Aplicações para o Dióxido de Carbono

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Chemical Engineering Journal 427 (2022) 130980

Contents lists available at ScienceDirect

Chemical Engineering Journal


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

Review of recent technologies for transforming carbon dioxide to


carbon materials
Jae Hyun Park 1, Jeongwoo Yang 1, Dohyeun Kim, Hyeonseo Gim, Won Yeong Choi, Jae W. Lee *
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141, Republic of Korea

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

Keywords: Since the Industrial Revolution, as fossil fuels have been applied to a wide range of fields, greenhouse gas
Carbon dioxide (CO2) emissions have continuously increased. In particular, in order to mitigate carbon dioxide emissions, which ac­
Transformation count for the largest percentage of greenhouse gases, various scientific technologies have been developed since
Porous carbon
the Paris Agreement launched in 2015. Representatively, CCUS (carbon capture, utilization, and storage) tech­
Carbon capture
Carbon utilization
nology, which can convert atmospheric carbon dioxide into other high value-added materials, has been attracting
attention. However, since carbon dioxide is very stable due to the double covalent bonds between carbon and
oxygen atoms, various paths such as supercritical transformation, electrochemical conversion, and metal-based
and inorganic substance-based conversion have been applied to convert it. This review introduces and provides a
comprehensive overview of the latest studies as well as existing technologies to transform carbon dioxide into
carbon materials.

1. Introduction rocks. Recently, however, problems such as the limit of the potential
storage capacity and the possibility of leakage have been pointed out. To
Greenhouse gas refers to a specific gas that absorbs or reflects address the limitations of CCS technology, advanced technology for
infrared radiation from the earth’s surface to space, raising the tem­ recycling the captured CO2 (carbon capture and utilization, CCU) has
perature of the earth’s surface. The emission of these greenhouse gases emerged [8–12].
has increased rapidly during the modern industrial period, causing large CCU technology is a generic term for technology that converts
natural disasters such as desertification, glacier reduction, and increased captured CO2 into more valuable materials rather than simply storing it.
sea levels [1]. In order to prevent such climate change, regulations on The maturity of the technology is low compared to CCS, but it is strongly
greenhouse gas emissions have been progressively adopted since the appreciated for its potential. In particular, the weight of 400 ppm, which
Paris Agreement in 2015. In particular, since carbon dioxide (CO2) ac­ is the average CO2 concentration in the atmosphere, is about 3 × 1012
counts for>80% of total greenhouse gas emissions, the regulation of CO2 tons on the earth, and this is a great carbon resource that is quantita­
has been intensively discussed [2–4]. tively superior to that of the buried oil [2,13–16].
In this respect, numerous studies to suppress CO2 emissions or to Recently, advanced CCU to convert CO2 captured into highly valu­
store the emitted CO2 (carbon capture and storage, CCS) have been able carbon-based compounds such as diamond [17,18], graphene [19],
conducted [5–7]. The former entails research on limiting the use of fossil fullerene [20], carbon nanotubes (CNTs) [21,22], porous carbon [23],
fuels, one of the main sources of CO2 emissions, and developing alter­ and carbon nanofibers (CNFs) [24,25] has been drawing a great deal of
native energy systems. In particular, instead of fossil fuels, research on attention. However, since each atom in CO2 is connected by double
renewable energy as energy generating system and research on sec­ covalent bond, it is very difficult to break this bond and to convert it into
ondary batteries as energy storage system have been conducted. The another compound at room temperature. The CO2-derived materials
latter body of research on CO2 storage is focused on methods of noted above were subjected to extreme conditions, including not only
capturing the released CO2 and then disposing or storing it in foliated high temperature but also the high-pressure supercritical or liquid CO2

* Corresponding author at: Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon 34141,
Republic of Korea
E-mail address: jaewlee@kaist.ac.kr (J.W. Lee).
1
Both authors are co-first authors and contributed equally to this work.

https://doi.org/10.1016/j.cej.2021.130980
Received 15 April 2021; Received in revised form 14 June 2021; Accepted 19 June 2021
Available online 25 June 2021
1385-8947/© 2021 Elsevier B.V. All rights reserved.
J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

rather than atmospheric CO2 gas. Thus, an additional process is required 70 according to the few-layer-graphene weight ratio. The electrical
for conversion from the atmospheric gas phase. In this respect, regard­ conductivity increased to 10-2 S cm− 1 with 7 wt% of few-layer-graphene.
less of how high the product value is, if the cost of the synthesis exceeds The surface property at low temperature of graphene nanosheets was
this value, the economic impact will be lost. In this respect, this review also investigated [27]. Based on the nitrogen isotherm, the Mg-derived
introduces various CCU technologies that transform atmospheric CO2 as carbon material was found to have a high surface area (594.7 m2 g− 1)
the sole source into carbon materials. First, experiments using dry ice or and pore volume (0.85 cm3 g− 1).
supercritical state CO2 as raw material in a conventional way of con­ As this carbon material has previously mentioned properties, many
verting carbon dioxide into carbon materials will be addressed. Second, studies on its application to various fields have been conducted. For
molten salt systems that synthesize carbon material via electrochemical example, the resultant graphene material was used to remove an azo dye
reactions are suggested as an alternative method to complement the [27], because it had an appropriate pore diameter (6.28 nm) as an azo
conventional technologies with a critical problem of harsh experimental dye (Reactive Black 5, RB5) adsorbent. Because the Mg-derived carbon
conditions. Also, as attempts to increase the possibility of continuous material from dry ice has a high specific surface area and π-π bond in the
operation and scale-up, metal and inorganic-based conversion methods, graphene nanosheet, the removal efficiency of an azo dye was excellent
which can perform CO2 conversion through moderate experimental in various environments.
conditions and facile continuous systems compared to other strategies The CO2 and Mg combustion-derived carbon was also utilized as H2
based on superior reducing ability, are focused. In addition, the storage system at low temperature [28]. As presented in Fig. 1D and 1E,
strengths and limitations of the introduced technologies are also sum­ rectangular-shaped graphitic carbon nanocages were generated with
marized for future CO2-related research and development. aggregation and higher crystallinity than conventional reduced gra­
phene oxide (GO) and other bulk graphene. Because the interaction
2. Conventional conversion technologies with extreme between the carbon at the graphene edge and hydrogen molecules is
conditions stronger than in the case of other carbon materials, the hydrogen storage
capacity at low temperatures and room temperature was superior to that
2.1. Conversion from the solid phase of dry ice of other carbon materials.
Nickel selenide-coated cube-shaped lidless graphitic boxes
Dry ice, which is the solid form of CO2, sublimates at 194.65 K (graphitic-boxes/NiSe) were synthesized and utilized for a quasi-solid-
(-78.5 ◦ C) at atmospheric pressures and it can be manufactured by state dye-sensitized solar cell (DSC) [29]. In this work, the carbon
compression and expansion processes. Due to the abundance of raw nanostructure derived from dry ice and Mg was utilized as a support for
materials, numerous experiments applying dry ice for transformation anchoring NiSe spheres as shown in Fig. 1F. Furthermore, it was
into carbon materials, as listed in Table 1, have been reported. In observed that the sample has properties of NiSe and graphitic carbon,
particular, dry ice has been applied to a CO2 reaction with metals to respectively, as presented in Fig. 1G and 1H. These graphitic boxes have
produce metal oxides and solid carbon. The metal used mainly in this π-π bonds that allow electrons to flow faster and large specific surface
reaction is magnesium. This reaction is delineated as follows: area over which the catalyst can spread evenly. Therefore, the electrode
using the catalyst embedded in graphitic boxes has higher power con­
2Mg(s) + CO2 (g)→2MgO(s) + C(s) (1)
version (8.26%) than a pure NiSe electrode (7.45%).
Burning Mg metal with dry ice resulted in nano-caged carbon ma­ There have also been attempts to make the existing carbon nanoc­
terials [19]. More specifically, Mg ribbon was reacted between dry ice ages more suitable for application by adding a post-treatment to the
slabs. After the combustion of Mg in dry ice was completed, the black existing process [30]. In this study, the method of synthesizing carbon
powder was washed with HCl solutions at 25 ◦ C overnight to remove materials using the Mg-derived template from dry ice was modified to
MgO that was formed and any remaining Mg metal. By removing Mg- incorporate large amounts of functional groups by the nitric acid
derived materials via the acid washing, they obtained a porous carbon treatment. The synthesized materials have a hierarchical pore structure
material because the Mg-derived impurity acted as a template. The because of the Mg-derived template, and also have functional groups
resultant carbon was then characterized by various physical and such as phenolic and lactone by the nitric treatment of graphene
chemical analyses. As seen in Fig. 1A, the carbon had a few-layer gra­ structure. The carbon material thus showed low electrical resistance and
phene, as revealed by Raman spectroscopy. As shown in Fig. 1B, high capacitance at a high current density when used in supercapacitors.
graphitic carbon was formed, as determined through peaks at 26◦ and Furthermore, numerous studies using other metals instead of Mg to
43◦ in the XRD analysis. Fig. 1C shows the SEM-EDX spectrum, which synthesize porous carbon with different properties from the Mg-based
indicates that most of the Mg metal used as a reducing agent reacted and carbon have been reported. For example, Ca was used as a reaction
was then removed by etching. agent for CO2 reduction [31]. They synthesized graphene by reducing
Other characteristics of these substances were also reported. Some CO2 using Mg or Ca metal flames. This graphene was used as a
studies have measured the conductivity and dielectric constant of a Mg- conductive additive to supercapacitor electrodes to improve their elec­
derived carbon material synthesized through the previous synthesis trical conductivity. This graphene-mixed activated carbon electrode
process [26]. The dielectric constant was found to increase from 3.3 to showed an outstanding specific capacitance of 220 and 180F g− 1 at a

Table 1
Reducing agents to transform CO2 under extreme conditions by utilizing carbon dioxide in the form of dry ice.
Reducing Agents Methods Morphology Applications Ref.

