Reactores 2

Whang et al.
BMC Chemical Engineering

https://doi.org/10.1186/s42480-019-0007-7
(2019) 1:9
BMC Chemical Engineering
REVIEW Open Access
Heterogeneous catalysts for catalytic CO2

conversion into value-added chemicals
Ho Seok Whang, Jinkyu Lim, Min Suk Choi, Jonghyeok Lee and Hyunjoo Lee*
Abstract
As climate change becomes increasingly evident, reducing greenhouse gases including CO2 has received growing
attention. Because CO2 is thermodynamically very stable, its conversion into value-added chemicals such as CO,
CH4, or C2H4 is difficult, and developing efficient catalysts for CO2 conversion is important work. CO2 can be
converted using the gas-phase reaction, liquid-phase reaction, photocatalytic reaction, or electrochemical reaction.
The gas-phase reaction includes the dry reforming of methane using CO2 and CH4, or CO2 hydrogenation using
CO2 and H2. The liquid-phase reaction includes formic acid formation from pressurized CO2 and H2 in aqueous
solution. The photocatalytic reaction is commonly known as artificial photo-synthesis, and produces chemicals from
CO2 and H2O under light irradiation. The electrochemical reaction can produce chemicals from CO2 and H2O using
electricity. In this review, the heterogeneous catalysts used for the gas-phase reaction or electrochemical reactions
are discussed, because the liquid-phase reaction and photocatalytic reaction typically suffer from low productivity
and poor durability. Because the gas-phase reaction requires a high reaction temperature of > 600 °C, obtaining
good durability is important. The strategies for designing catalysts with good activity and durability will be
introduced. Various materials have been tested for electrochemical conversion, and it has been shown that specific
metals can produce specific products, such as Au or Ag for CO, Sn or Bi for formate, Cu for C2H4. Other
unconventional catalysts for electrochemical CO2 reduction are also introduced.
Keywords: Carbon dioxide, Dry reforming, Reverse water-shift reaction, Hydrogenation, Electrochemical reduction
Background where they can do harm, and CO2 can also be used to
Global energy consumption has soared due to increasing produce valuable chemicals [4–6].
population and industrialization, and anthropogenic Because CO2 is thermodynamically the most stable car-
CO2 emissions have rapidly grown because the main en- bon species, its conversion into value-added products usu-
ergy resources being consumed today are fossil fuels. In- ally requires the expenditure of considerable energy.
creasing CO2 concentration in the atmosphere is leading Various chemical processes have been reported that can
to global warming and a range of environmental prob- convert CO2 into chemicals such as CO, hydrocarbon, or
lems. Global average temperatures have increased by 0.8 oxygenated hydrocarbon. Gas-phase reaction, liquid-phase
°C over the last 70 years [1]. International efforts have reaction, electrochemical, and photocatalytic reaction
been proposed to reduce CO2 emissions, such as the methods have been reported. Gas-phase reactions include
multinational Paris agreement. At the same time, many the dry reforming of methane (CH4 + CO2 → 2CO + 2H2),
studies have focused on the development and application CO2 hydrogenation (CO2 + H2 → CO + H2O, which is also
of renewable energy sources as a means of reducing de- called the reverse water-gas shift reaction; CO2 + 4H2 →
pendence on fossil fuels [2, 3], as well as technologies CH4 + 2H2O). The liquid-phase reaction includes the pro-
for capturing and utilizing CO2. CO2 utilization would duction of formic acid using CO2 dissolved in aqueous
reduce greenhouse gases in the atmosphere and oceans phase (CO2 (aq) + H2 (aq) → COOH). Several review pa-
pers about CO2 hydrogenation can be found in the litera-
tures [7–9]. However, CO2 hydrogenation or formic acid
* Correspondence: azhyun@kaist.ac.kr formation requires H2, which is mainly produced from
Department of Chemical and Biomolecular Engineering, Korea Advanced
Institute of Science and Technology, Daejeon 34141, Republic of Korea
© The Author(s). 2019 Open Access This article is distributed under the terms of the Creative Commons Attribution 4.0
International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and
reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to
the Creative Commons license, and indicate if changes were made. The Creative Commons Public Domain Dedication waiver
(http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated.
Whang et al. BMC Chemical Engineering (2019) 1:9 Page 2 of 19
methane by steam reforming, which also produces a large

amount of CO2.
Electrochemical CO2 reduction has received a great deal
of attention recently, but the low solubility of CO2 in
aqueous solution has been a major obstacle. The use of a
gas diffusion electrode has enabled the direct use of gas-
eous CO2 for electrochemical conversion. This electro-
chemical conversion process does not require H2 as a
reactant. Photocatalytic CO2 conversion also received
growing attention because of its similarity to photosyn-
thesis, but the process typically suffers from low product-
ivity and poor stability.
Efficient catalysts can minimize the energy needed for
reactions by reducing the activation energy. Various cat-
alysts are being actively investigated to enhance CO2
conversion and to control selectivity toward specific tar- Fig. 1 Thermodynamic equilibrium plots for DRM at 1 atm, 0–1000 °
get products. In this review, we will focus on the hetero- C and at a reactant feed ratio of CO2/CH4 = 1. These equilibrium
geneous catalysts for gas-phase CO2 conversion and calculations were conducted using the Gibbs free energy minimization
electrochemical CO2 conversion. In the gas-phase CO2 algorithm on HSC Chemistry 7.1 software. (Reprinted with permission
conversion, catalysts used for the dry forming of me- from ref. [17]. Copyright 2013 Elsevier)
thane, CO2 hydrogenation producing CO, and CO2 hy-
drogenation producing CH4 will be discussed. In the (RWGS) reaction (Eq. (4)) or carbon gasification reac-
electrochemical CO2 conversion, the specific catalysts tion (Eq. (5)) can occur. The RWGS reaction affects the
used to produce CO, formic acid, and hydrocarbons will H2/CO ratio; because the RWGS reaction happens more,
be discussed. Reviews of formic acid formation or photo- the H2/CO ratio decreases and CO2 conversion in-
catalytic CO2 conversion can be found in the literature creases. The steam produced from the RWGS reaction
[10, 11]. can react with carbon and produce syn-gas.
Catalytic CO2 conversion in gas phase

