, or polyhydroxyur­
ethanes [188]. The various routes of epoxide and CO2 copolymerization,
are provided in Fig. 2. The reaction of epoxides and CO2 may follow the
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)
have found applications in biomedicine and polyurethane foams, new
applications are being investigated for the reaction route b), where
various forms of polymers can be synthesized depending on the type of
epoxides. Representative applications of route b) are the preparation of
polyhydroxurethanes to produce non-isocyante polyurethanes (NIPUs),
C. Kim et al.
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
used for conventional production of polyurethane [40,95,156].
2.2.3. Industrial applications
Various economically viable CDU-based polymers have been
commercialized, such as polycarbonate (PC), polyol and polyurethane
(PU) production. Covestro Inc. is one of the companies which have
commercialized carbon-based polymer production. Their polyether-
polycarbonate polyol product, cardyon™, is known to reduce CO2
emissions by 20 % compared to the conventional polyol production
process [140], and is used to create flexible polyurethane foams. Their
core work was to develop a process to displace conventional polyol with
a carbon-based polyol, which was based on the development of a double
metal cyanide catalyst. Covestro AG built a demo sized plant in 2016,
producing 5,000 ton/y of polyol using CO2 obtained from a neighboring
chemical facility [10].
Novomer Inc. is also one of the leading companies in the production
of polyol. Their research is focused on the catalytic conversion of CO2 to
produce polycarbonate polyol, polypropylene carbonate, and poly­
ethylene carbonate. Development of the Salen-Co based homogeneous
catalyst sparked the research on CO2 conversion, and their recent output
of polypropylene carbonate for polyurethane production (Converge®)
can displace the conventional petrochemical-based polyol, including up
to 50 % of CO2 within their structure. Also, LCA of their polyol process
shows carbon emission mitigation of 67% compared to conventional
polyol production processes [53]. The technology and production rights
of Converge®have been taken over by Saudi Aramco on 2016, and
global market production is currently under development [29].
The Mg-based catalyst for efficient production of polyols, developed
by Econic Technologies, is currently in its pre-commercialization stage
[12]. The Mg-based catalyst promotes epoxy copolymerization of
polyolefins and cyclohexene oxides, which results in the production of
polyols and polyurethane. A key point of their technology is that the CO2
composition within polyol is increased, due to the use of a homogeneous
polyol catalyst.
Another application of CDU-based polymer is the process developed
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Journal of CO2 Utilization 65 (2022) 102239
by Asahi Kasei, where CO2 is utilized to produce polycarbonates (PC)
and high purity ethylene carbonates (EC). Their process producing CDU
PC was commercialized with a plant capacity of 150,000 t/y, and is
capable of reducing CO2 emissions (0.173 t/tPC) as well as substituting
the use of highly toxic phosgenes used in the conventional process [65].
A more recently developed process for producing high purity EC was
constructed with a capacity of 38,000 t/y EC, produced for developing
the solvent for lithium-ion batteries [1].
Newlight Technologies, Inc. developed a CDU-based high perfor­
mance thermoplastic, named AirCarbon®. AirCarbon®is produced by
re-assembling carbon, oxygen, and hydrogen, where carbon is obtained
by extraction from CH4 or CO2, incorporating a biocatalyst developed by
Newlight Technologies [19]. The process for producing AirCarbon®was
commercialized in 2013, and the products are being provided to
customer companies for use as packaging material.
2.3. Urea synthesis
2.3.1. Overview of technology
Urea was first obtained by Friedrich Wohler in 1828 by reacting
silver cyanate with ammonium chloride. Mass production became
available later on when Basarov started producing urea using ammonia
and CO2, and process development enabled economically efficient pro­
duction of urea. It is mainly used as agricultural fertilizer, and is also
utilized as a NOx reduction agent in diesel vehicles, a monomer for
polyurethane and an additive for cosmetics. The worldwide production
of urea was 233 Mt in 2019, and is estimated to increase to 300 Mt by
2030 [30].
2.3.2. Current stage of development and research trends
Recently, studies are being conducted to increase the yield rate of
urea and also to produce it while reducing carbon emissions. Urea
production via ammonium carbamate (AC) decomposition is one of the
representative methods. The related reactions are shown in Eqs. 5 and 6.
2NH3 + CO2 →NH2 COONH4 (5)
C. Kim et al.
NH2 COONH4 ⇌H2 N(C = O)NH2 + H2 O
As shown in the reaction equations the overall process is a 2-step
reaction. In the first step, AC is produced in an exothermic reaction,
then in the second step, the AC is dehydrated to form urea in an endo­
thermic reaction. While Eq. 5 reacts spontaneously with an ammonia to
CO2 ratio of 2–3 vol% in a temperature region of 180–210 ∘C and a
pressure of 150 bar without a catalyst, Eq. 6 is a slow equilibrium re­
action, and a commercial catalyst for intensifying the yield rate is yet to
be developed. The created urea is retrieved in low pressure, then the
unreacted AC is recycled back into Eq. 5. Thus it is essential to enhance
the process performance of the recycled NH3 and CO2, to maximize the
yield rate. Accordingly, recent studies are focused on enhancing Eq. 6,
by means of inorganic catalysts such as Cu(II) and Zn(II), or organic
catalyst such as DBU. One example is the study by Barzagli et al. [37],
where the production of urea at a mild condition of 100∘C and 3.7 bar
was reported. Results of the study show that, using an organic catalyst
DBU with the DMSO solute, an yield rate of 35% was achieved.
Other research efforts are being made from a more eco-friendly
perspective, such as urea synthesis via an electrochemical reaction of
N2 and CO2 in aqueous conditions. Chen et al. [45] published a study to
electrochemically generate urea under ambient conditions, by simulta­
neously fixing N2 and CO2. A flow reactor cell was fabricated with a
working electrode with Pd-Cu nanoparticles supported on TiO2 nano­
sheets as catalysts, a Ni foam anode, and an electrolyte based on an
aqueous KHCO3 solution. The proposed reaction mechanism is illus­
trated in Fig. 3(a). First, the N2 molecules are chemisorbed onto the
catalyst surface, forming activated N2 with reduced N–N bond order.
The existence of activated N2 promotes CO2 reduction to occur on
adjacent metal sites, forming CO. Then the intermediate *NCON* is
formed, which is subsequently hydrogenated to produce urea, at a
Faradaic efficiency of 8.92 % at − 0.4 V vs. reversible hydrogen elec­
trode (RHE). This research shows the potential for converting the con­
ventional process, which requires high initial investment costs and
energy input, into a low-energy, low-cost small scale process, which
allows localized production of urea in different parts of the world.
Various forms of research are being conducted to commercialize an
alternative route to produce urea. One of the representative research
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:
1
2RNH2 + CO + O2 →RNH(C = O)NHR + H2 O
2
2RNH2 + CO2 →RNH(C = O)NHR + H2 O
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.
Journal of CO2 Utilization 65 (2022) 102239
(6) These types of substitution reactions utilize Cs-based or K-based
catalysts. When an amine is deprotonated the basic condition of the
catalyst is relevant, and thus CO2 utilization in urea production is ad­
vantageous when alkylamine is the substrate. However, when the sub­
strate is an aromatic amine, only benzylamine is available. CO
utilization shows higher reactivity compared to CO2 utilization, in the
presence of a catalyst and an operating condition of 100–120 ∘C. How­
ever CO is more expensive compared to CO2 and also toxic, raising safety
issues during process operation. A CO2 utilization process has to be
operated at a temperature of 170–180 ∘C, to activate the thermody­
namically stable CO2. Also, H2O is produced as a byproduct, meaning
that the catalyst has to be stable enough not to undergo hydration in
high temperatures. By optimizing the process, eliminating the water
byproduct can increase the yield rate by promoting the forward reac­
tion. Recent studies show that with the appropriate selection of anions,
even Cs-based catalysts are stable in hydration conditions, providing
high yield of over 95% and a turnover frequency (TOF) of 858h− 1.