Mg Combustion Few-layer graphene or Carbon nanocube – [19]


Adsorbent for an azo dye removal [27]
Hydrogen adsorbent [28]
– [26]
Supercapacitor [30]
Quasi-solid-state dye-sensitized solar cell [29]
Mg, Ca Combustion Few-layer graphene Supercapacitor [31]
Mg + Zn, Mg + Ni Combustion Few-layer graphene – [32]
Li Combustion Graphene Electric material [33]
Si-Ni composite 600 ◦ C for 10 h in autoclave Graphene-Si composite Li-ion batteries [34]

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

Fig. 1. (A) Raman spectrum, (B) XRD pattern, and (C) EDX spectrum of few-layer graphene (adopted from [19] with permission from Royal Society of Chemistry).
(D, E) TEM micrographs of graphitic carbon (GC) at different magnification levels and selected area electron diffraction (adopted from [28] with permission from
Elsevier). (F) Formation processes of the nanocomposite of graphitic-boxes/NiSe. (G) The XRD patterns, and (H) Raman spectra of the as-prepared NiSe, graphitic
boxes, graphitic-boxes/NiSe composite (adopted from [29] with permission from Elsevier). (I) Schematically illustrating the reduction of CO2 with Si to produce Si-
graphitic carbon composite. (J) XRD patterns, (K) Raman spectrum, and (L) high-resolution Si 2p XPS spectrum of Si-graphitic carbon composite (adopted from [34]
with permission from Elsevier).

current density of 0.1 A g− 1 in a 6 M KOH aqueous system, when uti­


Si (s) + CO2 (g)→C(s) + SiO2 (s)(with Ni as a catalyst) (3)
lizing graphene obtained in Mg and Ca flames, respectively.
2Ca(s) + CO2 (g)→2CaO(s) + C(s) (2)
2.2. Conversion at supercritical point
Thereafter, magnesium and other metals were mixed to synthesize a
carbon material having different characteristics from typical carbons by
Supercritical CO2 (31.1 ◦ C and 7.4 MPa) has advantages of its low
magnesium reduction [32]. Specifically, graphene was synthesized from
toxicity and environmental impact. It accordingly has been utilized in
dry ice with Zn or Ni particles mixed with Mg ribbon. As a result, the
important commercial and industrial solvents in various extraction
mixture with the other metal particles and Mg ribbon leads to a higher
processes. Due to the relatively low temperature of the process and the
yield of graphene than pure Mg ribbon.
stability of CO2, compounds can be extracted with little damage or
Reduction of CO2 with ultrapure Li metal was also conducted to
denaturing. Supercritical CO2 has higher chemical reactivity and can
fabricate graphene materials that exhibit a high degree of purity and can
provide a better reactant than normal CO2 or dry ice. Many research
serve as electrochemical impurity-free materials [33]. In this work, the
groups thus have exploited this reactivity of supercritical CO2 for its
defects were decreased and carbon and oxygen bonds on the surface
transformation to carbon materials as summarized in Table 2.
increased comparing with reduced graphene synthesized from hummers
First, there were cases where the supercritical state was reached by
method. Subsequently, the electrochemical performance of CO2-derived
using existing dry ice as a source of CO2. MgO and carbon were produced
carbon was examined and its potential for use as an electronic material
when CO2 and Mg were reacted in a closed cell for 3 h at 1000 ◦ C with 10
was reported.
kbar [35]. The authors of the aforementioned work proposed that the
Recently, carbon materials have been produced with a non-metal
first step is Mg-CO2 reaction in the homogeneous phase, followed by Mg-
reductant. A Ni/Si composite was introduced as a reductant for the
CO reaction occurring on the surface of the magnesium droplets, where
conversion of dry ice into graphitic carbon through a silicothermic re­
the melting point of Mg is 650 ◦ C.
action, producing a graphitic carbon-Si nanoparticle composite [34]. As
in Fig. 1I, small amounts of ultrafine Ni crystals with two functional Mg (g) + CO2 (g)→MgO(s) + CO(g) (4)
groups were coated on the Si surface, facilitating CO2 reduction re­
actions and graphitic carbon formation. The synthesis of the composite Mg (l) + CO (g) → MgO (s) + C (graphite) (5)
was verified through physical and chemical analyses. In the XRD results
There have also been attempts to synthesize diamond, which is a
(Fig. 1J), silicon particles and graphite carbon structures are seen
carbon material [17]. The reactions were performed with Na metal and
simultaneously. This crystalline structure can be seen through Raman
supercritical CO2 at 440 ◦ C and 800 atm for 12 h. A cubic diamond
spectroscopy in Fig. 1K. The XPS analysis shows that Si-C chemical
structure was identified by XRD and Raman spectroscopy, indicating the
bonds of the Si/C material were formed, as shown in Fig. 1L. As the Si/C
successful formation of well-crystallized diamond from supercritical
composite provided effective suppression of silicon expansion, ion
CO2. As seen in the SEM images in Figures 2A and 2B, a diamond
diffusion, and inhibition of side reactions with the electrolyte, the Si-C
structure and graphite were synthesized.
composite electrode exhibits superior Li-ion storage performance.
Additionally, various alkali metals have been used. Metallic K and Li
were reacted in an autoclave at 400–600 ◦ C and 820 atm by reduction of

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

Table 2 which is even higher than that of a commercial Pt counter electrode


Various synthesis processes under extreme conditions by utilizing carbon diox­ (7.5%).
ide in supercritical state. A carbon conversion process using a dielectric barrier discharge
Reducing Specific Conditions Products Applications Ref. microplasma in supercritical CO2 was reported [39]. As shown in Fig. 2C
Agents and 2D, the plasma was formed by applying an AC voltage difference
Na 440 ◦ C, 800 atm,12 Diamond, – [17] between the needle and plate in CO2 gas. The minimum negative charge
h Graphite density (N− = j/evd , N− : negative charge density (cm− 3), j: current
K, Li 460 ◦ C, 820 atm, 10 Diamond, – [18] density (mA cm− 2), e: the elementary charge (1.602 × 10-16 mA s− 1), vd :
h Graphite
the drift velocity of the negative charge (cm s− 1)) required for the re­
Mg 1000 ◦ C, 10 kbar, 3 Carbon [35]
action was calculated, and the value should be higher than 5 × 1018

h nanotube,
Nested cm− 3. The dependencies of the carbon materials properties on temper­
fullerene ature, environmental pressure, and power frequency during the syn­
Li 650 ◦ C, 1000 atm, Carbon sphere – [36] thesis process were then investigated. As a result, it was observed to
10 h
K, Li, Na 480 ◦ C, 850 atm, 10 Porous carbon Li-ion storage [37]
produce various carbon morphologies such as amorphous carbon,
h graphite, and nanostructured carbon materials as shown in Fig. 2E. In
Li 500 ~ 650 ◦ C, 50 3D cauliflower- Dye-sensitized [38] particular, carbon nanotubes and carbon nano-horns were mostly
psi, 10 h fungus-like solar cell formed near the critical point rather than under other supercritical CO2
graphene
conditions.
– Dielectric barrier Amorphous – [39]
discharge (DBD) carbon, Shock-induced decomposition was combined with chemical reaction
micro-plasma Graphite, and applied in a new way to convert CO2 in dry ice state into nano-
method (302.4 K, Nanotube carbon materials [40]. Few-layer graphene sheets were synthesized by
7.4 Mpa) applying a shock wave to CO2 with CaH2 under loading, causing a harsh
CaH2 Shock induced Few-layer Electrocatalyst [40]
environment with 1985 K and 7.92 GPa in the samples, as seen in
conversion (1985 K, graphene for ORR
7.92 Gpa) Figure 2F (the shock wave-derived synthesis system is illustrated in
Glutaric 100 ◦ C, 51.5 atm, 3D graphene- Lithium-ion [41] Figure 2G and a digital photograph is provided in Fig. 2H). In other
acid zinc 48 h like carbon battery words, the reaction occurred instantaneously in a supercritical state. In
Discarded 530 ~ 650 ◦ C, 3 h Carbon [42]