Dry reforming of methane CO2 þ H2 →CO þ H2 O; ΔH° ¼ 41 kJ mol‐1 ð4Þ
The dry reforming of methane (DRM) (Eq. (1)) can con- C þ H2 O→CO þ H2; ΔH° ¼ 131 kJ mol‐1 ð5Þ
sume two greenhouse gases (CO2 and CH4) simultan-
eously and produce synthesis gas (abbreviated syn-gas, a Also, deactivation occurs easily due to sintering and
mixture of CO and H2). The ratio of H2 to CO products coke deposition, which degrades long-term durability
is 1, which is much lower than other reforming reac- [12, 18–20]. Carbon is produced due to the Boudouard
tions, such as the steam reforming of methane (SRM) reaction and methane cracking (Eq. (6) and Eq. (7)). The
and partial oxidation of methane (POM) (Eqs. (2) and carbon is thermodynamically the main product at tem-
(3)). The low ratio of H2/CO is useful for synthesizing peratures lower than 570 °C [17]. DRM can proceed
long chain hydrocarbons via the Fischer-Tropsch reac- above 640 °C with methane cracking. The Boudouard re-
tion [12–14]. action can’t occur above 820 °C. Carbon can be pro-
duced by the Boudouard reaction, and methane cracking
occurs from 570 to 700 °C [21]. Coke deposition is
CH4 þ CO2 →2CO þ 2H2; ΔH° ¼ 247 kJ mol‐1 ð1Þ thermodynamically favored at low temperature. The car-
bon produced by methane cracking is likely to react with
CH4 þ H2 O→CO þ 3H2; ΔH° ¼ 246 kJ mol‐1 ð2Þ steam or carbon dioxide at high temperature. Thus, the
. DRM reaction should be performed at high temperature.
CH4 þ 1 O2 →CO þ 2H2; ΔH° ¼ ‐36 kJ mol‐1 ð3Þ
2
The DRM reaction is endothermic, requiring a high 2CO þ C→C þ CO2; ΔH° ¼ ‐172 kJ mol‐1 ð6Þ
reaction temperature of > 700 °C, which results in high CH4 →C þ 2H2; ΔH° ¼ 75 kJ mol‐1 ð7Þ
energy cost [15, 16]. Figure 1 shows the DRM equilib-
rium plots at various temperatures and 1 atm [17]. The Various heterogeneous catalysts have been developed,
high temperature is required to attain high product including metal supported catalysts, perovskites, and
yield. Side reactions such as the reverse water gas shift solid solution catalysts [22–26]. Precious metals (Pt, Rh
or Ru) are known to have high activity and durability, al-

though at high price. Non-precious metals (Ni or Co)
have been widely investigated as well. In this section,
each component of DRM catalysts will be explained, and
the strategies to enhance their activity and durability for
DRM will be demonstrated.
Compositions of the catalysts: Metal, supports, promotors