Various efforts have been made on the production of disubstituted urea
via the production of a novel catalyst. Choi et al. [47] proposed the use
of K3PO4 to catalyze the amine-CO2 carboxylation for producing 1,
3-disubstituted ureas with high yields. The schematic of the reaction
and the catalyst configuration is shown in Fig. 3(b) Truong et al. [167,
168] presented the use of alkali metal azolides as catalysts for ami­
ne-CO2 carboxylation to disubstituted ureas. Nguyen et al. [129] pro­
posed the use of polystyrene-functionalized basic ionic liquids (PS-BILs)
as catalysts for producing disubstituted ureas. Among the various can­
didates the [bis-imidazolium]/[bis-bicarbonate] showed the highest
activity and good recyclability of up to seven consecutive runs.
2.3.3. Industrial applications
CDU-based urea production is a mature technology, where all of the
urea production incorporates CO2 as raw material. The expected de­
mand of urea is estimated to expand at a growth rate of 2.1% between
2021 and 2026, forming a market size of 212 million USD [32]. Thus
urea production is expected to play a significant role as a main CDU
application. The role of industries would be to develop optimized pro­
cesses for cost efficient production of urea, such as integrating the en­
ergy loss from the ammonia production process.
2.4. Mineral carbonation
(7) 2.4.1. Overview of technology
Incorporating CO2 to mineral as a CDU application was first pro­
(8) posed by Seifritz [153]. Mineral carbonation technologies produce
carbon-based minerals by reacting CO2 with industrially developed
5
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

6
C. Kim et al.
promising results regarding mineral carbonation using ultrasound. Said
et al. [148] showed the enhanced performance of calcium extraction
from steel slag using ultrasound. Their results showed that ultrasound
can remove the porous layer which forms after calcium is liberated from
the slag, extracting 96 % of the Ca in the smallest particles of the slag.
Santos et al. [151] presented results on the improved performance of
mineral carbonation to produce aragonite, with the use of ultrasound.
The use of ultrasound reduced the required concentration of Mg, as well
as decreasing the reaction temperature to 24–70 ∘C. A recent study by
Wang et al. [173] presented the conversion of gypsum to CaCO3 via
ultrasonic carbonation, where pure vaterite was obtained by applying
50 % ultrasonic amplitude for 30 min. While scale-up of the
ultrasound-integrated process is yet to be realized, and current limita­
tions such as large amounts of electricity usage [133] must be dealt with,
ultrasound may prove to be an effective mineral carbonation route in the
near future.
2.4.3. Industrial applications
The carbonated mineral market consisting of products produced
from conventional processes is estimated to be 10–60 billion USD/y, and
is expected to increase to 550 billion USD/y in 2030. Due to this large
market potential, various construction companies are investing on the
CDU mineral carbonation process, such as Blue Planet, Calera, Skyonic,
Carbicrete, Carbon Capture Machine, and Carbon8 Systems. The Calera
Corp has published over 250 patents on the mineral carbonation pro­
cess, in which electrolysis is used to separate Ca and Mg used for
carbonation.
The Sleipner project injects CO2 into the Utsira saline formation of
the North Sea [38]. It is estimated that 30 million tonnes of CO2 will be
stored in the Utsira saline formation over the project life time of 30
years.
CarbonCure Technologies developed a CO2 curing process to pro­
duce concrete, where liquid CO2 is injected into a pressurized tank
where wet concrete is being mixed. The efficiency of CO2 absorption into
the concrete is known to be approximately 50–80 % [124]. The process
can be retrofitted into existing concrete plants, and is currently being
widely applied in ready-mix concrete plants in North America [8].
Carbon8 Systems developed the Accelerated Carbonization Tech­
nology (ACT), which utilizes CO2 to mineralize various thermal wastes,
including steel slags, incinerator ash, etc. [7] The first ACT plant was
built in 2012, which produces more than 65,000 t/y of carbonated
products, namely CircaBuild®, and CircaGrow® [203].
Carbonfree Chemicals developed a CO2-mineralization process for
manufacturing inorganic products, such as NaHCO3, baking soda,
caustic soda, etc. The process, namely the SkyMine®process, in­
corporates an electrochemical method to produce low-concentration
NaOH from salt and water [172]. This solution is used to capture CO2
to produce high-purity NaHCO3. The first SkyMine®plant was con­
structed in 2015, utilizing CO2 at a capacity of 83,000 t/y [9].
Carbfix, which is a carbon fixation frim in Iceland, injects CO2 into
basaltic rock, after mixing CO2 with water. Carbfix recently partnered
up with Climeworks, which is a direct air capture (DAC) firm, to capture
4000 tonnes of CO2 per year out of air, and to inject it into basaltic
formations in Iceland [3]. Currently an accumulated amount of 81,165
tonnes of CO2 have been injected by this process [4].
3. CDU in the development phase – Technologies with potential
for large scale reduction
In this section, various technologies that retain potential for large
scale CO2 reduction, but with less technological maturity compared to
technologies in the demonstration phase, are introduced. While these
technologies are still in the development phase and various hurdles need
to be overcome for commericialization, the large market available for
these technologies are attracting many corporations and research
groups.
7
Journal of CO2 Utilization 65 (2022) 102239
3.1. Carbon monoxide
3.1.1. Overview of technology
Carbon monoxide (CO) is obtainable from CO2 reduction, and has
high industrial value while retaining large CO2 mitigation potential.
Stoichiometrically, 1 mol of converted CO2 produces 1 mol of CO, which
means that 1.57 tCO2 can be consumed by producing 1 tonne of CO.
Upon mixing with H2 to obtain syngas, the widely utilized Fisher-
Tropsch process allows the conversion of syngas to a variety of hydro­
carbons and other value-added chemicals, making CO an attractive
option for commercial CDU application. Also, syngas can be processed to
produce methanol, which is a valuable chemical on its own, and can also
be further processed to produce olefins via the MTO reaction, as intro­
duced in Section 2.1. Furthermore, 99 % of the CO produced within the
steel industry is collected and reused within the facility or used to create
electricity in power plants, providing diverse applications for large scale
CO2 mitigation.
CO can be obtained from CO2 through various pathways, such as
electrochemical, catalytic, photochemical, and plasma conversion.
Electrochemical conversion of CO2 can be considered a green process if
the electricity produced from renewable energy sources, such as solar or
wind power, can be utilized. Photochemical conversion processes
directly incorporate solar energy, and allows production of chemicals
with minimal CO2 emissions given the appropriate light source and
catalyst. Plasma conversion allows rapid heating required for the
methane reforming process, by adjusting the frequency of plasma gen­
eration. While the carbon abatement potential of these technologies are
clear, additional research is required for large scale demonstration of
these technologies to take part in the CO2 mitigation objectives.
3.1.2. Current stage of development and research trends
Electrochemical CO2 reduction technologies producing CO can be
categorized according to the operating temperature. Low temperature
electrochemical conversion is processed at temperatures below 100∘C,
and make use of polymer membranes and acidic or basic aqueous
electrolytes. Water is first decomposed into O2 and hydrogen ions at the
anode, then the produced hydrogen ion is transferred through the
membrane to participate in reduction reactions with CO2, producing
valuable chemicals such as CO, formic acid, methane, and alcohols [64].