addition, N-doped graphene was synthesized by using an N-doping
oil nanosphere
source with shock wave decomposition of CO2. This material showed
excellent performance as an electrocatalyst for the oxygen reduction
dry ice with K and Li [18]. As a result, polycrystal diamond particles reaction in an alkaline electrolyte.
were synthesized in a size range of 4–450 μm, and it was found that Additionally, in some cases, the reaction proceeds through mixing
much larger diamonds could be produced by using a lower melting point with other organic substances and supercritical CO2. Graphene-like
alkali metal. For example, metallic K had a higher transformation ratio carbon was synthesized by a two-step process utilizing supercritical
for CO2 to diamond (9.60%) than metallic Li (0.58%) with more im­ CO2 [41]. The copolymerization of CO2 occurs with propylene oxide at
purities of graphitic carbon and amorphous carbon. 60 ◦ C and 51.5 atm utilizing glutaric acid zinc catalysts to obtain pol­
Studies to synthesize other types of carbon materials other than ycarbonate. The prepared polycarbonate powder was then mixed with
diamond have also been conducted [36]. CO2 reduction reactions were Na2CO3 and the mixture was carbonized. Through these steps, CO2 can
conducted with Li metal at various conditions of temperature and CO2 be easily converted into porous carbon materials. The electrode made
pressure, and it is found that the reaction temperature was an important through CO2 conversion as active agent exhibited excellent electro­
factor for determining the carbon morphology. At high temperature (T chemical performance for anode of lithium-ion batteries (LIBs).
> 650 ◦ C), graphene spheres surrounding an amorphous carbon core Also, waste oil was utilized to prepare carbon microspheres with a
were synthesized. In contrast, CNTs and graphite were mainly yielded at size of 1–10 μm using a supercritical CO2 system [42]. These carbon
temperatures lower than 650 ◦ C. The various morphologies of carbon microspheres consist of graphitic carbon microspheres with relatively
were due to the Li nano-droplets acting as a catalyst. low graphitization. The yield of solid products was the highest at 600 ◦ C
The carbon materials were synthesized via the reduction of super­ (42.2 wt%), where the temperature was controlled between 530 and
critical CO2 from dry ice by alkali metals [37]. Na, K, and Li were used as 650 ◦ C. As the temperature increases, the waste oil pyrolyzed into small
reductants for the CO2 reaction, which was conducted at 480–500 ◦ C molecules or free radicals, which can react with other molecules to form
and 850 atm for 10 h. Because of the different melting points, the pentagonal and hexagonal ring structures. Due to presence of the su­
diameter of the alkali metal droplets and their properties were also percritical CO2, condensation of the decomposed molecules results in
different in certain circumstances. It is suggested that CO2 molecules the growth of clusters made of graphitic layers as the temperature in­
were adsorbed on alkali metal droplets and reacted, resulting in the creases and the time is extended. It was thus demonstrated that super­
production of a porous carbon material. These alkali metal-derived critical CO2 could be useful when mixed with various organic substances
porous carbon materials were utilized for Li-based energy storage sys­ to synthesize carbon materials.
tems. A Na-derived carbon electrode also showed excellent electric ca­
pacity and a similar tendency with other carbon materials. It is also 3. Electrochemical conversion process with an electrode system
noted that annealing of the material can improve the electrochemical
performance by increasing the graphitization of carbon. CO2 conversion using a molten salt electrolyte under electrochemical
In addition, Li metal reacted with CO2 at different temperatures reactions, unlike conventional transformation from dry ice or at the
between 500 ◦ C and 650 ◦ C [38]. The generation of Li2CO3 with gra­ supercritical point, has recently been reported. The molten carbonates
phene can isolate the graphene sheets during the synthesis, and Li2CO3 advanced applications to capturing and converting greenhouse gas CO2
can prevent stacking of the graphitic carbon layer. As a result, 3-D into valued carbon materials [21,43]. This process of electrochemical
cauliflower-fungus-like graphene, which possesses high conductivity converting CO2 into fuels and carbonaceous materials in molten salts is
and excellent catalytic activity, was directly produced from supercritical called molten salt CO2 capture and electrochemical transformation
CO2. This 3-D carbon material was applied to the DSC as a counter (MSCC-ET) [44].
electrode, and exhibited a high energy conversion efficiency of 8.1%, The use of molten salt electrolyte systems for electrochemical CO2
reduction provides superior functionality compared to other electrolyte

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

Fig. 2. (A, B) SEM micrographs of diamond microparticles synthesized in a high-pressure CO2 reduction process (adopted from [17] with permission from American
Chemical Society). (C) Schematic diagram of apparatus used for generation of dielectric barrier discharge (DBD) microplasma in supercritical CO2 environments. (D)
Schematic diagram of electrodes for DBD microplasma. (E) SEM micrograph of various carbon materials from dielectric barrier discharge (DBD) microplasma in
supercritical CO2 environments (adopted from [39] with permission from Elsevier). (F) Schematic representations of Shock wave process for the synthesis of gra­
phene material from dry ice. (G) Diagram of shock-loading apparatus. (H) Photo of real experimental setups (adopted from [40] with permission from Elsevier).

systems. Fig. 3A shows the outstanding potential of the molten salt molten carbonate electrolyte should be able to not only dissolve CO2, but
system compared to aqueous solution, ionic liquid, and solid electrolyte also transport reaction intermediate such as O2– ions for the post-
systems [45]. These benefits of molten salt electrolyte systems for CO2 reaction [48].
electrochemical reduction are based on their chemical properties. First, In the case of system using the molten salts, most of the alkali car­
the molten salt systems have relatively high conductivity and thus can bonates based on Li, Na, K, and their carbonate mixture are used because
have higher energy efficiency compared to other electrolyte systems. In they have wide electrochemical windows and excellent dissolving abil­
addition, due to the high heat capacity of molten salt, it is easier to ity for CO2 [49]. Alkali carbonates have advantages with properties of
maintain the temperature during the electrochemical reduction process rapid reaction kinetics, which can readily react with acidic CO2 [22].
[45–47]. The detailed CO2 reaction in the carbonate molten salt system and
In the MSCC-ET process, the molten salt plays an important role to carbonate anions reduction reaction are shown below. The dissolved
effectively capture CO2 and provides ions and reactants for electro­ CO2 reacts with carbonate or oxygen anions and the O2– can be in-situ
chemical reaction. The MSCC-ET process generally involves the generated through the reduction of CO2– 3 , further capturing CO2 in the
following steps: capturing of CO2 through dissolution in the molten salt, form of CO2–3 . As a result, the electrolysis only consumes CO2, and the
electrochemical reactions on the electrode, and separation and collec­ generated carbonate anions are reduced at the cathode and produce a
tion of reduced carbon materials [45]. Accordingly, the applicable carbon material during the process [43,45].

Fig. 3. (A) Comparison of electrolyte types for electrochemical reaction with aqueous solutions, ionic liquids, molten salt, and solid electrolyte. (B) Schematic
diagram of MSCC-ET process including renewable thermal energy system (adopted from [45] with permission from Elsevier).

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

CO2−3 ↔ CO2 (g) + O2− (carbonates decomposition equilibrium reaction) compositions and types of molten salt systems were observed [59–61].
(6) Several studies have shown that reactions such as CO2 capture and
molten salt decomposition are affected depending on the type and
CO2 (g) + O2− → CO2−3 (CO2 capture reaction) (7) composition of the molten salt, and through this, the change in the
characteristics of the carbon material was confirmed [62,63]. First, the
CO2−3 + 4e− → C (s) + 3O2− (1 step reduction reaction) (8) morphology difference was identified by the type and condition of
molten salts and carbon spheres and carbon nanotubes were generated
CO2−3 + 2e− → CO2−2 + O2− / CO2−2 + 2e− → C (s) according to the different molten salt systems [21]. Also, the change of
+ 2O2− (2 step reduction reaction) (9) carbon structure (carbon spheres, CNTs) was confirmed through another
work [64]. For Li-Na-K carbonates systems, CNTs are observed. How­
In addition, a system that fuses with the molten salt and solar energy ever, when carbonate is combined with Li-Ca-Na and Li-Ca-K, carbon
was recently developed [50]. In Fig. 3B, the fused MSCC-ET process and spheres are generated rather than CNTs.
thermal energy supply system is depicted briefly [45]. As the MSCC-ET Several carbon structures were also displayed such as honeycomb-
process occurred in the high-temperature system, the energy for high- like porous carbon, CNTs, and carbon spheres [22]. The Li-Na-K
temperature conditions can be powered by renewable energy such as molten carbonate mixture without alkaline earth carbonate generates
solar energy. In this case, the high-temperature thermal energy from porous carbon or honeycomb-like carbon. The honeycomb-like porous
solar energy can decrease the energy required for the endothermic CO2 carbon product is shown in Fig. 4A and 4B. Otherwise, a molten car­
conversion and it facilitates the reaction kinetics [51]. bonate mixture with alkaline earth carbonates such as CaCO3, SrCO3,
Carbon materials with different morphologies can be obtained by and BaCO3 produces some carbon flakes, sphere-like carbons, and
varying the molten salt composition, electrode materials, the applied irregular carbon particles.
current, and the temperature in the MSCC-ET system [44,52]. Basically, The other studies confirmed that the thickness of the carbon nano­
changes in the extent and rate of several reactions that occur in the tube product is changed according to the molten salt system type
MSCC-ET process can affect the carbon reduction reaction and carbon [65,66]. It shows that the foam of CNTs was generated through molten
growth, resulting in differences in the properties of the carbon product salt electrolysis [65]. In this work, the molten salt with Li-Ca carbonate
[43]. Accordingly, many studies have controlled the MSCC-ET process can produce CNT carbon foam. The Li-Ca carbonate with Ba and Sr
through various variables and electrolytic conditions, and numerous carbonates exhibits the largest diameter of CNTs.
carbon materials such as porous carbon, graphene, carbon nanotube, The properties of CO2-derived carbon products are affected by con­
carbon nanosphere, and carbon nanofibers have been synthesized ditions such as temperature, voltage, and current for electrochemical
[53–57]. As shown in Fig. 4A − 4D, various properties of carbon prod­ reaction. The difference alters the reaction kinetics at the electrode/
ucts are obtained from CO2 through different MSCC-ET processes electrolyte interface, particularly carbon deposition and CO evolution
[22,58]. reactions, among reactions in the MSCC-ET process [67]. Several studies
Changes in the properties of the carbon produced from different

Fig. 4. Micromorphology of the carbon products from different conditions: (A, B) honeycomb-like porous carbon (adopted from [22] with permission from Royal
Society of Chemistry); (C, D) carbon nano-onion (adopted from [58] with permission from Wiley Online Library). (E) Schematic diagram of catalytic effect on oxygen
evolution in anode, and SEM images of carbon products (adopted from [73] with permission from Elsevier). (F1 − F4) SEM images of the CNT product from different
catalyst layer thickness, (F5) size distribution graph for each condition, (F6) normalized lognormal fits of the distribution for each sample, and (F7) median diameter
of products as a function of catalyst thickness (adopted from [76] with permission from American Chemical Society). (G) Micromorphology of the carbon products
from different electrode systems (adopted from [79] with permission from Elsevier).