Precious metals such as Pt, Rh and Ru are highly active
for DRM and also resistant against coke deposition [27–
30]. The precious metal-based catalysts show high activ-
ity in spite of the very small amount of metal catalyst Fig. 3 Schematic diagram of the dealloying and realloying behavior
of a Ni-Fe alloy particle during DRM. (Reprinted with permission from
used. For example, the Ru/ZrO2-SiO2 catalyst shows ref. [36]. Copyright 2017 American Chemical Society)
high activity and durability, as shown in Fig. 2, even
though the Ru content was only 0.13 wt% [31].
Non-precious metals such as Ni or Co have been used Supports can affect catalytic activity and durability for
more for DRM due to their cheap price and abundance DRM [37]. The interaction between a support and metal
[32–34]. Ni catalysts have shown a level of activity com- can change the dispersion of the metal, resistance
parable to precious metals [30]. Alloyed metal catalysts against sintering, and the electronic structure of the
are widely used for DRM because they have a different metal [28, 31]. Figure 4 shows the X-ray absorption fine
electronic structure than monometallic materials [35]. structure (XAFS) analysis results of Rh catalysts depos-
For example, the Ni-Fe alloy catalyst exhibited interest- ited on various supports of Al2O3, TiO2, etc. The X-ray
ing behavior for DRM, as shown in Fig. 3. Monometallic absorption near edge structure (XANES) analysis in
Ni or Fe catalysts have shown poor durability, because Fig. 4a shows that the Rh electronic structure has chan-
the monometallic Ni catalyst is easily deactivated by ged as a result of the support materials. TiO2 supported
coke deposition, and Fe is inactive for DRM. During the Rh has a metallic character, while ɣ-Al2O3 supported Rh
DRM reaction, the Ni-Fe alloy surface is partially oxi- has an oxidic character. Figure 4b shows extended X-ray
dized; Ni maintains an oxidation state, while Fe is oxi- absorption fine structure (EXAFS) spectra. The Rh-Rh
dized by CO2. The oxidized FeO causes dealloying of the peak at 0.24 nm has different intensities with various
surface, and the FeO then oxidizes the carbon deposited supports. When the intensity is higher, the Rh-Rh coord-
on the surface, returning to Fe. The Fe2+/Fe redox cycle ination number is higher, indicating lower dispersion.
plays a key role in enhancing durability in the DRM re- The support materials affect the dispersion of the metal
action [36]. and chemical environment. [28].
Fig. 2 a TEM images of fresh catalyst Ru/ZrO2-SiO2 catalyst; the insets indicate high angle annular dark field (HAADF)-scanning transmission
electron microscope (STEM) images. b DRM results for a Ru-based catalyst with a space velocity of 80,000 ml/gcat·h at 800 °C. (Reprinted with
permission from ref. [31]. Copyright 2017 Elsevier)
Fig. 4 Rh K-edge a XANES spectra and b EXAFS data for Rh catalysts deposited on various supports. (Reprinted with permission from ref. [28].
Copyright 2002 Springer)
The strong-metal support interaction (SMSI) causes a nanoparticles do not have carbon deposition. In this sec-
high dispersion of metals resulting in small sized metal tion, various strategies to control the nano-structures of
nanoparticles with enhanced DRM activity. In addition, it catalysts to prevent coke deposition will be discussed.
increases resistance against sintering with enhanced dur- In order to prevent the sintering of nanoparticles, an
ability [31, 38, 39]. The acidity and basicity of the support inorganic oxide overlayer was formed on Ni nanoparti-
also affects catalytic properties. CO2 is activated by form- cles [53–57]. As shown in Fig. 6, Ni nanoparticles with
ing formate with surface hydroxyl on an acidic support. an average size of 5 nm were immobilized on SiO2
CO2 is activated by forming oxy-carbonate on a basic sup- spheres, then porous SiO2 overlayers were formed on
port. On an inert support such as SiO2, both CO2 and the Ni nanoparticles. The resulting Ni/SiO2@SiO2 cata-
CH4 are activated by metal with faster deactivation. A lyst showed high durability for DRM; activity was main-
DRM catalyst supported on an inert material (SiO2) is tained for 170 h at 800 °C without Ni sintering [53].
usually less active and less durable than on an acidic sup- Using this nano-structure, the effects of Ni size and
port (Al2O3) or basic support (La2O3) [23, 30, 40, 41]. support were evaluated independently. To evaluate the
Promoters have been widely used for DRM. Alkali size effect, various sizes of Ni nanoparticles were depos-
metal oxides such as K2O or CaO have been used to in- ited; 2.6, 5.2, 9.0, 17.3 nm. CH4 turnover frequency
crease the basicity of the catalyst enhancing CO2 adsorp- clearly increased as Ni size decreased. The size effect
tion [42–44]. CeO2 or ZrO2 were used to increase could be evaluated exactly because the Ni size was barely
oxygen mobility [22, 45–50]. The transition between Ce3 changed even after the DRM reaction at 800 °C. The dif-
+
and Ce4+ can occur easily on CeO2. The coke formed ferent metal oxide overlayers of Al2O3, MgO, ZrO2,
on Ni sites could be oxidized by using the redox cycle of TiO2, SiO2 were formed on Ni/SiO2 with a Ni particle
CeO2 with enhanced coke-resistivity [47]. The surface size of 5.2 nm. The Al2O3 and MgO overlayers showed
hydroxyl group can participate in the DRM surface reac- enhanced CH4 turnover frequency, while the other over-
tion. Zhu et al. reported that the energy barrier for CH layers hardly showed enhancement [55].
and C oxidation by surface OH was slightly lower than
the barrier for surface O [51]. Ni et al. showed that the
surface hydroxyl groups were increased by adding B2O3
to Ni catalyst, as shown in Fig. 5. The surface hydroxyl
groups oxidize the carbon formed from methane decom-
position, with enhanced resistance against coke depos-
ition [52].
Coke-resistant catalysts
The key objective of catalysts developed for DRM is how
to prevent coke deposition. Highly durable catalysts
Fig. 5 Mechanism of carbon suppression on Ni/B2O3–Al2O3 catalyst.
should avoid sintering because large Ni particles have se-
(Reprinted with permission from ref. [52]. Copyright 2012 Elsevier)
vere coke formation at the surface, while small Ni