The specific products obtained from electrochemical systems differ ac­
cording to the catalyst and membrane type. Among the different cata­
lysts, Au, Ag, and Zn catalysts are known to provide the highest
selectivity for CO production [79]. High temperature electrochemical
conversion systems operate at approximately 800∘C, and incorporate
solid oxides as electrodes and the electrolyte. Upon operation, the
electrical energy provided decomposes the CO2 provided to the cathode
into CO and oxygen ion. Then the oxygen ion is transferred to the anode
through the electrolyte to produce oxygen gas by reaction with elec­
trons. High temperature electrochemical conversion incorporate the
cermet family of cathodes such as Ni and Yttria Stabilized Zirconia
(YSZ), and tend to have a higher conversion rate of CO2 compared to the
low temperature electrolyzers [200], regardless of the type of electrode
used. Recent research regarding electrochemical CO production focus on
the development and tuning of catalysts to enhance conversion and
selectivity, the design of electrolyzers [109], and the design of processes
integrated with the capture process to maximize energy efficiency and
improve profitability. Chung et al. [49] reported the development of a
catalyst for decomposing CO2 at low temperatures, which is produced by
sputtering of a liquid polymer and shows high stability and produc­
ibility, and also high conversion rate from CO2 to CO. Nguyen et al.
[128] proposed a method for increasing the Faradaic efficiency of CO
production by adjusting the coverage of reduced graphene oxide layers
on porous Zn electrocatalysts. Park et al. [138] recently developed a
metal-ceramic complex cathodic catalyst which operates at high tem­
peratures and shows stable performance even with certain amounts of
impurities included. Characterization images of the developed catalyst
 C. Kim et al.
are shown in Fig. 5. Rosen et al. [146] reported that the CO conversion
rate is extremely enhanced when ionic liquid is applied to the low
temperature electrolysis system.
Catalytic conversion technologies include a wide range of technol­
ogies that utilize catalysts and a reducing agent for converting CO2 to
CO. Dry methane reforming and CO2 hydrogenation reactions are
representative techniques. Dry methane reforming makes use of
methane as the reducing agent to convert CO2 to syngas, which has the
effect of mitigating two different types of greenhouse gases [85],
methane and CO2. Typical catalyst selections include transition metals
such as Ni, Ru, Rh, Pd, Ir, and Pt, which all show high activity when used
for methane reforming reactions. Among these candidates, Ni shows the
highest cost efficiency and is widely studied for commercialization of the
process. CO2 hydrogenation is the process of employing H2 as the
reducing agent to reduce CO2 to CO, and different chemicals may be
obtained according to the type of catalyst used. During CO2 hydroge­
nation two reactions occur competitively, the reverse water-gas shift
reaction (Eq. 4) and the methanol synthesis reaction (Eq. 3). The
selectivity of the reaction products are determined by the type of cata­
lyst used. CuO-ZnO/TiO2, Cu/ZnO/Cr2O3, and Cu/ZnO/Al2O3 all show
high selectivity of over 70% towards the production of CO [162]. Song
et al. [159] recently published a study on the development of the
NiMoCat catalyst, which is prepared by placing Ni-Mo alloy nano­
particles on the magnesium oxide support. The NiMoCat catalyst is re­
ported to have a long life time when used for dry methane reforming,
and shows no sign of coking or sintering. The synthesizing process and
images related to catalyst production is shown in Fig. 6. Joo et al. [91]
implemented the atomic layer deposition (ALD) method to produce a
catalyst for dry methane reforming, showing high conversion rate of
methane and improved life-time.
Photochemical conversion is the process of converting CO2 using the
excited state electron obtained by solar energy, and various products can
be obtained according to the number of electrons and photons incor­
porated in the reactions. A schematic of the photocatalytic CO2 reduc­
tion process is shown in Fig. 7 Typically for CO production, a
homogeneous reaction system based on a transition metal complex is
used. Various options of sensitizers, dopants, radiation sources are
considered for new catalyst development. An early example of such a
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.
8
­
Journal of CO2 Utilization 65 (2022) 102239
system is the Re-carbonyl system, where it was reported to selectively
produce CO when used in the form of a single component molecular
catalyst, acting both as a photosensitizer for absorbing light and as a
photocatalyst for accelerating the reaction [77]. Recently, Liu et al.
[117] proposed the use of a CuII complex molecular catalyst for reduc­
tion of CO2 to CO. Using [Ru(phen)3](PF6)2) as the photosensitizer, the
reaction was carried out with visible light, and the developed catalyst
showed a high TON of 9900 and a CO selectivity of 98 %. Zhang et al.
[197] developed a method for deriving single-atom catalyst from the
metal-organic framework. Using Co as the base metal, pyrolysis of the
ultrathin Co metal-organic layers during g-C3N4 formation resulted in
the anchoring of single Co(II) sites. The produced photocatalyst showed
a CO evolution rate of 464.1 μmol/gh, which was three times faster than
the bulky Co-MOF catalyst. Nguyen et al. [127] developed a novel
catalyst, Ag-decorated reduced TiO2/WO3 hybrid nanoparticles, for
converting CO2 to oxygen and CO when exposed to visual rays. The
catalyst performance was shown to have an apparent quantum yield of
34.8 %, with maximum selectivity of 100 % CO. Won et al. [181] greatly
enhanced the efficiency and life time of a photocatalytic system by
applying porphyrin dye.
Plasma conversion of CO2 is the process of using non-thermal plasma
to split CO2 to CO and O2, or via the dry reforming of methane (DRM)
process, where CO2 and methane are converted to CO and H2. Plasma
conversion has the advantage over catalytic conversions that carbon
adsorption on catalysts are prevented [157], which is a critical factor of
catalyst deactivation. Aerts et al. [34] presented the experiments and
computational analysis results of CO2 splitting via dielectric barrier
discharge (DBD) plasma. Investigation of the operating conditions
showed that the discharge gap and the specific energy input (SEI) has a
significant effect on the conversion and energy efficiency. For DRM,
recent studies focus on the hybrid application of plasma and catalysts to
maximize the process efficiency. Chu et al. [48] presented the use of
microwave plasma coupled with a catalytic reactor to convert CO2 and
CH4 to syngas under atmospheric pressure. The hybrid system showed
approximately twice as high conversion levels for both CO2 and CH4,
compared to the system using only the microwave plasma.
Martin-del-Campo et al. [42] proposed the integrated use of the rotating
gliding arc plasma and Ni-supported catalysts in a spouted bed reactor
C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

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

9
C. Kim et al.
efficiencies high enough to compete with other CO producing technol­
ogies, and further improvements are required for commercialization of
the process [122].
ReCarbon Inc. made progress on converting methane-CO2 to syngas
via plasma conversion at a foodwaste site, and is recently working on the
construction of a commercialized power plant based on these results.
The Emission Blade, a microwave plasma generation device, conducts
DRM to produce syngas in a Plasma Carbon Conversion Unit (PCCU)
[26].
3.2. Light olefins
3.2.1. Overview of technology
Light olefins are carbon-based chemicals that compose the building
blocks for various polymers. Light olefins include ethylene, propylene,
and butadiene, and are conventionally obtained by the naphtha cracking
process, ethane cracking process, and coal-to-olefin process from natural
gas, coal, and crude oil. The basic conversion equations of this process
are shown in Eqs. 9 and 10.
CO2 + H2 ⇄CO + H2 O (9)
CO2 + H2 ⇄(− CH2 − )n + H2 O (10)
Olefins can be obtained from CO2 via thermochemical and electro­
chemical pathways. For the thermochemical pathway, direct and indi­
rect hydrogenation are available options. For direct hydrogenation,
multi-functional catalysts are used to produce C2-C3 olefins. As for in­
direct hydrogenation, CO2 is first converted to CO, then proceeds with
the FT reaction, or is further converted to methanol to undergo the MTO
reaction. A summary of the thermochemical reaction routes from CO2 to
olefins is provided in Fig. 9. For the electrochemical pathway, Cu-based
catalysts are incorporated to directly produce light olefins by CO2
reduction.