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

observed a change in the properties of the carbon produced from Table 3


different conditions of molten salt systems [68,69]. The effect of tem­ Briefly summary of the differences in carbon products through various condi­
perature on the properties of the produced carbon was also identified tions in the reported MSCC-ET studies.
[22]: when the molten salt electrolysis reaction proceeded at high Compositions Conditions Voltage Electrode Products Ref.
temperature, the CNT structure was observed with a high yield. or (Cathode /
The morphologies and particle size of the carbon products were also Current anode)

affected by the electrolysis cell voltage and temperature [67]. This study Li-Ca-Na, Li- 750 ◦ C 10 ~ Fe / Ni Carbon [21]
showed the change of particle size through cell voltage and temperature Ca-Ba 200 mA sphere,
(carbonate) cm− 2 Tangled CNT
difference with the same molten salt system. Also, in various electrolysis
Li-Na-K-Ca, Li- 600 ◦ C 250 mA Fe / Ni Amorphous [22]
compositions, the quasi-sphere structure of carbon, carbon nanotubes, Na-K-Sr, Li- cm− 2 carbon,
and thinner carbon nanosheet structures were displayed during tem­ Na-K-Br Carbon
perature ramping [70]. (carbonate) sphere, CNT
Additionally, various cell voltages and temperatures induce the for­ LiCl-KCl- 450, 550, 2.8 V Ni / Hollow, [24]
CaCO3 660 ◦ C Graphite rod Flake-
mation of several carbon forms such as hollow carbon spheres, carbon formed,
sheet, quasi-spherical-like carbon, coral-like carbon, and carbon nano­ Flake-
fibers [24]. Furthermore, the change in the properties of the carbon formed
product according to the current density of the electrochemical reaction LiCl-KCl- 660 ◦ C 2.8, 3.5, Ni / Flake- [24]
CaCO3 4.5 V Graphite rod formed,
was confirmed [66]. The surface area increased in the same composition
Carbon
and type of molten salt system as the current density increased. sheet, CNF
The properties of CO2-derived carbon products can be altered by the Li (carbonate) 730 ◦ C 50 mA Galvanized CNF [57]
electrochemical reaction activity. For this reason, several studies cm− 2 steel / Ni
observed a change in the properties of the produced carbon through the Li2CO3-Li2O 770 C

200 mA Galvanized Carbon [58]
cm− 2 steel wire nano-onion
addition of a catalyst to the molten salt system and observed the relation
/Ir & Pt
between the carbon product and catalytic effect for the electrolysis anode
process [71,72]. The application of additives such as catalysts affects the Li-Na-K 450, 500, 100 mA Fe / Ni Porous [59]
kinetics of oxygen evolution reactions and carbon growth at the elec­ (carbonate) 550 ◦ C cm− 2 carbon, CNT
CaCl2-CaO- 850 ◦ C 3V Stainless Rod-like [60]
trode/electrolyte interface, and thus changes the properties of reduced
Na2CO3 steel / carbon
carbon materials [73,74]. It was confirmed that the unique carbon nano- Graphite
onion structure was displayed in lithium carbonate molten systems with Li-Na-K 577 ◦ C 200, Galvanized Honey comb [64]
Ni catalyst [58]. The carbon nano-onion product is shown in Fig. 4C and (carbonate) 400 mA Fe wire/ Ni, like carbon
4D. Without a catalyst, the CNT structure is observed; however, in the cm− 2 Cu wire
Li-Ca, Li-Sr, 750 ◦ C 6 ~ 20 Galvanized CNT [65]
case of reaction with the catalyst, the carbon nano-onion growth was
Li-Ba mA iron wire/
observed during the synthesis. The feasible homogeneous catalytic (carbonate) cm− 2 Ni wire
strategy by soluble NaVO3 in the carbonate molten salt was proposed for Li-Na > 700 ◦ C 50, 100, Fe / Ni Porosity [66]
enhanced electrochemical conversion of CO2 to carbon with a high (carbonate) 200 mA increased
cm− 2
graphitization degree [75].
Li-Na-K 450, 550, 5, 6 V Ni / SnO2 Heart- [67]
The carbon nanotube growth in the electrode was observed clearly (carbonate) 650 ◦ C rod (inert) shaped,
when a catalyst was used in the molten salt system. Fig. 4E shows that Flake-
the resultant carbon product morphology differs between non-catalytic formed,
and catalytic cases in the MSCC-ET process [73]. It was also found Wire-formed
Li-Na-K 450 ◦ C 3~6V Ni / SnO2 Porous [67]
that the thickness of the catalyst layer can affect the structures of the
(carbonate) rod carbon
produced CNTs in Fig. 4F [76]. (surface area
Besides the molten salt composition, type, and electrolysis reactivity increased)
change, studies have reported that properties of the carbon product are Li-Na-K, Li 600, 10 ~ Fe / Ni Amorphous [68]
(carbonate) 750 ◦ C 300 mA carbon, CNT
modified by changing the electrolyte or electrode of the molten salt
cm− 2
system [77,78]. It was demonstrated that the morphology of the carbon CaCl2-NaCl- 750 ◦ C 2.6 V Graphite rod Carbon [70]
products is affected by the electrode type [79]: the morphology of the CaO / TiO2, sphere
CNTs was changed according to various cathode types such as Cu, RuO2 (Porous
Monel, Nickel chromium, Fe, Ti, and graphite foil (Fig. 4G). It has also carbon)
Li (carbonate) 750 ◦ C 25 ~ Galvanized MWCNT [71]
been found that the morphologies and microstructures of the graphite
100 mA steel wire /
product were influenced by a type of anode, and the current efficiency is cm− 2 Ni
much higher and the energy consumed is lower than in the case of using Li (carbonate) 750 ◦ C 100 ~ Fe on steel / CNT [73]
Ni⋅TiO2 anode than when RuO2⋅TiO2 anode was used [80]. 400 mA Cu, (Ni
The various carbon products from reported MSCC-ET studies with cm− 2 /Al2O)3, Pt
Na-K 800 ◦ C 3.5 V Ni / SnO2 Hollow CNF [75]
several electrolysis conditions are summarized in Table 3 (carbonate) rod
[21,22,24,57–60,64–68,70,71,73,75,79,81]. Furthermore, carbon ma­ Li (carbonate) 770 C

100 ~ Galvanized CNT [79]
terials generated by molten salt systems are also used as electrode ma­ 200 mA zinc coated
terials for supercapacitor and battery systems. The carbon produced via cm− 2 steel / Ir
LiCl-KCl- 450 ◦ C 2.8 V Ni sheet Hollow [81]
molten salt electrolysis has several desirable properties, such as high
CaCO3 CO2 carbon
specific surface area and high electrical conductivity. These properties bubbling sphere
facilitate in energy conversion and storage applications such as capac­
itor and battery systems. Some studies produced carbon from molten-
salt electrodeposition and utilized it as supercapacitors, sodium ion
batteries (SIBs), and LIBs [82–84].