Fig. 6 Schematic illustration of Ni/SiO2@SiO2 catalyst with high coke resistance for the DRM reaction. (Reprinted with permission from ref. [53].
Copyright 2014 John Wiley and Sons)
Similarly, core-shell structures have been investigated; Fig. 7 [70]. Developing catalysts with high activity and
an outer shell such as SiO2 separates the catalytic core durability is essential to obtain a maximum yield.
material such as Ni nanoparticles while preventing sin- Two reaction pathways, the redox mechanism and for-
tering [58, 59]. The core-shell structures have been mate decomposition mechanism, have been reported for
widely used in DRM, CO oxidation, and methane com- CO formation from RWGS. A case with a Cu catalyst
bustion reactions [60–62]. Li et al. developed a Ni yol- followed the redox mechanism; CO2 oxidizes Cu0 to
k@Ni@SiO2 catalyst, where a SiO2 shell with Ni Cu+ generating CO, and H2 reduces Cu+ to Cu0 forming
nanoparticles embedded in the middle surrounds a Ni H2O [71]. In the formate decomposition mechanism,
yolk core. This catalyst was highly active for DRM, and CO2 hydrogenates to formate, followed by cleavage of
it maintained activity without sintering for 90 h at 800 ° the C=O bond [72]. Catalysts for RWGS should contain
C [62]. active sites to dissociate hydrogen and adsorb CO2. Pre-
Mesoporous materials have been widely used as sup- cious metal-based catalysts have been widely used for
ports because they provide a large surface area and facile RWGS because of their superior activity for hydrogen
mass transfer [63, 64]. Mesoporous Al2O3 in particular dissociation. The effect of Pt particle size on the
has been widely used because it can have a strong inter-
action with a metal active phase, and it has high thermal
stability [65, 66]. Conventional impregnation with a
metal precursor might cause pore blockage. Wang et al.
developed ordered mesoporous Ni-Ce-Al oxide for
DRM with self-assembly induced by solvent evaporation
[67]. The Ni nanoparticles were uniformly deposited in
the pore channel of the mesoporous support. The cata-
lysts showed high durability because the Ni nanoparti-
cles did not sinter severely due to spatial confinement. It
maintained high DRM activity for 80 h at 700 °C.
CO2 hydrogenation
Reverse water-gas shift reaction
CO2 can react with H2 to produce CO via the reverse
water gas shift reaction. The RWGS reaction was first
observed in 1914 by Bosch and Wild when they tried to
produce H2 from steam and CO over FeOx catalyst [68].
RWGS can produce syn-gas, which is useful for synthe-
sizing valuable chemicals such as ammonia, methanol,
and fuels, from CO2 [69]. However, the RWGS reaction Fig. 7 Thermodynamic equilibrium of CO2 hydrogenation at 1 bar
and a H2/CO2 molar ratio of 4. (Reprinted with permission from [70].
is endothermic, requiring high temperature, and CO is
Copyright 2012 Royal Society of Chemistry)
the dominant product above 600 °C as can be seen in
selectivity of CO and CH4 was identified using rutile and activation barriers for oxygen removal were the
TiO2 as a support. Small Pt particles preferred CO for- main factors for identifying effective catalysts for CO2
mation. Pt-CO species were the key intermediate decid- reduction.
ing CO selectivity in the RWGS reaction [73]. Willauer et al. prepared K-Mo2C supported on
The Au@UIO-67 catalyst was synthesized for the γ-Al2O3 [81]. By modifying with a K promoter, CO se-
RWGS reaction. UIO-67, which is porous metal-organic lectivity and stability increased, with only 7.3% deactiva-
framework, was used to disperse Au nanoparticles, then tion after 68 h. CO2 adsorption was enhanced and CO2
the interaction between the metal and support was en- dissociation barriers were reduced on the K-promoted
hanced. Au@UIO-67 showed high activity and CO se- catalyst. Illas et al. reported that polycrystalline α-Mo2C
lectivity for RWGS [74]. A Pd–In/SiO2 catalyst was catalyst showed 16% CO2 conversion and 99.5% CO se-
synthesized by the wet impregnation method and used lectivity at 673 K in RWGS [82]. The presence of a
for RWGS. While the Pd/SiO2 showed 88% CO selectiv- (101)-Mo/C surface on the catalyst provides active sites
ity, Pd-In/SiO2 showed 100% CO selectivity without for RWGS. Ma et al. synthesized a highly efficient and
CH4 formation. The difference was derived from the stable Cu/β-Mo2C catalyst for the RWGS reaction [83].
modified CO adsorption energy. CO adsorption on the Because of strong interaction between the Cu and
Pd-In bimetallic surface was much weaker than that on β-Mo2C which dispersed the Cu particles uniformly on
the Pd surface [75]. the support, Cu/β-Mo2C showed high activity and stabil-
For the large scale conversion of CO2, non-precious ity compared with Pt- and Cu-based catalysts. Recently,
metal catalysts are preferred due to cost and scarcity. Ni Ajayan et al. reported a metal-free carbon-based catalyst
and Cu-based catalysts are promising because they also for CO2 hydrogenation [84]. Pyridinic N was doped at
show high activity and selectivity for RWGS. But they the edge sites of graphene quantum dots. The N dopants
usually suffer from sintering at high reaction played a key role in inducing thermocatalytic CO2 hy-
temperatures. drogenation activity. CO was produced dominantly at
Various ways of improving thermal stability have been lower temperatures and CO selectivity increased to 85%
investigated. Rossi et al. prepared highly dispersed Ni at 300 °C.
nanoparticles supported on SiO2 using magnetron sput- Recently, Ajayan et al. reported a metal-free
tering deposition. The prepared catalyst showed better carbon-based catalyst for CO2 hydrogenation [84]. Pyri-
activity at T > 600 °C and stability than a conventional dinic N was doped at the edge sites of graphene
catalyst prepared by the wet impregnation method [76]. quantum dots. The N dopants played a key role in indu-
Ni/Ce-Zr-O catalysts were synthesized and used for cing thermocatalytic CO2 hydrogenation activity. CO
RWGS. Ni species were incorporated into the lattice of a was produced dominantly at lower temperatures and
Ce-Zr-O solid solution. High activity, stability and se- CO selectivity increased to 85% at 300 °C.
lectivity were achieved for the conversion of CO2 to CO
[77]. Cu/ZnO catalysts with various Cu/Zn ratios were