3.2.2. Current stage of development and research trends
Since the reactions related to thermochemical conversion of CO2 to
olefins is mature, most of the recently published studies focus on the
development of catalysts to improve the overall performance.
Dorner et al. [56,57] developed catalysts based on Fe, Mn, and K for
CO2 hydrogenation to C2-C5 + olefins. The developed catalyst combines
the RWGS and FT chain growth reactions, and the Fe/Mn/K catalyst acts
as a bifunctional catalyst. Sai Prasad et al. [147] studied the FT reaction
of CO/CO2/H2 bio-syngas with Fe-based catalysts. At reaction condi­
tions of 300 ∘C and 10 bar, they obtained 39.19 % distribution of C2-C4
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
and Zn promoted Fe catalyst to achieve C2-C12 olefin selectivity of 80 %
at 39 % CO2 conversion. Analysis showed that using Zn enhances the Fe
Fig. 9. Various routes for producing light olefins from CO2 and H2 obtained
with renewable energy. Reprinted with permission from Centi et al. [43]
Copyright (2013) Royal Society of Chemistry.
10
Journal of CO2 Utilization 65 (2022) 102239
catalyst performance by enhancing H2 adsorption, and that the Na
promoter increases the CO2 adsorption and inhibits hydrogenation of
olefin, increasing selectivity. Witoon et al. [180] implemented the
Fe/Co/K/Al oxides catalyst for CO2 hydrogenation to olefins, with
alternating preparation methods to alter CO2 and H2 adsorption. The
results showed that by preparing catalysts by precipitation with NH4OH
as the reducing agent, followed by reduction using NaBH4 as the
reducing agent, showed the highest olefin yield of 16.58 % at 350 ∘C and
20 bar.
Kolesnichenko et al. [104] studied the conversion of methanol and
DME to olefins using zeolite catalysts modified with Rh compounds.
Their results show that the implementation of Rh centers increases the
selectivity of lower olefins synthesis. Hanaoka et al. [76] studied the
performance of zeolite catalysts for the DEM-to-olefins reaction. The
results showed that ferrierite zeolite with NH+ 4 showed the highest
n-butene yield.
Another significant pathway for converting CO2 to olefins is the use
of electrochemical reactions, where CO2 is reduced to produce olefins of
various carbon numbers, depending on the catalyst used.
Tomboc et al. [165] proposed the electrochemical conversion
mechanism of CO2 to ethylene, using Cu-based electrocatalysts. They
categorized the Cu-based electrocatalysts into four groups, namely
metallic Cu, Cu alloys, Cu compounds, and supported Cu-based cata­
lysts, and identified the detailed mechanisms for selective CO2 reduction
reaction for each of the different types of catalysts. Kim et al. [102]
synthesized a monodisperse nanoparticle of CoFe2O4 to produce
Na-promoted CoFe2O4 catalysts supported on carbon nanotubes, which
showed high CO2 conversion of 34% and light olefin selectivity of 39 %.
Jeong et al. [86] proposed the method of controlling the spacing be­
tween Cu facets within the atomic-scale to maximize binding energies of
CO2 reduction intermediates, enhancing the selectivity of C2 + products
during CO2 electrochemical reduction. Yang et al. [191] showed that
olefin production from CO and CO2 is possible using Na- and K-pro­
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,
affecting the CO and CO2 conversion. Gao et al. [67] proposed the use of
bifunctional catalyst composed of indium-zirconium composite oxide
and SAPO-34 zeolite, with the former composite responsible for CO2
activation and the latter composite responsible for selective C-C
coupling. The results showed high olefin selectivity as high as 80% at
CO2 conversions higher than 30 %. Yuan et al. [195] made use of
CoFe2O4 as a catalyst precursor for CO2 precursor, which showed high
selectivity for C2 + hydrocarbons. Analysis of the results showed that
high dispersion of Fe and Co helped inhibit the formation of methane,
and consequently promoted the formation of longer chain products.
3.2.3. Industrial applications
While various corporations produce olefins via the MTO reaction,
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
first converted to C2 + hydrocarbons, then transformed into aromatic
compounds on zeolites, and the methanol pathway, where methanol is
first synthesized from CO2, converted to olefins on zeolites, then finally
C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

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

11
C. Kim et al.
CO2 conversion and 39 % paraxylene selectivity was achieved, when
reacting H2/CO2 with a ratio of 3:1 at 30 bar and 350 ∘C [175]. Li et al.
[111] used the ZnZrO/HZSM-5 tandem catalyst to react H2:CO2 = 3:1
gas at 50 bar and 320 ∘C, showing 14 % CO2 conversion and 73 % aro­
matic compound selectivity. The reaction pathway via the tandem
catalyst, and the overall performance is provided in Fig. 10(a) and (b),
respectively. Tan et al. [196] used ZnCrOx/HZSM-5 catalyst for reacting
H2:CO2 = 3:1 at 30 bar and 340 ∘C, showing 20 % conversion of CO2 and
56 % aromatic selectivity. Zhang et al. [198] used ZnO/ZrO2/HZSM-5
catalyst to react H2:CO2 = 3:1 at 30 bar and 340 ∘C to obtain 9 % CO2
conversion and 60 % aromatic selectivity.
Regarding the FT pathway, Xu et al. [187] developed the
Na/Fe/HZMS-5 catalyst to react H2:CO2 = 3:1 at 10 bar and 340∘C,
achieving 27 % CO2 conversion and 53 % aromatic selectivity. The
overall mechanism and performance of the catalyst is shown in Fig. 10
(c) and (d)/(e), respectively. Sun et al. [177] used Na-Fe3O4/HZSM-5
catalyst to react H2:CO2 = 3:1 at 30 bar, 320 ∘C, and achieved 30 %
CO2 conversion and 20 % aromatic selectivity.
3.3.3. Industrial applications
Since the production of aromatic compounds is still at its early stage,
no commercialized plant exists.
3.4. Fuel (Power-to-liquids)
3.4.1. Overview of technology
The production of fuels from carbon dioxide, namely the power-to-
liquids (PtL) process, can be divided into two types according to the
intermediate product, methanol or CO [193]. A schematic of the overall
processes are given in Fig. 11. In the methanol-mediated fuel production
pathway, CO2 is first hydrogenated to produce methanol, then catalysts
suited for converting methanol to long-chain hydrocarbons are used to
produce fuel. The equation for CO2 to methanol is shown in Eq. 3, and
the conversion of methanol to hydrocarbons is shown in Eq.11.
nCH3 OH + H2 →CH3 (CH2 )n− 2 CH3 + nH2 O (11)
As for the indirect CO2 hydrogenation as CO as the intermediate
product, the RWGS process for producing CO from CO2 and H2, and the
FT synthesis step are integrated, to produce long-chain hydrocarbons as
the final product. The chemical reaction for converting syngas to hy­
drocarbons is shown in Eq. 12.
nCO + (2n + 1)H2 →Cn H2n+2 + nH2 O (12)
For both pathways, extensive amount of research has been conducted
for the separate steps, but there has been less interest in the integrated
process design to maximize efficiency. For example, considering the CO-
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].