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

4. Modified conversion in mild conditions nitrogen gas in the air, and when HMCCs were applied as a catalyst for
oxygen reduction reaction (ORR) of a fuel cell, higher electrochemical
4.1. Metal-based reactions performance than that of a commercial Pt/C catalyst was shown.
In addition to the reaction temperature, the carbon characteristics
In addition to the previous method of reducing solid or supercritical according to the reaction time have been studied [87]. In the afore­
CO2 and converting gaseous CO2 through an electrochemical reaction, mentioned study, the authors conducted the experiment by adjusting the
studies using metallurgical thermal reduction have also been conducted. reaction temperature from 800 to 900 ◦ C and reaction duration from 15
The strong reducing ability of the metal-based material dissociates the to 60 min. Because CO2 played roles of both the carbon source and the
chemical bonds of CO2 and yields carbon materials. This method is activation agent when forming carbon materials, the yield, morphology,
considered to be cost-effective for mass production because it is rela­ crystallinity, and pore structure of the synthesized nanoporous carbons
tively simple compared to other CO2 conversion technologies such as (NPCs) varied according to the reaction conditions, further revealing
hydrogenation, photocatalytic reaction, electrochemical reaction, and different CO2 uptake ability.
hydrocarbon synthesis reaction. The structure and characteristics of the The burn-quench method was also employed to prepare a composite
synthesized carbon materials are diverse depending on the type of metal of nanographene and manganese oxide to enhance the electrochemical
and reaction conditions, as listed in Table 4. performance of a supercapacitor [89]. A composite of nanographene
Mg-based reactions sheet (NGs) and MnO2 nanotubes (MTGs) or MnO2 nanoparticles
The magnesiothermic reduction using Mg metal as a reducing agent (MPGs) was prepared by adding KMnO4 aqueous solution as a precursor
is the most representative method among metallurgical thermal reduc­ for manganese oxide. As a result, increased specific capacitance and
tion reactions. A reduction using only metallic Mg has been conducted cyclic stability were demonstrated when the composite was used as a
under relatively moderate reaction conditions based on the superior CO2 supercapacitor electrode material.
reduction ability of Mg [85–89]. Mg-included reactions
Depending on the reaction temperatures, the state of Mg metal Due to the low-cost and simple experimental process of magnesio­
changes, and thus a different reaction mechanism proceeds, as presented thermic reduction, studies on employing additives in the Mg-based
in Fig. 5A [85]. Based on the different interfacial phase reaction reduction reaction have been conducted. Since carbon-based materials
mechanisms, various nanocarbons including mesoporous graphene are considered as promising candidates for active materials in energy
(MPG, @ 600 ◦ C), carbon tubular nanostructures (CTNs, @ 800 ◦ C), and storage systems, designing the characteristics of the carbon material is
hollow carbon nanoboxes (HCBs, @ 1000 ◦ C) are synthesized. As shown one of the important steps to enhance the performance. By adding a
in Fig. 5B − 5H, the characteristics and morphology of the synthesized template or an additional reactant, properties such as morphology,
nanocarbons can be controlled according to the reaction temperature, porosity, graphitic degree, and hetero-atom doping can be controlled,
and the possibility of using the synthesized nanocarbons as a super­ resulting in the synthesis of carbon materials suitable for given
capacitor electrode material was identified. applications.
It was reported that hollow-structured mesoporous carbon cubes Three-dimensional (3D) carbon nanotube foams (CNTFs) were syn­
(HMCCs) can be synthesized by reacting a Mg ribbon and CO2 through a thesized with nickel foam as a template. The template was dissolved by
burn-quench method under atmospheric conditions [86]. During the acid treatment, generating CNTFs with a superior specific surface area of
synthesis, pyrrole-type N atoms were doped in the carbon due to the 1959 m2 g− 1 [90]. Based on the unique hierarchical porous structure,

Table 4
Representative studies of metal-based CO2 reduction method with various metal types, experimental conditions, products, and applications.
Metal Additives Experimental Conditions Products Applications Ref.
Catalysts

Mg – Heating, 600 ~ 800 ◦ C, CO2 + Mesoporous graphene, Carbon tubular Supercapacitor [85]
Ar nanostructures, Hollow carbon nano-boxes
Mg ribbon – Ignition(Burn-quench) Hollow-structured mesoporous carbon cubes ORR in fuel cell [86]
Mg – Heating, 800 ~ 900 ◦ C, 15 ~ Nano-porous carbon CO2 capture (adsorption) [87]
60 min, CO2
Mg – Burning, dry ice Multilayer graphene oxide – [88]
Mg – Ignition(Burn-quench) Nanographene sheet Supercapacitor [89]
Mg Ni foam (template) Heating, 650 ~ 850 ◦ C, 0 ~ 4 Carbon nanotube foams Lithium-ion battery [90]
h, CO2 + Ar
Mg Stainless steel mesh,Silicon Heating, 800 ◦ C, 5 ~ 120 min, Hierarchical carbon tubular nanostructure Supercapacitor [91]
wafer (template) CO2 + Ar
Mg Ni foam (template) Heating, 800 ◦ C, CO2 + Ar 3D carbon nanotube Supercapacitor [92]
Mg Zn Heating, 680 ◦ C, 1 h, CO2 Nano-porous graphene Supercapacitor [93]
Mg Zn 680 ◦ C, 1 h, under CO2 + N2 N-doped graphenic carbon Li-O2 battery [94]
Mg Ni Heating, 680 ◦ C, 1 h, CO2 CNF-grafted graphene Lithium-Sulfur battery [25]
Mg ribbon NH4HCO3 Ignition(Burn-quench) Nano-graphene sheet Lithium-ion battery [95]
Mg CaCO3, MgCO3,Mg(OH)2, Ignition(Self-propagating Few-layered graphene Dye-sensitized solar cell [96]
glucose, PVA synthesis)
Mg Si (to form Mg2Si) Heating, 700 ◦ C, 10 h, CO2 Carbon-coated Si Lithium-ion battery [97]
Mg Mg2Si Heating, 500 ~ 700 ◦ C, 2 h, Nano-porous Si@C Lithium-ion battery [98]
CO2
Mg N2H4⋅H2O Sol-pyrolysis combustion N-doped carbon foam ORR in fuel cell, Lithium- [99]
ion battery
Mg Ethanolamine Sol-pyrolysis combustion N-doped carbon nano-mesh ORR in fuel cell [100]
Iron oxide – Solar furnace, 773 K Carbon – [101]
Li metal – Autoclave, 700 ◦ C, 100 MPa, C60 – [20]
10 h
Cu-Pd alloy – Heating, 1000 ◦ C, 40 min, Graphene – [102]
film CO2 + H2 + N2
Ni/Al2O3 – Heating, 500 ◦ C, 6 h, CO2 + H2 CNF – [103]

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

Fig. 5. (A) The formation mechanism of nanocarbons including MPG, CTN, and HCB. (The gray, red, and green colored spheres represent C, Mg and O atoms,
respectively.) (B) XRD patterns, (C − E) Raman spectra, and (F − H) TEM images of MPG, CTN, and HCB (adopted from [85] with permission from Springer Nature).
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Fig. 6. (A) A schematic presentation of conversion of carbon dioxide into hCTNs supported by the substrates. (B) Various images of hCTNs (adopted from [91] with
permission from Elsevier). ((B1) A photograph of differently shaped and sized substrates used for hCTNs growth. The top-left and top-right are the as-received
stainless steel spring and a similar substrate with hCTNs grown on it. A stainless-steel wire and sheets are also shown. The bottom-right is the silicon substrate
with hCTNs grown on it. (B2) SEM images of hCTNs grown on a stainless-steel mesh, showing that hCTNs can be uniformly covered on the whole mesh. (B3) A high
resolution SEM image presenting tubular structure and rough surface of hCTNs. (B4 − B6) The morphologies of hCTN networks can be tailored by varying the flow
gases. (B7 − B10) The density of hCTN networks on the stainless-steel mesh can also be controlled by adjusting the reaction time.)

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

the CNTFs demonstrated excellent electrochemical properties when conversion was conducted under a mixture of CO2 and N2 [94]. Due to
applied as an anode in LIBs. Hierarchical carbon tubular nanostructures the introduction of N2 gas, N-doped graphenic carbon was synthesized
(hCTNs) were fabricated by using substrates under various experimental and structural changes were also observed. Based on the properties of N-
conditions as shown in Fig. 6A [91]. The type of substrate (stainless steel doping, conductivity, and porosity, the electrochemical performance as
mesh, stainless steel spring, and silicon wafer), reaction position, and the cathode material of Li-O2 battery was highly enhanced compared to
reaction time were varied to understand the changes in carbon proper­ the pure CO2 case.
ties. The synthesized materials showed flexible properties and mor­ Ni particles were introduced to the magnesiothermic reduction re­
phologies including pore characteristics of hCTNs according to the action to make CNF-exfoliated graphene by a facile one-step heating
experimental conditions (Fig. 6B). process [25]. During the reaction, Ni acts as a nucleation site for the
Three-dimensional carbon nanotube foams (CNTFs) coated with fiber growth, exfoliating the graphene prepared from the reduction of
cobalt hydroxide were synthesized by nickel foam-added magnesio­ CO2 by Mg as illustrated in Fig. 7G. The synthesized graphene grafted by
thermic reduction of CO2 followed by hydrothermal reaction for appli­ CNF (G-CNF) consists of graphene and carbon nanofiber as shown in
cation to a supercapacitor [92]. The obtained CNTF@Co(OH)2 had high Fig. 7H, and it was utilized as not only the cathode material but also the
electrical conductivity and surface area and coated Co(OH)2 could interlayer in lithium-sulfur (Li-S) batteries.
provide additional energy storage. An asymmetric supercapacitor was Uniquely, the burn-quench method followed by in-situ quenching
assembled using CNTF@Co(OH)2 as a positive electrode and bare CNTF allowed the fabrication of mesoporous few-layer graphene [95]. During
as a negative electrode, exhibiting superior power density and energy the quenching process in the NH4HCO3 solution after the ignition of Mg
density of 7.2 kW kg− 1 and 13.0 Wh kg− 1, respectively. ribbons under a CO2 atmosphere, NH3 gas was generated by the
Zn powders were added to the magnesiothermic reduction reaction decomposition of NH4HCO3 owing to the high temperature of the
process as a porosity promoter [93]. While Mg and CO2 react to form ignited Mg ribbons⋅NH3 brought out N-doped exfoliation of the syn­
solid carbon materials, Zn also reacts with CO2 to be form ZnO. How­ thesized graphene, resulting in high energy storage capacity in LIBs.
ever, at a high temperature of 900 ◦ C, ZnO reacts with carbon to Self-propagating high-temperature synthesis (SHS) was adopted to
generate CO gas and Zn gas, leading to nanopore formation in the carbon prepare few-layer graphene (FLG) from various carbon sources [96].
material. Compared to the carbon material synthesized using only Mg SHS is a method of combustion synthesis, which leads to the reaction
(C-M), increased porosity of the carbon material when using both Zn and spontaneously propagating through the mixture. Various carbon sources
Mg (C-MZ) was observed, as shown in Fig. 7A − 7F. Through these such as inorganic (CaCO3, 3MgCO3⋅Mg(OH)2⋅3H2O), organic (glucose),
processes, the final product of nanoporous graphene had high specific and polymer (polyvinyl alcohol) materials participated in the CO2
surface area of 1900 m2 g− 1, enabling excellent electrochemical per­ reduction process to synthesize carbon material with specific properties.
formance as a supercapacitor electrode material. As a result, FLG showed higher conversion efficiency than that of Pt
Another study utilized both Mg and Zn as reducing agents, but the counter electrode in a DSC.