synthesized using aurichalcite precursors. The interface CO2 methanation
between the Cu and ZnO affected the catalytic activity CO2 hydrogenation can also produce methane. The
for CO2 activation. As the Cu ratio increased, the Cu do- CO2 methanation has recently received much atten-
main size increased and the CO generation rate de- tion as a way to store intermittent electricity, which
creased [78]. Zheng at al. prepared CeCu composite is produced from solar cell or wind power [85]. The
catalysts with different Ce/Cu mole ratios for RWGS. surplus electricity can electrolyze water, producing
The Ce3+-oxygen vacancy-Cu0 structure was stabilized. H2. Then CO2 and the H2 can have reaction to pro-
Cu sites became more electron deficient following elec- duce methane, which can be used as a fuel. Various
tron transfer from Cu to Ce, with enhanced adsorption precious metals, such as Ru, Rh, Pd, have been used
of CO2 and H2. The Ce1.1Cu1 catalyst showed the high- as catalyst. Ni deposited on various supports have
est catalytic performance for the RWGS reaction [79]. also been used for the CO2 methanation [85]. Amal
Transition-metal carbides (TMCs) are promising for and Dai et al. produced methane from CO2 and H2
RWGS because they can dissociate hydrogen and C=O using porous perovskite materials [86, 87]. The per-
bonds. With their abundance and low cost, many re- ovskite materials with ABOx crystalline structure have
searchers have reported on TMCs based-catalysts for been particularly interesting materials in solar cells or
RWGS. A recent study revealed that Mo2C showed catalytic applications [86]. Ni-Rh nanoalloy nanoparti-
higher CO2 conversion and CO selectivity in the RWGS cles were formed by ex-solution on mesoporous
than other TMCs such as TiC, TaC, ZrC, WC, and NbC LaAlO3 perovskite and showed good performance for
[80]. The experimental and density functional theory CO2 methanation with turnover frequency of 13.9
(DFT) results showed that the oxygen binding energy mol/mol/h [87]. Similarly, mesoporous Ni/Co3O4 was
prepared with high activity for CO2 methanation at intensity increased, CO2 conversion also increased
low temperature [88]. linearly, indicating that hot electrons generated upon
light irradiation were responsible for the CO2 conversion
enhancement.
Light-assisted CO2 hydrogenation In-situ UV spectroscopy results measured under CO2
Light is considered an important and ultimate energy flow also confirmed that CO2 adsorbed on the Ru sur-
source for CO2 reduction, in a process also known as face can absorb visible light. DFT calculations showed
artificial photosynthesis. Various semiconductor-based that the band-gap energy decreased from 8.2 eV for free
photocatalysts have been investigated for CO2 reduction CO2 to 2.4 eV for CO2 adsorbed on Ru, as shown in
[89, 90]. However, they typically have shown low activity Fig. 8b. This small band-gap energy enabled the absorp-
and poor durability. Instead of using light for exciton tion of visible light. The DRIFT measurement in Fig. 8c
production, light can be used as an auxiliary energy shows that CO2 was cleaved to CO with light irradiation
source to minimize overall energy usage. Recently, on a Ru catalyst. By using both light and heat, the overall
unique light-assisted surface reactions have been re- energy could be reduced to 37% of the case when only
ported [91–93]. They can occur through excitation of heat was used, to achieve the same CO2 conversion of
electrons in hybridized orbitals of adsorbed reactant 15%. Additionally, the CO2 conversion was easily initi-
molecules on the metal catalyst surface. ated or terminated simply by turning the light on or off.
We recently reported light-assisted CO2 hydrogenation
on heterogeneous metal catalysts [94]. Various metals Electrochemical CO2 reduction
were tested in a photoreactor by changing temperature, The electrochemical CO2 reduction reaction (CO2RR)
light intensity, and light wavelength. CO2 conversion involves CO2 conversion on an electrode powered by
was enhanced on a Ru or Rh catalyst upon light irradi- electric bias. Because CO2 is highly stable with a linear
ation, as shown in Fig. 8a. They produced CH4 select- molecular shape having two C=O bonds, it requires a
ively. But Pt, Ni, Cu only produced CO without any high overpotential to initiate the reaction [95]. An
enhancement upon light irradiation. As the light overpotential is the difference between the actual applied
Fig. 8 a CO2 conversion enhancement with light irradiation at various temperatures, b schematic diagram of hybridized orbital change and hot
electron generation with light irradiation, c DRIFT analysis results with CO2 flow on Ru catalysts with and without light irradiation. (Reprinted with
permission from ref. [94]. Copyright 2018 Springer Nature)
potential and theoretical thermodynamic potential. Het- Metals producing CO: Au, Ag, Zn, and Pd
erogeneous electrocatalysts should be used to reduce the Au, Ag, Zn, and Pd generate CO as a predominant prod-
overpotential. The performance and reaction pathway uct from CO2RR [101]. CO is an important feed chem-
highly depend on the electrocatalyst. CO2 is electro- ical for various chemical processes [95]. The key
chemically reduced to chemicals or fuels at the cathode, descriptor for CO production is the binding energy of
and the counter anode reaction is water oxidation pro- *COOH. The metals bind to *COOH sequentially
ducing oxygen, typically known as oxygen evolution re- yielding *CO after dehydration, as shown in Fig. 9 [100,
action (OER) [96]. 103, 104]. The reaction pathway toward CO is two
A distinct feature of the electrochemical CO2 re- electron-consuming, which is relatively facile [100].
duction is its compatibility with renewable sources. When CO is the main product, there is no separation
Because CO2 is thermodynamically stable, the CO2 issue because gaseous CO would be naturally separated
conversion involves high energy consumption [95, from liquid electrolyte.
97]. This energy can be obtained from renewable Various works controlling the nano-structures of these
sources, such as solar or wind power, and the ob- metals have been reported to have high CO production
tained electricity can drive the electrochemical from CO2RR; monodispersed Au or Ag nanoparticles