12
Journal of CO2 Utilization 65 (2022) 102239
requires high process temperatures above 800∘C, where as FT synthesis
operates at relatively lower temperatures of 250 ∘C, but requires higher
operating pressures. Due to the difference in operating conditions of the
two processes, a significant amount of energy loss is inevitable when
sequentially connecting the two processes. Thus to maximize the energy
efficiency and product yield, it is essential to optimize the process
configuration, and to develop catalysts most suitable for an integrated
configuration. To avoid overlap with the previous sections, the
methanol-to-fuel and syngas-to-fuel reactions are the main focus of this
section.
When producing hydrocarbons via hydrogenation of CO2, the num­
ber of hydrocarbons follow the Anderson-Schulz-Flory (ASF) distribu­
tion [62,63], which shows the distribution of hydrocarbon formation
based on the chain-growth probability (α). Thus, while it is not possible
to specifically determine the types of hydrocarbons to be produced, it is
possible to manipulate the dominant hydrocarbon among the products,
by altering the α value with different catalysts. Conventional studies
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
catalysts increases the portion of n-paraffin within the final product, and
sequential upgrading processes can be installed to decrease the viscosity
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
produce chemical materials.
3.4.2. Current stage of development and research trends
For both the methanol-mediated and CO-mediated pathways, the
main focus of research is the catalyst development, since specific cata­
lysts must be used to increase the selectivity towards desired products.
Regarding the methanol-mediated pathway, a catalyst produced by
combining metal oxides with zeolites are used, and the type of catalyst
determines the confinement of the hydrocarbons, altering the final
product. Gao et al. [68] presented the use of a bifunctional catalyst for
directly hydrogenating CO2 to liquid hydrocarbon. By developing a
catalyst consisting of reducible indium oxides (In2O3) and zeolite
HZSM-5, C5+ products were obtained with a 78.6 % selectivity. The
oxygen vacancies of the In2O3 surface promote CO2 hydrogenation, and
the high C-C coupling is overcome by the zeolite pores, enhancing
long-chain hydrocarbon production.
Research regarding the CO-mediated pathway has been focused on
the single reactor process, and on the bifunctional catalyst capable of
promoting both the RWGS and FT synthesis. Mainly, Fe-based bifunc­
tional catalysts [55] are studied. Choi et al. [46] presented the devel­
opment of a new catalyst producing C5+ hydrocarbons with a 65 %
selectivity, by in-situ carburization of CuFeO2 to Hägg carbide. Wei et al.
[177] developed a Na-Fe3O4/HZSM-5 catalyst with three types of active
C. Kim et al.
sites. The Fe3O4, Fe5C2 and acid active sites, promote a tandem reaction
to produce C5-C11 products with 22 % conversion and 78 % selectivity,
at 320 ∘C and 30 bar. Jiang et al. [87] developed Fe- and FeCo-based
catalysts, achieving 54.6 % conversion and 47.0 % C5+ selectivity.
Tarasov et al. [164] showed the performance of Co-based bifunctional
catalyst in CO2 hydrogenation to hydrocarbon. At 260∘C, the 10%
Co/MIL-53(Al) catalyst showed 35.0% selectivity to C5+ with 25.3 % of
CO2 conversion. Shi et al. [155] presented the results of applying Na as a
promoter to the CoCu/TiO2 catalyst, to enhance selectivity towards
longer hydrocarbons. Their results showed that the addition of the
promoter increased the C5+ selectivity from 4.9 to 42.1 %, while
decreasing the CH4 selectivity from 89.5 to 26.1 %. Cui et al.[50] pre­
sents an approach for increasing the CO2 conversion and C5+ selectivity,
by coupling homogeneous and heterogeneous catalysts. Applying the
RuCl3 catalyst for RWGS and Ru0 catalyst for FT synthesis, and adding
LiCl as a cocatalyst and LiI as a promoter, the overall reaction could
proceed at a low temperature of 180 ∘C and achieve C5+ selectivity of
71.1 %.
A few studies focus on the kinetic modeling of the CO2 to hydro­
carbons reactions, based on the developed catalysts. Ghosh et al. [72]
presented results on the experimental and kinetic modeling results of the
methanol-mediated CO2 conversion to hydrocarbons, using the
In2O3/HZSM-5 bifunctional catalyst. Using a Langmuir Hinshelwood
Hougen Watson (LHHW) reaction mechanism the model was success­
fully validated with experimental data and was able to predict the hy­
drocarbon product distribution according to the ratio change among the
bifunctional catalytic bed components. Brübach et al. [41] proposed a
kinetic model of the CO-mediated hydrocarbon production reaction,
based on the potassium-doped, alumina supported, Fe catalyst
(Fe/K@ γ-Al2O3). Using a LHHW-type kinetic model their model was
able to reproduce the experimental results within the operating condi­
tions of 280–320 ∘C, 10–20 bar, and H2-to-CO2 molar ratio of 2–4.
Panzone et al. [134] also developed a kinetic model for CO2 hydroge­
nation using a Fe-K/Al2O3 catalyst based on a LHHW kinetic mechanism.
Their model considers the overall reactions capable via the CO-mediated
pathway, including alcohols and acids production, and includes oxy­
genates formation which are a critical byproduct of the CO2 hydroge­
nation reaction. These studies are important as the consecutive step for
developing the reactions to large-scale production plants.
Summarizing the mentioned studies, typical operating conditions of
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
efficient in terms of energy usage. However, additional research is
required to improve the one-step process, such as increasing the CO2
conversion rate of 30–40 %, which is low compared to the two-step
process of 80 %. In addition, process configurations need to be revised
and validated, such as adding process units for recycle and eliminating
excessive amount of water produced during the overall process.
Currently only model-based studies exist on the process configuration of
one-reactor conversion system [80,103], and thus experimental vali­
dation of the processes and further optimization of the configuration are
important for increasing the energy efficiency.
3.4.3. Industrial applications
The PtL technology is widely studied in Europe, and various projects
are being conducted to commercialize CO2-based fuel production.
Currently the largest consortium under operation is the Norsk e-fuel
project, which consists of European energy companies such as Sunfire,
Climeworks, Paul Wurth, and Norsk Vind [22]. The Norsk e-fuel project
is planning to operate a PtL plant for producing aviation fuel with a
capacity of 10 million liters of liquefied hydrocarbon by 2023. A
scaled-up plant producing 100 million liters of PtL fuel is planned to be
operated by 2026, which is estimated to mitigate CO2 by 250kton/y
[21].
The “Green Fuels for Denmark” project is a Danish consortium con­
sisting of major transportation corporations of Denmark, such as
13
Journal of CO2 Utilization 65 (2022) 102239
Copenhagen Airports, A.P. Moller-Maersk, DSV Panalpina, DFDS, SAS,
and Ørsted [14]. The project aims at decarbonizing the transportation
sector, by producing renewable methanol and renewable jet-fuel to
reduce 5 % of fossil fuel usage at Copenhagen Airport by 2027, and 30 %
by 2030. The core idea is to increase green H2 production using offshore
wind power (1.3 GW electrolyzer by 2030), then to react the H2 with
CO2 obtained from point sources to obtain methanol and jet-fuel. The
consortium is planning to provide 250 kt/y of green fuel by 2030,
abating CO2 emissions by 850 kt/y [15].
Porsche AG is cooperating with Siemens Energy on the Haru Oni
project aiming to produce e-fuels [24]. The Chile-based plant is expected
to produce e-fuel at a capacity of 130,000 L by 2022, and is planning to
construct a scaled-up plant producing 550 million liters of e-fuel by 2026
[23]. The main reaction pathway is to first produce methanol from green
hydrogen and CO2, then to convert the produced methanol to e-fuel.