Fig. 7. (A − D) Low and high magnification TEM images of C-M (A, C) and C-MZ (B, D). (E) SAED and (F) diffraction pattern of C-MZ (adopted from [93] with
permission from Elsevier). (G) Schematic of suggested mechanism for G-CNF formation in the presence of Mg and Ni. (H) FFT image of graphene sheets part and CNF
part in TEM image of G-CNF (adopted from [25] with permission from Elsevier). (I) Schematic illustrating the synthesis of NPSi@C at 500, 600, and 700 ◦ C (adopted
from [98] with permission from Wiley Online Library). (J) Overall fabrication of NCM sheets from gas state CO2 via sol-pyrolysis combustion method (adopted from
[100] with permission from American Chemical Society).

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

A composite of silicon and carbon material was prepared by the energy, active wustites are oxidized to Fe3O4 by CO2, and at the same
oxidation of Mg-based intermetallic compounds [97]. An intermetallic time CO2 is reduced to CO and graphite according to the following
compound of Mg2Si was fabricated via a heat treatment of the mixture of equation:
Si and Mg powders, and then oxidized by CO2 to form composite of
(3/(1 − y) ) Fe1− y O + (4 − 3/(1 − y) ) CO2 →Fe3 O4 + (4
carbon-coated silicon. The resultant product has macroporous charac­
teristics and showed efficient performance as an anode material of LIBs. − 3(1 − y) ) CO (10)
It was also reported that a composite of silicon and carbon material
was derived by oxidizing Mg2Si using CO2 [98]. The commercial Mg2Si (3/(1 − y) ) Fe1− y O + (4 − 3/(1 − y) ) CO→Fe3 O4 + (4
powder was heat-treated under CO2 at various temperatures and uni­ − 3/(1 − y) ) C (graphite) (11)
form nanoporous Si@carbon (NPSi@C) was formed. As the reaction
temperature increased, the graphitic degree and thickness of the carbon In some cases, CO2 conversion was carried out through an atmo­
increased, and the size of the well-distributed pores became small, as spheric heating process by introducing hydrogen gas to help CO2
shown in Fig. 7I. Based on the properties adjusted by the reaction con­ reduction. Mario Ruben’s group presented a one-step synthesis of gra­
dition, NPSi@C showed excellent electrochemical performance in LIBs. phene using CO2 as a carbon source through atmospheric pressure CVD
A flammable alkaline solution of hydrazine monohydrate by employing Cu-Pd alloy film as a substrate [102]. CNFs of high purity
(N2H4⋅H2O) was employed to synthesize the N-doped carbon foam were also obtained by hydrogenation of CO2 at 500 ◦ C and 1 atm using a
(NCF) through a fast combustion method [99]. The alkaline solution Ni/Al2O3 catalyst to cause a series reduction of CO2 to CO and carbon
played the roles of fuel, nitrogen source, capturing CO2, and dissolving [103].
Mg, forming a homogeneous mixture of reactants. When another alka­
line solution of ethanediamine (C2H8N2, EDA) was used instead of hy­
4.2. Inorganic material-based reactions
drazine monohydrate, the carbon synthesis was also successful through
the same method, demonstrating the versatility of the synthesis process.
In addition to the aforementioned metal-based materials, studies on
Because the resultant NCF has a foam-like structure with high porosity
converting CO2 using inorganic materials such as sodium borohydride
and N-doping, it showed excellent electrochemical performance in both
(NaBH4) and ammonia borane (NH3BH3) have been conducted
the fuel cell and LIBs. An ethanol amine solution with low toxicity and
[104,105]. These inorganic substances have a superior reducing ability
corrosiveness was adopted to prepare an ultrathin N-doped carbon
compared to the existing metal substances, which allows CO2 to be
nanomesh (NCM) [100] as illustrated in Fig. 7J. When compared to NCF
efficiently converted into carbon materials even at atmospheric pres­
that was synthesized by using hydrazine monohydrate, this NCM has
sure, as summarized in Table 5. Above all, the greatest advantage that
similar nitrogen content but higher specific surface area and pore vol­
can be obtained when using the inorganic reducing agent is that it can
ume due to increased nano-porosity. It was also applied as an electrode
simultaneously dope B atoms contained in inorganic materials in the
material for ORR in a fuel cell, and it exhibited superior electrochemical
process of synthesizing carbon materials [106,107]. Carbon materials
performance.
doped with B atoms have superior stability and electrochemical per­
Other-metal-based reactions
formance compared to bare carbon materials, and on this basis are
A new decomposition mechanism of CO2 with wustite (Fe1-yO) using
mainly used in energy storage devices such as fuel cells and super­
solar energy was proposed [101]. Under highly concentrated solar
capacitors [108,109]. There have also been attempts to obtain superior

Table 5
The comparison of studies using inorganic materials such as NaBH4 or NH3BH3 as a reducing agent for application to various fields through CO2 conversion.
Precursors Reduction Conditions Applications Explanations Ref.
Agents

CO2 NaBH4 Electrode: 700 ◦ C Lithium-Sulfur Combination with electrospinning for N-rich interlayer [104]
Interlayer: 600 ◦ C battery
CO2 NH3BH3 – – DFT analysis [105]
CO2 NaBH4 500 ◦ C Adsorbent Sulfonic acid functional group derived by H2SO4 [107]
CO2 NaBH4 500 ◦ C Fuel cell Additional heat treatment at 750, 850, 1050 ◦ C [108]
CO2 NaBH4 500 ◦ C Supercapacitor Boron doped porous carbon for supercapacitor [109]
CO2 + N2 (Flue NaBH4 500 ~ 1000 ◦ C Fuel cell KOH treatment [110]
gas)
CO2 + N2 (Flue NaBH4 500 ◦ C Fuel cell Formation of Fe-N-B-C bond through additional heat treatment at 850 ◦ C [111]
gas)
CO2 + N2 (Flue NaBH4 500 C

Fuel cell Additional heat treatment at 1000 C

[112]
gas)
CO2 NaBH4 500 ◦ C – B-doped porous carbon was synthesized for the first time through CO2 [23]
conversion by NaBH4 reducing agent
CO2 NaBH4 500 ◦ C Fuel cell – [113]
CO2 NaBH4 500 ◦ C Fuel cell For additional N doping, heat treatment is performed with urea at 850 ◦ C [114]
CO2 NaBH4 600 ◦ C Lithium-Sulfur Combination with electrospinning for free-standing electrode [115]
battery
CO2 NaBH4 500, 850, 1050 ◦ C Fuel cell Promote ORR activity through Fe-B-C catalyst [116]
CO2 NaBH4 500 ◦ C Fuel cell Synthesis of B-doped porous carbon with Mn3O4 through additional heat [117]
treatment with manganese precursor at 850 ◦ C
CO2 NaBH4 500 ◦ C Lithium-ion battery Cobalt oxide particles are bound to the carbon material [118]
CO2 NaBH4 500 ◦ C Methane Ni@C-B2O3 catalyst is synthesized through an additional heat treatment in Ar [119]
decomposition atmosphere of 950 ◦ C
CO2 NaBH4 700 ◦ C Supercapacitor Use CaCO3 template to make porous carbon with hierarchical structure [120]
CO2 NaBH4 700 ◦ C Supercapacitor Synthesis of CCNT with Ni as catalyst [121]
CO2 NaBH4 600 ◦ C – Synthesis of MWCNT fiber, a material that can withstand at 1000 ◦ C without [122]
collapse, using Ni catalyst
CO2 NH3BH3 ~750 ◦ C – Graphene oxide synthesis using CO2 [124]
CO2 NH3BH3 650, 750, 850 ◦ C Fuel cell Boron and nitrogen co-doping [125]