CO2RR. Additionally, electrochemical CO2 conver- [105–108], ligand-free Au nanoparticles with < 2 nm
sion can be used for renewable energy storage [95, [109], inverse opal Au or Ag thin films [110, 111], ultra-
98]. Since the renewable power is inherently inter- thin Au nanowires [112], Au nanoneedles with sharp
mittent and undistributed, storing the electricity in tips [113, 114], concave rhombic dodecahedral Au nano-
chemical bonds might be useful [98]. Fuels such as particles with high-index facets [115], TiC-supported Au
CH4 can be used in current conventional power sys- nanoparticles [116], hexagonal Zn particles [117], elec-
tems. Various chemicals, from several C1 products to trodeposited Zn dendrites [118], anodized Zn foil [119],
multi-carbon products, can be directly generated small sized Pd nanoparticles with rich edge sites [120,
from electrochemical CO2RR [99–101]. 121], Au electrode with adsorbed CN− or Cl− ions [122],
Various products can be obtained from the elec- Ag nanoparticles with surface-bonded oxygen [123],
trochemical CO2RR. Table 1 shows several represen- amine-capped Ag nanoparticles [124]. Although it is
tative CO2RR pathways with thermodynamic hard to compare their performance because of their
standard potentials versus a reversible hydrogen different reaction conditions, the conversion of CO2 to
electrode (RHE) [96, 102]. Neutral pH buffer elec- CO usually reaches 90 ~ 100% faraday efficiency at the
trolytes have been widely used for electrochemical relatively low overpotential of 0.4 ~ 0.7 V.
CO2RR studies, and the potentials at neutral pH
were shown [96]. The CO2RR typically competes Metals producing formate: Sn, Bi, Hg, Cd, and Pb
with the hydrogen evolution reaction (HER). Sup- Sn, Bi, Hg, Cd, and Pb can produce formic acid
pressing HER is one of the most important issues in (HCOOH) or formate (HCOO−) in the CO2RR [101].
the development of electrocatalysts for CO2RR. In The key descriptor toward formate formation is the
this next section, the electrocatalysts are classified binding energy of *OCHO [103]. If the electrode surface
according to products of CO, formate, and is bound to intermediates via oxygen rather than carbon,
multi-carbon species. The metals generating each formic acid will be generated, as shown in Fig. 13 [103].
product are explained. Unconventional catalysts are It was also suggested that formate could be generated
additionally introduced. through an *COOH intermediate at some reaction
Table 1 Representative reaction pathways of CO2RR in neutral pH buffer electrolyte condition with thermodynamic standard
potentials
Reaction in neutral pH buffer electrolyte E0 (V vs RHE)
− −
Cathode reaction (CO2RR) CO2 + H2O + 2e → CO + 2OH − 0.10
− −
(CO2RR) CO2 + 2H2O + 2e → HCOOH +2OH − 0.02
(CO2RR) CO2 + 5H2O + 6e− → CH3OH + 6OH− 0.03
− −
(CO2RR) CO2 + 6H2O + 8e → CH4 + 8OH 0.17
(CO2RR) 2CO2 + 8H2O + 12e− → C2H4 + 12OH− 0.08
− −
(HER) 2H2O + 2e → H2 + 2OH 0
Anode reaction (OER) 2H2O → O2 + 4H+ + 4e− 1.229
Fig. 9 Volcano plots of CO2RR activity toward a CO and b HCOOH as a function of binding energies of *COOH, and *OCHO, respectively, and
c CO2RR mechanisms to CO or HCOOH. (Reprinted with permission from ref. [103]. Copyright 2017 American Chemical Society)
conditions [125, 126]. Because the pathway generating Sn or Bi. Pd also exhibited good performance for formic
formates follows a two electron pathway, like CO, some acid production although it also significantly produced
electrocatalysts might exhibit good CO2RR performance CO [138, 139].
for formic acid production [101]. However, the faradaic
efficiency for formic acid production is usually lower Metal producing multi-carbon species: Cu
than that for CO production [127]. Nevertheless, formic Cu is the only element that can make a C-C bond dir-
acid is the only liquid product which can be obtained ectly from CO2RR with meaningful selectivity [95, 101].
with high selectivity from CO2RR at this stage [101]. Multi-carbon products such as C2H4 can be generated
Various studies which have controlled the nano- with Cu. Figure 10 shows the possible products obtain-
structures of these metals have been reported for for- able from electrochemical conversion on a Cu electrode.
mate production; nanostructured Sn/SnOx thin film It was reported that CO, formate, CH4, C2H4, and H2
[128], Sn or Sn oxide nanoparticles with < 5 nm [129, could be obtained on a Cu electrode [140]. Ethanol,
130], reduced SnO2 porous nanowires [131], hierarchical n-propanol, allyl alcohol, a trace amount of methanol,
mesoporous SnO2 nanosheets [132], electrodeposited Sn glycolaldehyde, acetaldehyde, acetate, ethylene glycol,
dendrites [133], atomic layer deposited Sn or Sn sulfide propionaldehyde, acetone, and hydroxyacetone were
on nanoneedle templates [134], ultrathin Bi nanosheets simultaneously observed in the large overpotential re-
[135], oxide-derived Pb [136]. Due to toxicity of Hg, Cd, gion, higher than 1 V [140].
and Pb, most works have mainly used Sn or Bi. The for- The reaction mechanism of CO2RR on a Cu electrode
mate can be obtained with a faraday efficiency of 60 ~ is highly complicated. Figure 10 provides the possible
90% at an overpotential of 0.8 ~ 1.4 V [95, 101]. reaction pathway maps. Many other pathways on the Cu
On other metals, the selectivity of CO2RR can be con- electrode have also been proposed [141–143]. The *CO
trolled by changing the reaction conditions to produce intermediate is generally regarded to be a key intermedi-
formic acid. For example, CO2RR on W, Fe, Co, Ni, Zn, ate for further reduction, because *CO can be obtained
Pt, Rh, and Ir have been investigated at high pressure at mild potentials, and C2H4 was observed only with sig-
[137]. They showed significant activity toward formate nificant concentrations of *CO [144–146]. The proton-
formation, although their selectivity was not as high as ation of *CO to *CHO needs to overcome an activation
Fig. 10 Proposed reaction pathways of electrochemical CO2RR on Cu electrode in CO2-saturated 0.1 M KHCO3(aq). (Reprinted with permission
from ref. [140]. Copyright 2012 Royal Society of Chemistry)
barrier of 0.74 V, which is considered a rate-determin- Unconventional electrocatalysts