The Spanish oil firm Repsol is planning to fund 100 million dollars
for constructing a zero-emission fuel production plant. In association
with Saudi Aramco, the they are planning to operate a e-fuel production
plant via the FT reaction, with a capacity of 2100 t/y by 2024 [28].
Another large-scale e-fuel project is being in progress by the Reliance
Industries, which are planning to convert all transportation energy
sources to carbon-zero fuel by 2035 [27]. Their projects focus on cata­
lytic and electrochemical conversion of CO2 to useful feedstock.
Other CO2-based fuel production projects within the industry include
the e-diesel project by Audi, and the Air to Fuels™ (A2F) by Carbon
Engineering. The Audi e-diesel is a project to produce diesel from green
hydrogen and CO2 obtained from a biogas facility. The project is oper­
ated in partnership with Sunfire GmbH, and has been producing e-diesel
(the long-chain hydrocarbon products obtained from the process) since
2015 [2]. The A2F process of Carbon Engineering combines direct air
capture (DAC) with H2 obtained from water electrolysis and CO2 hy­
drogenation to produce liquid hydrocarbon fuels [5]. First fuel pro­
duction from the A2F process was achieved in 2017 and further scale-up
and commercialization studies are under research, in partnership with
the PtL firm, Greyrock Energy [16].
4. CDU in the development phase – Technologies with potential
for small scale reduction
4.1. Formic acid
4.1.1. Overview of technology
Formic acid is utilized throughout various industries, such as for
leather and fiber production, and as eco-friendly snow removers and
coagulants for rubber production. The amount of formic acid production
was 870 kt in 2021, and the market is estimated to grow to 1.8 billion
USD by 2027. The current formic acid market is small compared to other
chemicals such as ammonia, but its demand is expected to increase with
the development of direct formic acid fuel cell (DFAFC) technology and
with extended applications as a hydrogen carrier [52]. Production of
formic acid via CO2 is achieved through various pathways, including
catalytic chemical conversion and electrochemical conversion. Pre­
liminary life cycle assessment (LCA) results show that formic acid has
the highest potential for CO2 mitigation compared to the conventional
process [160]. However, the catalytic and electrochemical technologies
for converting CO2 to formic acid are still in their development stage,
and further studies on the catalysts and process configuration, and
experimental validation from large-scale pilot operation are required for
commercial applications.
Catalytic chemical conversion involves the hydrogenation of CO2 to
obtain liquid chemicals, and formic acid is considered one of the most
valuable products of catalytic conversion, other than methanol, ethanol,
light olefins, gasoline, and diesel.
Electrochemical conversion involves the coupled conversion of CO2
and H2O by applying electrical energy to an electrolyzer⋅H2O is oxidized
at the anode, while CO2 is reduced at the cathode by receiving the
C. Kim et al.
electron and hydrogen ion to produce formic acid or formate. Only 2
moles of electrons are required per 1 mol of CO2 reduction, and thus
formic acid is considered the most economic chemical obtainable
through electrochemical conversion. The selectivity of the products
obtained from the cathode mainly rely on the type of metal/metal oxide
catalysts used. Formic acid is the primary product when catalysts such as
Sn, In, Pb or their oxide forms are used [89].
Photoelectric methods incorporate solar energy to reduce CO2 to
produce valuable products. There two types of photoelectric methods
based on the material used for the reactions, namely photocatalytic
conversion and photoelectrochemical conversion. Photocatalytic con­
version reduces CO2 within a solution where the photocatalytic nano
particles are suspended. Photocatalysts mainly consist of semiconductor
material, where electrons are emitted upon solar exposure to be deliv­
ered to the CO2. While photoelectric conversion of CO2 is the most eco-
friendly technology to reduce CO2, since it reduces CO2 by mimicking
the photosynthetic process of plants, its research is still in the basic
phase and there are many hurdles to overcome for commericialization.
4.1.2. Current stage of development and research trends
Recent research results regarding CO2-based formic acid production
is focused on the development of catalysts for thermochemical conver­
sion, electrocatalyst development for reducing the required over­
potential, and studies on extracting H2 from formic acid.
Formic acid production via CO2 hydrogenation usually occurs in
aqueous amine conditions, since the direct reaction of CO2 and H2 is
thermodynamically unfavored. During early stages of research, focus
has been made on development of homogeneous catalysts for enhancing
CO2 hydrogenation reactivity within the aqueous amine environment.
Noble metals such as Ru, Rd, and Ir, and transition metals including Ni,
Cu, and Fe have been incorporated as homogeneous catalysts. Tanaka
et al. [163] developed a new catalyst, PNP-Ir(III) hydride complex,
where PNP is a alkylphosphine-based pincer ligand acting as an efficient
electron donor. In aqueous KOH conditions and at 120∘C and 60 bar, the
proposed catalyst showed good performance with a TOF of 73,000 h− 1
for 48 h. Filonenko et al. [61] studies the Ru PNP-pincer catalyst-based
CO2 hydrogenation and dehydrogenation system. Using 1,8-diazabicy­
clo[5.4.0]undec-7-ene (DBU) as a base promoter, the developed cata­
lyst showed TOF performance of 1,100,000 h− 1 for formic acid
production at 120∘C and 27 bar. Liu et al. [114] developed an Ir catalyst
containing an imine-diphosphine ligand. Using a 5 M KOH as the base,
the developed catalyst showed performance of TOF 450,000 h− 1 at
140 ∘C for 20 h. However, despite the good performance shown by
previous studies, homogeneous catalysts have a critical limitation for
large-scale applications, due to the difficulties of catalyst separation
from the final product [74]. Thus to overcome this limitation, recent
studies have focused on the development of heterogeneous catalysts for
CO2 hydrogenation.
Su et al. [161] studied the performance of carbon-supported palla­
dium nanocatalysts based on the ammonium bicarbonate/formate redox
equilibrium. They tested the performance of CO2 hydrogenation at
varying operating conditions, and showed that the highest performance
was obtained at 55 bar with Pd/AC (activated carbon) nanocatalyst,
showing TOF of 1103 h− 1. Umegaki et al. [169] studied the hydroge­
nation of supercritical CO2 using Ru nanoparticles as the catalyst. At
operating conditions of 80 ∘C and 130 bar, the catalyst performance
showed a TOF of 2117 h− 1. Park et al. [135] developed and studied the
performance of Ru molecular catalyst on a bpyTN-30-CTF support. The
use of the bpyTN-30-CTF support increased the porosity and metal
anchoring sites, enhancing the performance and stability of the catalyst.
Notably, the performance of the catalysts were validated on a contin­
uous hydrogenation reactor, reaching a total TON of 524,000 during 30
days of operation.
Regarding electrochemical reduction of CO2 to produce formic acid,
high overpotential, low product selectivity, and electrode poisoning are
the main hurdles that need to be overcome. Conventional metal catalysts
14
Journal of CO2 Utilization 65 (2022) 102239
for include Pb, Ru-Pd, Hg, Sn, In, and Cd [119]. In, Bi, Hg, and Pb cat­
alysts have shown high Faradaic efficiencies of above 80% at high cur­
rent densities. Other metal catalysts, including Zn, Cu, and Cd promoted
the reduction of CO2 to formic acid, but showed low Faradaic effi­
ciencies and current densities. Among the D-group metals, such as Pd,
Rh, and Ir, Pd has been known to show the highest performance, having
achieved 100 % Faradaic efficiency at high current densities. Rh and Ir
catalysts have shown low Faradaic efficiency toward formic acid, and
the products are dominated by CO and H2. Despite the high electro­
chemical performance of some of the metal catalysts, the large over­
potential still imposed a problem, providing motivation for development
of the metal-complex catalysts. Transition metal complexes, suchs as Rh,
Ir, and Ru complexes, have shown to lower the require overpotential
while retaining good electrochemical performance. Ishida et al. reported
large amounts of formate production using the [Ru(bpy)2(CO)2]2+. The
electrochemical conversion pathways of CO2 reduction to formic acid,
and a summary of the various metals implementable as catalysts is
presented in Fig. 12.