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

electrochemical performance by synthesizing a material with additional the performance of energy storage devices such as a fuel cell and a
N atoms using flue gas containing nitrogen and CO2 [110–112]. It is supercapacitor.
considered a remarkable CO2 conversion method considering that it not Recently, a composite of metal oxide and CO2-derived carbon ma­
only simply forms a carbon structure without CO2 separation from flue terial was fabricated in a single step of CO2 conversion [118,119]. More
gas, but also improves its chemical properties at the same time. specifically, CO2 was used as a mild oxidizing agent for the synthesis of a
Generally, N or B-doped carbon materials are synthesized by pyrol­ metal oxide via an oxidation step of the metal precursor. To improve the
ysis of organics at a very high temperature exceeding 800 ◦ C. In contrast, performance of LIBs, synthesis of a hybridized cobalt oxide/porous
carbon materials were fabricated under mild reaction conditions of 1 carbon composite having a sandwich-like morphology, where cobalt
atm and below 500 ◦ C for the synthesis of B-doped porous carbon (B-PC) oxide particles are cohesively incorporated between several carbon
from CO2 reaction with the reducing agent NaBH4 for the first time [23]. flakes, was carried out using CO2 [118].
The porous carbon material was successfully synthesized by only a On the other hand, a single-step CO2 conversion into hierarchical
simple one-step heat treatment in the CO2 atmosphere as shown in porous carbon has been proposed by using NaBH4 and nano-template
Fig. 8A. Also, since B atoms have linkages to carbon lattices that facili­ CaCO3 to change the structural properties of synthesized carbon
tate the electron transfer, the B-PC material synthesized from CO2 has [120]. The aforementioned study showed a new possibility of combining
shown enhanced electrocatalytic activity for the ORR [113]. CO2 utilization and the production of a hierarchical porous carbon
B/N dual-doped porous carbon (BNC) has been synthesized through material through a facile one-step method using templates for a superior
a CO2 reduction process using NaBH4 and continuous N-doping using supercapacitor. As shown in Fig. 8B, when CO2 is converted to carbon by
urea [114]. The electrocatalytic performance of BNCs for the ORR was NaBH4 at 500 ◦ C, CaCO3 is used as a template for mesopores, and CO2
investigated and compared with B-PC to grasp the effect of B/N dual produced by the decomposition of CaCO3 in the heat treatment at 700 ℃
doping. When both B and N atoms were co-doped, more outstanding forms micropores, which leads to the synthesis of CaCO3-templated
ORR performance was confirmed. porous carbon (CPC) with a hierarchical characteristic.
A free-standing electrode in the form of CNF doped with an excessive Another study investigated the synthesis of CNTs from a mild CO2
amount of N atoms was also synthesized, through electrospinning of a atmosphere (500–700 ◦ C & 1 atm) by improving the continuous CVD
solution containing polyacrylonitrile (PAN) and NaBH4 and consecutive method using NaBH4 as a reducing agent and NiCl2 as a Ni catalyst
heat treatment in a CO2 atmosphere. Nitrogen-rich porous fiber (NRPF) precursor [121]. The intrinsic properties of synthesized CO2-derived
prepared by the above-described method can impregnate an excessive CNTs (CCNTs) in terms of porosity caused by the CNT fiber shape as well
amount of sulfur active material based on the porosity created by CO2 as oxygen and boron atoms present on the surface led to superior per­
conversion. Therefore, one of the problems with existing Li-S batteries, formance of supercapacitors.
the low active material ratio, has been successfully improved [115]. This
CO2 (g) + NaBH4 (s)→ NaBO2 (s) + CH4 (g)(ΔG =∼ − 400 kJ) (12)
series of studies provided a new route by which to synthesize B, N-doped
porous carbons, and this method can be effectively carried out to syn­
CH4 (g)→CNT(s) + 2H2 (g)(with Ni as catalyst) (13)
thesize materials doped with other elements in the carbon framework
utilizing CO2 as a carbon source [116]. Based on the mechanisms noted above, boron-coated CNTs (CB-
Since the method with an inorganic material could proceed in rela­ CNTs) were synthesized, which improved antioxidative properties by
tively mild conditions more easily than the existing CO2 conversion doping a large amount of B atoms [122]. As depicted in Fig. 8C, CB-CNTs
method, many approaches have been proposed to synthesize a material were produced through a simple one-step heat treatment process of
having electrochemical properties such as metal oxide during the con­ NaBH4-Ni mixture in a CO2 atmosphere, which contained>30 at.% of
version process or after conversion. For example, boron-doped porous boron content on the surface. Although amorphous carbon decomposes
carbon incorporated with Mn3O4 was synthesized through a two-step from 300 ◦ C in an oxidizing atmosphere, rich boron atoms of CB-CNTs
process [117]. Boron-doped porous carbons synthesized by NaBH4 synthesized in this study combined with oxygen atoms at 200 ◦ C to
were impregnated with Mn(NO3)2⋅4H2O that was further decomposed to form a boron oxide layer (B2O3) that protects CNTs. This led to superior
form Mn3O4 at an elevated temperature. The enhanced electrochemical thermal stability where decomposition did not occur even at 1000 ℃
behaviors by B-doped porous carbon combined with Mn3O4 improved under air conditions and high electrical conductivity equivalent to 4 S

Fig. 8. Schematics of synthesis process and resultant morphologies for (A) boron-doped carbon (adopted from [23] with permission from Elsevier); (B) CaCO3-
templated porous carbon (adopted from [120] with permission from Elsevier); (C) boron-coated CNT (adopted from [121,122] with permission from Royal Society of
Chemistry and American Chemical Society).

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

cm− 1. thermal stability. However, by using this oxidizable property, carbon


The inorganic materials in these studies are not limited to NaBH4. For sheets with metal oxides series such as TiO2, Nb2O5 were synthesized
example, ammonia borane (NH3BH3), which was introduced as a hy­ using a mild oxidant CO2 gas [131,132]. These metal oxides synthesized
dride hydrogen storage material [123], was employed as a reducing through reaction with CO2 improved the electrochemical performance
agent to convert CO2 into carbon materials [124]. When converting CO2 of MXenes.
using NH3BH3, the carbon fixation process is followed by a grapheni­ Yury Gogotsi’s group proposed a unique method to fabricate a
zation step to synthesize the material. The fixation step is carried out by Nb2O5@Nb4C3Tx hierarchical composite through a facile one-step
CO2 reaction with NH3BH3 under mild pressure and temperature con­ oxidation in a CO2 atmosphere at 850 ◦ C, as depicted in Fig. 9A [133].
ditions (P < 3 MPa, T < 100 ◦ C), which produces solid compounds Since the high conductivity of the inner non-oxidized Nb4C3Tx layers,
containing various functional groups, whereas these solid materials are and the electron “bridge effect” of the disordered carbon formed be­
pyrolyzed at high temperatures (T > 600 ◦ C) and atmospheric pressure tween them, the oxide-MXenes with a hierarchical structure decorated
to generate GO-boron nanocomposites [124]. Due to the amphoteric with Nb2O5 on the surface have high capacity and a superior rate
nature of CO2, it can react to an acid and base simultaneously. Therefore, response.
CO2 reacts with NH3BH3, which could be a useful reducing agent and A one-step synthesis method of thin sheets with disordered graphitic
one of the simplest Lewis acid and base adducts for effective CO2 con­ carbon, incorporating oxidized nanocrystals TiO2, was also introduced
version. Based on these mechanisms, the reaction of CO2 and NH3BH3 through oxidation of 2D Ti3C2 [134]. This work succeeded in making a
was performed to synthesize B/N co-doped GO at relatively low pressure graphitic structure decorated with TiO2 nanoparticles through flash
without any metal catalyst to obtain superior fuel cell performance oxidation of Ti3C2 in an air atmosphere at a very high temperature of
[125]. 1150 ℃ or oxidation in a CO2 atmosphere between 150 ◦ C and 300 ◦ C.
Other reducing agents also have been used for CO2 reduction. Porous This synthesized material via the oxidation process secured a stable
carbon was fabricated via a milling process through the mechano­ specific capacity even at a very high current density when applied to
chemical reaction of CO2 with sodium hydride (NaH) [126]. This work LIBs.
confirmed that the microstructure and morphology of carbon were CO2 as a mild oxidant has been shown to be an excellent choice for
affected by the ball milling conditions. CO2 transformation with MXenes to obtain metal oxide-disordered
Nitrogen-doped multilayer graphite was synthesized from CO2 with carbon hybrid materials because of the ignition of thin MXenes flakes
polyaminoborane (PAB) via two steps: First, CO2 is reacted by PAB at upon exposure to air during oxidation. As an example, the partial
temperature up to 115 ◦ C in a high-pressure micro-DSC under 3.10 MPa oxidation of Mo2CTx to produce amorphous carbon composites deco­
CO2, resulting in a solid material with functional groups. Additional rated with MoO2 metal oxide utilizing CO2 as a mild oxidant was
pyrolysis of this solid product up to 750 ◦ C then leads to the production attempted [135]. Fig. 9B shows the SAED pattern images, and it can be
of nitrogen-doped multi-layer graphite incorporated into the solid res­ interpreted that each sample has high crystallinity with respect to Mo2C
idue [127]. or MoO2. In the case of Mo2CTx-850, the pattern for Mo2C disappears
Nanostructured carbon materials for an anode electrode in next- and only the pattern of MoO2 is identified, which indicates that the
generation SIBs were also synthesized. Previously, hard carbon mate­ Mo2CTx-850 layer has amorphous properties. In addition, it was
rials, prepared by different carbon precursors such as PAN [128], and confirmed that more MoO2 particles were formed on the layer surface as
cellulose [129] were applied to SIBs. However, the rate performance of the oxidation temperature increased, as shown in Fig. 9C. In the XRD
the SIBs comprising them was not satisfactory. In an attempt to resolve data, it was seen that the peak for Mo2CTx MXenes disappeared and
this problem, research on preparing a carbon material via CO2 conver­ peaks for MoO2 were formed through the CO2 oxidation process at
sion with Fe3O4-H2 was carried out. As a result, the synthesized material 500 ◦ C and 850 ◦ C, as seen in Fig. 9D. When the heat treatment tem­
secured high capacity, fast charging response, and stable cycle perfor­ perature was increased from 500 ◦ C to 850 ◦ C, the intensity of the peak
mance for SIBs [130]. increase, indicating that MXenes can be effectively oxidized by using
CO2.
4.3. CO2 conversion with MXenes and other materials The treatment of CO2 on MXenes is used not only in LIBs, but also in
Li-S batteries. Li-S batteries are considered next-generation batteries
Recently, CO2 has been widely utilized for the activation of MXenes. that can replace LIBs with limited capacity because of the low cost of
MXenes are fabricated through the removal of a group of element A from active materials and high theoretical capacity of 1675 mAh g− 1
the MAX phase (Mn+1AXnTx, 1 ≤ n ≤ 3), where A mainly refers to IIIA or [136,137]. However, they have the serious problem of a shuttle phe­
IVA semiconductor or metal, M refers to a transition metal such as Ti, nomenon in which active materials such as lithium polysulfides are
Nb, and Mo, X indicates the carbon or nitrogen, and T is a termination dissolved in an organic electrolyte and moved to the counter electrode to
group such as F, O, and OH. MXenes are considered very promising cause self-discharge. To solve this problem, a material in which TiO2
materials because they have excellent flexibility and conductivity. Un­ nanocrystalline particles are homogeneously distributed by reacting
fortunately, pristine MXenes are easily oxidized because of their low Ti3C2 with CO2 was fabricated [138]. TiO2 and lithium polysulfide,