ing step for further reduction to C1 products like So far, electrochemical CO2RR with single metal elec-
CH3OH or CH4 [145, 147]. The *CHO transforms to trodes has been discussed. The studies with single metal
*CH2O, *CH3O, and *CH4 following sequential proton electrodes can provide insight in terms of reaction
coupled electron transfer (PCET) [142, 147]. The mechanisms and the properties of each metal on
*CHO is also a key intermediate for making C-C CO2RR. Some unconventional electrocatalysts, such as
bonds via *CO-*CHO coupling [143]. oxide-derived metals, alloy metals, carbon materials,
Additionally, *CO-*CO coupling can also produce single-atom catalyst, have also exhibited interesting fea-
C-C bonds [141, 148–150]. However, the C-C coup- tures. Distinct selectivity or activity was obtained.
ling pathway has not been elucidated yet, although it
is known that Cu (100) is the best surface to generate Oxide-derived metals
*CO-*CO coupling with the lowest energy barrier Recent studies have revealed that oxide-derived metal
[150, 151]. As a result, C2H4 formation is favored on electrodes had improved catalytic performance com-
Cu (100) [151–153], whereas CH4 is more readily pared to pristine metals [172]. The most common way
produced on Cu (111) [147, 154]. The pathways for to prepare oxide-derived electrocatalysts is to oxidize
further reduction from *CO-*CO or *CHO-*CO to the metal, then reduce it to its original metallic state.
oxygenates, such as acetate, ethanol, 1-propanol, are Oxide-derived Cu produced more C2 products of C2H4,
more complicated, because water from the electrolyte C2H6, and ethanol than electro-polished Cu at the same
participates in the reaction donating oxygen [143, overpotential [168, 170, 172]. Even C3 and C4 products
148]. Because it is crucial to understand the reaction of C3H7OH, C3H6, C3H8, C4H10 were observed from Cl
mechanism to design better catalysts for CO2RR, ion-adsorbed oxide-derived Cu [173]. Oxide-derived Sn
more studies on mechanism or intermediates, such as showed much higher current density and faraday effi-
in-situ experiments, are needed. ciency than a pristine Sn electrode for formic acid pro-
To tune selectivity, nano-structured Cu electrodes duction [128, 133]. Oxide-derived Au [174] or Ag [175]
were studied, including Cu nanofoams [155], Cu nano- showed superior faraday efficiency for CO production,
wires [156–160], nanoporous Cu film [161], Cu nano- with 90 ~ 100% at only 0.3 V overpotential, as shown in
cubes [151–153], Cu truncated nanocubes [153], Cu Fig. 11a.
rhombic dodecahedrons [153], inverse opal Cu film There have been debates on the origin of the enhance-
[162], mesoporous Cu film [163], electro-redeposited ment of oxide-derived metal for CO2RR. Nano-structures
Cu [164], electrodeposited Cu dendrites [165], prism induced in the catalysts or residual subsurface oxygen
shaped Cu [166], nano-structured Cu by battery cycling have been suggested as the source of the enhancement.
[150], hierarchical Cu pillar electrode [167], oxide de- Nano-structured surfaces with rich grain boundaries were
rived Cu [160, 168–170]. The best CO2RR performance obtained after oxidation-reduction cycling [176, 177]. The
on Cu electrode was 60 ~ 70% faraday efficiency toward induced surface had more defect sites with higher binding
C2H4 production [170, 171]. energy to *CO and higher local pH which increased
Fig. 11 Electrocatalytic CO2RR on oxide-derived Au and polycrystalline Au. a Faraday efficiency of each product as a function of applied potential
and b proposed reaction mechanisms. (Reprinted with permission from ref. [174]. Copyright 2012 American Chemical Society)
selectivity toward CO2RR while suppressing HER [169, change in binding energy induced by atomic strains
176–178]. It was also suggested that some oxygen [184]. The reaction path to the C-C coupling was sup-
remained in the subsurface despite the highly reducing pressed by the geometric property of the ordered Au3Cu
conditions of the CO2RR. Ambient pressure XPS, in situ alloys, producing CH4 [185].
electron energy loss spectroscopy (EELS) experiments, The alloy catalysts deviate from the general scaling
and DFT calculations showed that the oxygen helped to relationship of binding strength to intermediates, and
activate CO2 on the surface in the initial step, as shown in by controlling mixing patterns, they can exhibit
Fig. 11b [179, 180]. However, a contradictory result was unique selectivity. For example, while ordered Cu-
also reported, saying that the residual oxide was very un- Pd nanoparticles selectively produced C1 products,
stable in the CO2RR condition, and that the amount of mainly CO, but phase-separated Cu-Pd nanoparticles
oxygen was negligible [181]. produced C2 products, mainly C2H4 [185]. Cu ensem-
ble sites were needed to make C-C bonds, and neigh-
Alloy metals boring Pd sites further helped hydrogenation by
By alloying with a secondary metal, the intrinsic catalytic hydrogen spillover.
performance of metal can be modified, and high selectiv- For multi-electron paths rather than a two-electron
ity or activity can be obtained for CO2RR [101, 127]. path, the key intermediates of *CHO or *COH should be
The enhancement was typically attributed to an elec- formed, but proton-coupled electron transfer on *CO to
tronic or geometric effect on the alloyed catalysts [101, form *CHO or *COH is a rate determining step [101]. It
127]. The presence of a secondary metal led to modula- was reported that if Cu was alloyed with a metal that
tion in the electronic structure of the active site. The could stabilize O, the adsorption configuration of *CHO
binding energy between the active site and reaction or *COH on the Cu-M sites could be adjusted and their
intermediate could be tuned, changing the reaction formation would be favored [186]. Consequently, the
pathway and the resulting selectivity [182–185]. The sec- overpotential for further reduction decreased and the se-
ondary metal can also change the surface geometric lectivity of CO2RR could be controlled. Many other alloy
structure, with different atomic arrangements of reactant catalysts were reported for CO2RR; Cu-In [187], Cu-Sn
or intermediates. The electronic and geometric effect [188] for CO production, Pd-Pt [189], Ag-Sn [190],
has been systematically studied for Au-Cu bimetallic Sn-Pb [191], Sn-Pd [192], Au-Pd [193] for formate
nanoparticle catalysts with different compositions [183, production.
184]. Figure 12a shows that the d-band center was
downshifted as Au content increased, and the change in Carbon-based materials
the electronic structure lowered the binding energy of Carbon-based materials have been actively studied as
*COOH and *CO. The Cu atom was bound to the oxy- promising electrocatalysts for electrochemical reactions,
gen end of the *COOH, while the Au atom formed a such as the oxygen reduction reaction (ORR), OER, and
Au-C bond [183]. The binding strength of each primary HER [194, 195]. Carbon materials have advantages for
bond and the adsorption configuration were tailored by electrochemical applications, including facile transform-
changing the composition of the bimetallic particles. ability to various dimensions and shapes [196]. Zero-
The ordered Au-Cu with three atomic overlayers of Au dimensional carbon dots or graphene quantum dots,
showed high performance for CO production due to the one-dimensional carbon nanotubes, two-dimensional