Recent studies on the electrocatalysts of CO2 hydrogenation present
results of enhancing formic acid productivity by employing solid-state
electrolytes. Formate produced by CO2 reduction in aqueous condi­
tions require additional separation processes to purify formic acid as the
final product, deteriorating the economic potential [186]. Xia et al.
[185] studied the performance of a CO2 reduction cell with a
three-chamber configuration, based on the use of Bi nanosheets as teh
electrode. Sequentially utilizing the solid-state electrolyte (SSE), anion
exchange membrane (AEM), and the cation exchange membrane (CEM),
formic acid is produced separated from the electrolyte. The results of
their study showed formic acid Faradaic efficiency of up to 93.1 % at
3.08 V. Fan et al. [60] conducted research on the use of an all-solid-state
electrochemical CO2 reduction system to enhance the concentration and
purity of formic acid. By combining the grain boundary-abundant Bi
nanoparticles, which originally showed high current density and Fara­
daic efficiency, and the porous solid electrolyte (PSE) layer to obtain
formic acid in the form of vapors, the authors obtained high purity
formic acid solutions with concentrations of near 100 wt%.
4.1.3. Industrial applications
Formic acid production via CO2 hydrogenation is yet to be
commercialized, and various research efforts are being made for formic
acid process development, but many obstacles have to be overcome.
Researchers in Germany and corporations such as BASF have conducted
much research on the topic, but their focus was on homogeneous cata­
lysts, which has the inherent problem of separating the catalyst from the
produced formic acid, hindering commercialization.
Another actively studied field for formic acid production is the use of
electrochemical conversion of CO2. Formic acid or formate may be
produced according to the electrolyte or catalyst system of the electro­
chemical reactor. Recent work on the topic include the electrochemical
reactor and reduction electrode by Liquid Light, the anion exchange
membrane system, Sustainion, by Dioxide Materials [190], the separa­
tion of formic acid and potassium sulfate via pH swing developed by
Seogang University, the catholyte-free CO2 reduction system [108],
which overcomes the restrictions imposed by CO2 in water and mass
transfer within the electrolyte, by KIER, and the cyclic two step elec­
trolysis developed by KIST [106]. Other researchers make use of solar
energy to increase the energy efficiency of the electrochemical system.
Kang et al. developed a photocatalyst based on Cu-Fe oxide, allowing
formate production with a 90% selectivity, without the application of
additional power voltage [93]. Yadav et al. developed a flexible polyer
film-based photocatalyst, which selectively produces formic acid upon
exposure to solar energy [189].
The ECFORM process developed by the DNV GL is a process for
directly converting CO2 to formic acid and formate. By applying a Sn-
based alloy catalyst, the electrolysis reactor is known to have a
formate selectivity of 75 %. A bench-scale plant with a CO2 utilization
C. Kim et al. Journal of CO2 Utilization 65 (2022) 102239

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

15
C. Kim et al.
acetic acid using CO2, H2, and methanol. Using a bimetallic catalyst
Ru-Rh with imidazole as the ligand, LiI as the promoter, and 1,3-dime­
thyl-2-imidazolidinone (DMI) as the solvent, methanol was hydro­
carboxylated to acetic acid with a yield of 70.3 %. The imidazole ligand
played an important role in enhancing the reaction via good coordina­
tion capability with the active center, showing TOF in acetic acid pro­
duction of 30.8 h− 1 at 200 ∘C. The reaction mechanism is shown in
Fig. 13(a).
Other studies report the use of plasma-driven catalysis for acetic acid
production from CO2. Wang et al. [174] proposed the use of non-thermal
plasmas with catalysts to directly produce acetic acid from CO2 and
methane. The proposed system couples a dielectric barrier discharge
(DBD) reactor with a ground water electrode to allow acetic acid for­
mation at mild operating conditions (30 ∘C, 1 atm). Utilizing a
Cu/γ-Al2O3 catalyst in the DBD reactor, acetic acid selectivity of 40.2 %
was obtained. The performance test results of the product selectivity
when using different operational modes (catalyst only, plasma only, and
combination of catalyst and plasma) are provided in Fig. 13(b).
The second pathway of CO2 utilization for acetic acid formation is
the direct reduction of CO2 through electrochemical conversion. Studies
regarding electrocatalysts have focused on the use of metal catalysts
such as Cu, Fe, and Mn. Genovese et al. [69] used Cu nanoparticles on
carbon nanotubes as the catalyst for promoting the C-C bond formation,
achieving Faradaic efficiencies for acetic acid formation of 56%. With
the use of Fe, Genovese et al. [70] achieved Faradaic efficiencies of
60.9%, using FeIII oxyhydroxide on N-doped carbon as the catalyst.
Other studies have combined the use of electrolyzer configuration with
catalyst development to improve the overall performance. The
three-chamber cell consisting of SSE, AEM, and CEM, which was used for
formic acid production in section 4.1.2, can be further extended for
electrocatalytic acetic acid production systems. The system proposed by
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
nanoparticles. Zhu et al. [202] present results for obtaining acetic acid
via CO reduction. By optimizing the edge-to-surface ratio to obtain a Cu
nanocube catalyst suited for the reaction, and coupling the catalyst with
the porous solid electrolyte (PSE) reactor, acetic acid was obtained at
neutral pH, with Faradaic efficiency of 43% and partial current density
of 200 mA ⋅ cm− 2. While the study does not directly incorporate CO2 for
electrochemical conversion, the high selectivity of the proposed reactor
could be successfully coupled with CO2 to CO reduction for carbon
mitigation. Acetate production performance using the developed cata­
lyst is presented in Fig. 13(c). De et al. [51] proposed the use of mo­
lecular manganese corrole complex as the electrocatalyst for CO2
conversion to acetic acid. Structure of the Mn-corrole catalyst is shown
in Fig. 13(d). MnIII-corrole was stabilized on carbon paper and used as
the CO2 reduction catalyst in a moderate acidic medium of phosphate
buffer. The experimental results showed that the cell was operable at
− 1.25 V vs. Ag/AgCl (1 M KCl) reference node, and a maximum FE of
63 %, and TOF of 8.25 h− 1 was obtained. The suggested mechanism is
that the MnIII bound oxalate intermediate readily forms acetate,
increasing the selectivity of the product.
4.2.3. Industrial applications
Since CDU-based acetic acid production is still in its early stage,
large-scale application of the processes are yet to be developed.
4.3. Carbon material
4.3.1. Overview of technology
Other than producing chemicals and fuels from CO2, various at­
tempts have been made to produce carbon material from CO2. Examples
of these efforts include the production of diamonds, carbon nanotubes,
and carbon blacks. Carbon materials with good electrical, mechanical
characteristics, and thermal stability allow them to be implemented for
energy conversion equipment such as fuel cells, super capacitors, and Li-
16
Journal of CO2 Utilization 65 (2022) 102239
ion batteries. Also, conversion of CO2 to construction material such as
CaCO3 gives them the potential to substitute conventional material such
as steel and cement.
4.3.2. Current stage of development and research trends
Different research groups have presented studies regarding the pro­
duction of various carbon materials. Wei et al. [178] reported the for­
mation of porous carbon via the reaction of supercritical CO2 with alkali
metals, at intense operating conditions of 500 ∘C and 300 atm in an
autoclave. Upon analysis of the product, it was shown that graphite
particles with relatively low graphitization, retaining Raman spectra
relative intensity ratio values in the range of 1.02–1.11, were produced.