Fig. 9. (A) Schematic of hierarchical composite’s structure before and after oxidation (adopted from [133] with permission from Wiley Online Library). SAED
patterns and TEM images of (B1, C1) Mo2CTx-850, (B2, C2) Mo2CTx-500, and (B3, C3) Mo2CTx. (D) XRD spectra of Mo2CTx, Mo2CTx-500 and Mo2CTx-850 (adopted
from [135] with permission from Elsevier).

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J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

which have polar properties, form strong chemical interactions with not appropriate to apply continuous processes.
each other and inhibit the movement of active materials to minimize It was therefore necessary to introduce a safer and more effective
irreversible capacity loss due to the shuttle phenomenon. In addition to method that can directly utilize CO2 gas itself, and one example of such a
battery fields, TiO2 was applied to lithium ion capacitors and it can be method is MSCC-ET, which can make carbon materials by directly
applied to various electrochemical energy storage devices [139]. processing CO2 gas under atmospheric pressure utilizing electricity
To enhance durability, the material produced through the reaction [43,74]. However, the MSCC-ET process has limitations in that it is not
between MXenes and CO2 is sometimes used as an additive. Synthesis of clear to understand the detailed processes of carbon reduction such as
a TiO2-supported carbon layer (C/TiO2) hybrid material utilizing Ti3C2 the gas behavior at the molten salt and electrode/electrolyte interface,
as a template has been reported. The combination of TiO2 formed by the and further studies are required for management and application of
reaction of Ti3C2 and CO2 can improve the mechanical properties and carbon products. The MSCC-ET also needs a complex batch system that
wear resistance of composites. Additionally, it was confirmed that the can satisfy all complicated factors such as stability and durability of cell
tribological properties and fracture toughness of the composite were components, appropriate mass and energy balance, effective cell design
improved by introducing the synthesized C/TiO2 material into a Si3N4 and power supply and maintenance of the desired potential. In addition,
matrix; these results are related to bridging between the carbon layers when considered on a large-scale process, a large amount of molten salts
and the loading-support of TiN produced by the introduction of TiO2 is required, and a lot of energy can be consumed to induce an electro­
[140]. The detailed oxidation conditions and the resultant carbon chemical reaction for synthesizing carbon materials, which may increase
composites for various MXenes are listed in Table 6. the production cost.
Numerous studies on making carbon materials through various CO2 To solve these problems, research is being conducted to directly
conversion paths have been reported. For example, uncommon reducing convert CO2 gas into carbon materials using a metal such as Mg, Zn, or
materials such as Zn-Ge-O photocatalysts and rhodium-bearing Ni. The metallic substances are effective reducing agents that enable the
magnetite were used for CO2 conversion [141,142]. Also, recently, a growth of solid carbon on the metal surface by adsorbing and reducing
study to make graphite carbon by reacting CaC2, which can be easily CO2 based on the superior ability to break strong chemical bonds. In
produced through bio-materials, and CO2 gas, has also been reported addition, it is considered a technology increasing the possibility of
[143]. CaC2 could be a useful precursor for a large amount of CO2 commercialization for CO2 conversion because of its moderate experi­
reduction because it can be synthesized on a large-scale through the mental conditions, a simple system compared to the previously
thermo-reaction between CaO and bio-based materials. The aforemen­ mentioned methods, and the low cost of the substance. Furthermore,
tioned work synthesized graphitic carbon nanosheets (GCNSs) via a metal-derived carbon materials, which have a superior structure that
facile one-step heat treatment process at 700 ◦ C, as can be seen from the enables the movement of ions more facilely, have been successfully
chemical reaction equation below. applied to fields with high commercial value such as batteries [25].
Recently, studies on CO2 conversion using inorganic materials such
2CaC2 (s) + CO2 (g) → 2CaO (s) + 5C (s) (14)
as NaBH4 and NH3BH3 have been conducted simultaneously
In addition to studies on converting CO2 to carbon, attempts to in­ [23,108,123]. Inorganic materials-based conversion processes are also
crease the yield of carbon sources by utilizing C2H2 [144], and using CO2 considered to be feasible technology in the commercialization process of
as an active material in the batteries are simultaneously being conducted CO2 conversion because they can synthesize carbon materials through
[145]. These results indicate that CO2 can be used not only as a pre­ relatively mild conditions and facile continuous processes based on their
cursor for the synthesis of porous carbon materials, but also as a useful superior reduction ability. Also, the N and B atoms contained in the
chemical substance in various fields. inorganic material can be successfully doped in the process of synthe­
sizing carbon material with a facile one-step process, which can greatly
5. Summary and future prospects improve the chemical properties of the produced material for superior
performance in various field applications.
The excessive emission of CO2 has caused serious social problems Although these studies have developed technologies for synthesizing
such as global warming, and to partially contribute to solving this carbon materials using CO2 as a resource, further improvements are
problem, many studies to synthesize various porous carbon materials needed to commercialize the CO2 conversion process. Above all, intro­
utilizing CO2 as a resource have been described in the previous sections. ducing CO2 conversion into an actual system requires additional cost
As one of these utilizations, dry ice or supercritical CO2 was mainly savings through process simplification. In this regard, studies have been
used as a carbon precursor by applying energy such as heat and plasma conducted to convert flue gas containing CO2, N2, and various gases
to produce carbon materials. However, these two conventional CO2 emitted from the plant directly into carbon materials using a reducing
conversion systems have serious problems. The dry ice was typically agent [110–112]. Through this synthesis process, materials with supe­
made by a compression and expansion process of CO2 under extremely rior performance in energy storage devices have been successfully syn­
high-pressure conditions. Because solid dry ice is not a gas or liquid, it is thesized. These results indicate that the process of separating CO2 from
the actual industry gases could be eliminated, offering the potential to
Table 6 design more simplified system and applying CO2 conversion to real in­
The examples of works where CO2 was used as a mild oxidizing agent for the dustry directly.
synthesis of oxidized MXenes. Additionally, strategies to improve the reaction conditions in the
Precursors CO2 oxidation Products Applications Ref.
synthesis process and compensate production costs by synthesizing
conditions expensive carbon materials with unique properties should also be
considered. All advantages of each reducing agent can be exploited via
Ti3C2 700 ◦ C LDC-S-TiO2/C Hydrogen [131]
production an approach of converting CO2 by mixing a metal and an inorganic
Nb2CTx 850 ◦ C Nb2O5/C/Nb2C Hydrogen [132] reducing agent and thereby obtain outstanding structural and chemical
composites production properties of carbon materials via a one-step process. As a result, the use
Nb4C3Tx 850 C

Oxidized Nb4C3Tx Li-ion battery [133] of metals or inorganic materials for CO2 conversion is considered a
Ti3C2 150, 300, 500 ◦ C Oxidized Ti3C2Tx Li-ion battery [134]
Mo2CTx 500, 850 ◦ C Mo2CTx-500, Li-ion battery [135]
promising strategy for commercialization because it offers the advan­
Mo2CTx-850 tages of relatively moderate experimental conditions, a simplified pro­
Ti3C2 900 ◦ C Oxi-d MXene900 Lithium-Sulfur [138] cess system. Also, these series of studies have shown the potential to
battery develop high-value carbon products with superior material properties
Ti3C2 700 ◦ C SN-15CT [140]

that exhibit outstanding electrochemical performance, which can

14
J.H. Park et al. Chemical Engineering Journal 427 (2022) 130980

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