Fig.12 Tailored properties of Au-Cu alloy nanoparticle catalyst for CO2RR with different compositions. a Electronic structure information obtained
with high-resolution X-ray photoemission spectroscopy (XPS), b scheme for the reaction mechanism on the surface of alloy catalysts, and c
overall mass activity to CO production at − 0.73 VRHE. (Reprinted with permission from ref. [183]. Copyright 2014 Springer Nature)
graphene, and three-dimensional graphene aerogel can be doped into CeO2, the oxygen defect sites of the CeO2
produced with well-developed material science techniques regulated the oxidation state of Cu by forming Cu
[97]. The carbon materials also possess high conductivity, ion-O vacancy pairs. The single atomic Cu catalyzed
high surface area, and good chemical and mechanical CO2RR, producing CH4 with 58% faraday efficiency
stability. [215]. DFT calculations have also predicted that the
Pure carbon materials are basically inert toward CO2RR. SAC structure can suppress HER while promoting
However, if heteroatoms such as N are doped in the car- CO2RR, with the proper choice of metal atom and
bon matrix, electrocatalytic activity is greatly enhanced. supports [216, 217]. Single atom alloys where a single
Negatively charged N sites are considered active sites for atomic metal is located on another metal surface have
CO2RR [197–199]. N-doping introduces a Lewis base site also been suggested by computational method as effi-
to the catalyst, which is beneficial to stabilize CO2 [196, cient catalysts for CO2RR [218].
197]. Various carbon materials, including N-doped carbon Although many intensive efforts have been dedicated
nanotubes [200, 201], N-doped graphenes [202], N-doped to develop electrochemical CO2RR, the performance is
graphene quantum dots [203] were reported for CO2RR still far from the performance obtained from gas-phase
following the two-electron pathway. N-doped diamond CO2 reduction. To enhance electrochemical CO2RR fur-
produced acetate as well as formate with N-sp3C active ther, various other efforts have been tried, by tuning
sites [204]. Other dopants such as S or B have also been other factors. Electrolyte compositions, pH, and concen-
used for CO2RR [205, 206]. trations affected activity and selectivity [96, 219–222].
Ionic liquids helped the activation of CO2 [223, 224]. An
electric field near the electrode was shown to stabilize
Single atom catalysts charged intermediates better [113, 220]. The additives
Single atom catalysts (SAC) represent atomically dis- could control selectivity via electron shuttling or the for-
persed metal catalysts on the surface of a support. They mation of surface films [225, 226]. A gas diffusion elec-
exhibit very distinct electronic structures and adsorption trode (GDE) cell allowed unprecedentedly high current
configurations of reactants and intermediates, with density [171, 227]. Stability, resistivity to catalyst poi-
unique selectivity [207]. SACs have been used for elec- sons, and activity on diluted CO2 feed are also important
trochemical ORR [208, 209], HER [210], formic acid oxi- for practical applications, but they have not yet attracted
dation reaction (FAOR) [211], and CO2RR [212]. Ni much interest at this stage. To develop this technology
single atoms on N-doped graphene can catalyze CO2RR to a commercially feasible level, those many factors
producing CO selectively, as shown in Fig. 13 [212]. should be optimized.
Other metal atoms of Fe, Co, Mn, and Cu with slightly
different d-band structure have shown different selectiv- Conclusion and perspectives
ity. The coordination environment neighboring the Ni Heterogeneous catalysts used for catalytic CO2 conver-
single atom has also been reported to affect the elec- sion into valuable chemicals such as CO, CH4, C2H4
tronic structure and the binding energy of key carbon have been discussed in this review. Because CO2 is
intermediates [213, 214]. When Cu was atomically thermodynamically very stable, its conversion usually
Fig. 13 Structural evolution of Ni single-atom sites on graphene during CO2RR (Reprinted with permission from ref. [212]. Copyright 2018
Springer Nature)
requires a lot of energy, but the production of that en- or dimethyl ether would also have high value. Metal-based
ergy also emits considerable CO2. Obtaining negative catalysts including precious metal or supported Ni catalysts
net CO2 emissions is not easy, and the design of efficient have been used for the production of CO or CH4. Not
catalysts for CO2 conversion is a key to reducing CO2 many good heterogeneous catalysts have been found for
emissions. the production of formic acid, instead homogeneous cata-
Catalytic CO2 conversion can occur in gas-phase, lysts have been typically used. Robust heterogeneous cata-
liquid-phase, or electrochemical cells. Because the solubility lyst producing formic acid might have high potential.
of CO2 is quite low in aqueous solution, the CO2 conver- Catalysts that use both heat and light as energy sources
sion in liquid-phase typically suffer from low productivity. have been developed, to minimize total energy use.
Thus this review mainly focused on the conversion using Electrochemical CO2 conversion has shown improved
gaseous CO2. Various metals, metal oxides, metal carbides, productivity using gas-diffusion electrode cells. It is also
and doped carbon materials have been used as catalysts for very promising because it directly uses CO2 and H2O for
CO2 conversion. Synthetic strategies have been developed chemical or fuel production. The technology for electro-
to endure high reaction temperatures and minimize coke chemical CO2 reduction is in its early stages, compared
formation for dry methane reforming. The CO2 hydrogen- to other CO2 conversion technologies, but it is being in-
ation can be efficient, but they use H2 gas. The H2 gas is vestigated very actively. A variety of materials have been
conventionally produced from methane steam reforming, tested as catalysts for electrochemical CO2 reduction,
which also produces considerable CO2. If H2 can be pro- and the catalysts should be tuned depending on the tar-
duced from water without CO2 emissions, CO2 hydrogen- get products. Au or Ag produces CO, Sn or Bi produces
ation in gas-phase would be a very powerful tool for formate, and Cu produces hydrocarbons such as C2H4.
efficient CO2 conversion. The gaseous product of CO or Considering the cell design of gas-diffusion electrodes,
CH4 have been mainly considered as products from the nano-structured catalysts should be optimized further.
CO2 hydrogenation, but liquid products such as formic acid Most studies so far have used concentrated pure CO2
for the conversion. But the conversion of dilute CO2, es- 10. Li K, Peng BS, Peng TY. Recent advances in heterogeneous photocatalytic
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Springer Nature remains neutral with regard to jurisdictional claims in Energy. 2012;37(15):11195–207.
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Whang et al.

BMC Chemical Engineering

REVIEW Open Access

Heterogeneous catalysts for catalytic CO2

methane by steam reforming, which also produces a large

Catalytic CO2 conversion in gas phase

or Ru) are known to have high activity and durability, al-

Compositions of the catalysts: Metal, supports, promotors

barrier of 0.74 V, which is considered a rate-determin- Unconventional electrocatalysts

224. Asadi M, Kim K, Liu C, Addepalli AV, Abbasi P, Yasaei P, Phillips P,

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