Lou et al. [118] presented the results of producing diamonds of sizes up
to 250 μm by reducing CO2 at low temperatures, using pure Na to reduce
dense CO2 at 440 ∘C and 800 atm. Ren et al. [145] presented the results
of producing carbon nanofibers (CNFs) by electrolytic conversion of
CO2. The electrolysis was carried out using inexpensive electrodes of Ni
and Ir, and the structure of the CNF could be manipulated by addition of
trace transition metals or an initiator such as Zn. Extending from the
previous study, Ren et al. [143] proposed the method of transforming
CO2 to multi-layered carbon nanotubes via molten electrolysis. This
technology incorporates electricity produced by solar energy, and pro­
duces O2 as a byproduct, meaning minimal emission of pollutants during
the process. A summary of the pathways for producing CNT “wool”,
which is an extension of the study by Ren et al. [145] presented in
Johnson et al. [88], is shown in Fig. 14. Kim et al. [97] proposed the
method of using boron hydride reducers to produce carbon nanotubes at
mild conditions. The operating conditions of this process is very mild
compared to previous studies, operating at 1 atm, and also the
post-processed carbon nanotubes can be applied to fuel cells and super
capacitor electrodes.
4.3.3. Industrial applications
While no commercialized application of CDU-based carbon material
production exists up to date, a few start-ups are working on the
demonstration of large-scale application of CNT production from CO2.
One of the leading corporations of CNT production is Carbon Corp, who
have research experience in terms of CNT and carbon nanofiber pro­
duction [88,144,145].
5. Overview of factors related to commercialization
For a CDU-based product to be commercialized, various factors,
including the chemical costs, market scale, and the technology readiness
levels (TRLs), have to be considered. The market sizes and costs for the
chemicals considered in this study are presented in Fig. 15. It should be
noted that the provided chemical prices are not values obtained by CDU-
based production, but by conventional production methods. Among the
CDU-based chemicals considered in the review, CO, light olefins, and
fuel were excluded from the figure since a realistic market size could not
be defined. An overall tendency is for chemical price to be inversely
proportional to market size, since prices become higher when chemicals
are produced in less quantity, and vice versa.
Considering the technology readiness level (TRL) of each technology,
which is a factor for indicating the maturity of a technology with an
index value from 1–9, Chauvy et al. [44] provided the TRL of various
technologies and the timeframe to actual deployment of the technology.
While not all of the technologies considered in this review are provided,
the TRLs are in correspondence with the categorization used in this re­
view. Thus the timeframe to deployment for each technology can be
estimated accordingly. According to the TRL values, methanol and cal­
cium carbonates have a high probability of commercialization in the
upcoming years. Both products have a sufficiently large market, and
thus focusing on the scale-up operation of pilot plants and process
validation of the developed technologies will be a good strategy for
promoting the realization of a CDU technology. For technologies
C. Kim et al.
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
Intelligence [125]. Values were averaged over the year 2021, and for chemicals
where prices for 2021 were not available, the most recent prices were used.
retaining TRLs of less than 6, research should be more focused on
fundamental development and bench-scale operations Fig. 16.
6. Conclusion and Perspectives on CDU
Many countries have invested in the development of CDU technol­
ogies as a means of approaching a net-zero economy. While the final
goal may be to achieve net-zero via total transition of the economy to­
ward renewable energy, realizing the technologies to every corner of the
society requires a great deal of time, when immediate action is essential
to meet short-term CO2 mitigation goals.
17
Journal of CO2 Utilization 65 (2022) 102239
Fig. 16. TRL and timeframe to deployment for various CDU-based chemical
production technologies. Copyright (2019) Elsevier.
In terms of large-scale application, methanol, polymer, urea syn­
thesis and mineral carbonation technologies are leading the race. Some
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
nologies are capable of carbon fixation for a long period of time. These
aspects have motivated governments to supply funding for development
of the core technologies, and have encouraged industrial partners to
participate in verifying the validity of the technologies, after being
verified at lab scale. Taking into account these three aspects, a potential
CDU application with high possibility of large-scale applications in the
near future is the production of chemicals via the direct conversion of
amine-captured CO2, including formic acid, CO, and methanol
C. Kim et al.
production.
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
product, hence reducing the additional input of energy required in
conventional CDU processes for amine regeneration. Since amine
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
[123], direct conversion of amine-captured CO2 can greatly improve the
costs required for CDU applications. The direct conversion of
amine-captured CO2 can be achieved either through a thermocatalytic
pathway or an electrochemical pathway. Early studies have been
focused on the thermocatalytic conversion, as presented in Yang et al.
[192] and Liu et al. [113]. In these studies, the superbase/polyethylene
glycol binary system, and N-substituted amino acid salts, were proposed
as solvents for capturing and activating the CO2 for subsequent re­
actions, respectively. Later on, studies regarding the production of for­
mic acid or methanol were introduced, using sterically-hindered amines
or metal hydroxide amines, as introduced and categorized in Kar et al.
[94]. Regarding electrochemical conversion, recent studies have pro­
posed conceptual processes and experiments for directly converting the
captured CO2 present in the form of a bicarbonate, to produce syngas
[66,107,110]. Since syngas can be converted into a variety of chemicals
through further reactions, realization of this technology could critically
affect the CDU industry. Considering the economic and environmental
benefits of direct conversion of amine-captured CO2, the technology has
potential for developing into a major component of CDU applications.
Also as a note on formic acid, while formic acid has a relatively small
market compared to other chemicals [44], the situation may change
with the accelerated development of the hydrogen economy. Given the
high volumetric capacity of H2 within formic acid (53 gH2/L), and the
fact that formic acid exists as a liquid at standard temperature and
pressure, formic acid has the potential to be applied as a liquid organic
hydrogen carrier (LOHC) [58]. A LOHC can deliver H2 to the usage site
at normal conditions, stabilizing the H2 transportation and storage
processes. Recent studies have shown the economic competitiveness of
formic acid as a LOHC compared to other chemicals [131], and startup
companies such as DENS (Dutch Energy Solutions) [11] have been
focusing on developing a commercialized solution integrating formic
acid dehydrogenation for fueling vehicles. The extended use of formic
acid as a LOHC will expand the market size and formulate a carbon
cycle, elongating the carbon fixation period.
It is worth noting that for CDU technologies to take a significant role
in CO2 abatement, careful coordination with the governmental policies
and the related market change is important [92]. Environmental pol­
icies, expressed in the form of carbon pricing, can shift the orientation of
CDU research by forcing market regulations such as carbon credit and
carbon taxes, or by providing financial support and incentives toward
specific products [33]. Carbon pricing includes the emissions trading
system (ETS), carbon tax, and the results-based climate finance (RBCF),
which work in complementary ways for policy decision-making and
imposing industrial regulations. The global carbon pricing revenue has
increased by 60% in 2021 compared to 2020 levels [33], and accord­
ingly the related market is expected to increase as well. Markets related
to carbon capture utilization and storage (CCUS), which includes CDU
and carbon dioxide storage technologies, is estimated to grow to 7.27
billion USD by 2025, and the capacity of CO2 abatement is expected to
be 77–2200 million tonnes [98]. Considering the large amounts of in­
vestments required for developing a CDU technology to a commercial
scale, it is important to focus research efforts to CDU technologies that
reduce large amounts of CO2 emissions, and are capable of being inte­
grated with technologies providing profitable products.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
18
Journal of CO2 Utilization 65 (2022) 102239
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgments
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korean government (MSIT) (no. NRF-
2020M3H7A1098271).
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