NEW CARBON MATERIALS

Volume 37, Issue 2, Apr. 2022

Online English edition of the Chinese language journal

Cite this article as: New Carbon Materials, 2022, 37(2): 277-289 REVIEW

Recent advances in the electroreduction of carbon dioxide

to formic acid over carbon-based materials
Wen-bin Li, Chang Yu*, Xin-yi Tan, Song Cui, Ya-fang Zhang, Jie-shan Qiu*
State Key Lab of Fine Chemicals, School of Chemical Engineering, Liaoning Key Lab for Energy Materials and Chemical Engineering, Dalian
University of Technology, Dalian 116024, China

Abstract: The electroreduction of carbon dioxide (CO2) driven by renewable energy is an important route for CO2 conversion and utilization.
Formic acid (HCOOH), as an important chemical and safe hydrogen storage material, is one of the main and promising materials for CO2
electroreduction. The physical and chemical properties of CO2 and the reaction mechanisms for its electroreduction to HCOOH are outlined and
the recent development of carbon-based catalysts, including metal-free carbon catalysts and carbon-supported catalysts, for CO2 electroreduction
to HCOOH is reviewed. The design of reactors for HCOOH production and strategies for their optimization are summarized and discussed.
Hybrid CO2 electrolysis technology is analyzed, such as electroreduction coupled with the methanol electrooxidation reaction. Lastly, key
challenges and development trends for CO2 electroreduction to HCOOH are presented, which are expected to provide guidance for the
development of this technique.
Key Words: Carbon-based materials; CO2 electroreduction; Formic acid; Reactor

1 Introduction including carbon monoxide (CO)[13-15], formic acid

The constant burning of fossil fuels results in large
amounts of greenhouse gases that are released into the
atmosphere, which causes an increase of the global carbon
dioxide (CO2) concentration continuously, and also causes the
imbalance of the carbon cycle[1-3]. To deal with climate change
problems that was caused by massive CO2 emissions,
including global warming, ocean acidification and ecosystem
destruction, the conversion and utilization of CO2 have
attracted the wide attention of researchers[4-7]. Electrochemical
CO2 activation and catalytic conversion driven by renewable
energy has become a significant technical route for CO 2
conversion and utilization due to its advantages of green, mild
operating conditions, and energy saving[8-11]. Electrochemical
CO2 reduction reaction (CO2RR) is a proton-coupled
multi-electron transfer process, and the reaction is relatively
complex, which involving multiple reaction intermediates and
different reduction products. CO2 is linearly symmetric in
structure and has chemical stability. In thermodynamics, the
activation of CO2 requires a large energy input with the C―O
bond energy of 803 kJ mol−1[12]. In terms of kinetics, the
catalytic conversion of CO2 is competitive with hydrogen
evolution reaction (HER). Therefore, the development of
electrocatalysts with high activity, selectivity and stability is
the key to achieve the CO2 activation and conversion.
Electrochemical CO2 conversion involves multi-electron
transfer, which can produce a variety of reduction products,
(HCOOH)[16-19], methane (CH4)[20], ethylene (C2H4)[2,9],
ethanol (C2H5OH)[21,22], etc. Among the CO2 electroreduction
products, HCOOH, as an important chemical basic raw
material, is the key reaction intermediate for synthesis of
down-stream products such as HCOOH ester, formamide and
other products. HCOOH is also an important hydrogen storage
material, which can safely and efficiently store hydrogen
energy in the form of liquid and ensure the safety of hydrogen
storage and transportation. At present, the industrial
production method of HCOOH is mainly methanol
carbonylation, which belongs to energy-intensive industry
with the issues of environmental pollution problems.
Therefore, the concerned electrochemical technology to
convert the CO2 into HCOOH is a significant and promising
technology, where the CO2 conversion to HCOOH is a
two-electron transfer process with an initial potential of −0.19
V vs. RHE. In contrast to the multi-electron transfer and
multiple-step process of CO2 reduction to C2+ products, the
electrocatalytic CO2 reduction to HCOOH has a relatively low
overpotential, featuring high energy efficiency and low cost in
terms of theory.
Currently, the electrocatalytic materials that are used for
CO2RR mainly include carbon-based materials[23,24], metal and
metal oxides[25,26], metal-organic skeleton (MOF) and covalent
organic skeleton (COF)[27,28], as well as molecular catalyst[29,30].
Among them, the carbon-based materials are highly concerned
and have made great progress in the field of CO2

Received date: 28 Oct. 2021; Revised date: 06 Dec. 2021

*Corresponding author. E-mail: chang.yu@dlut.edu.cn; jqiu@dlut.edu.cn
Copyright©2022, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
DOI: 10.1016/S1872-5805(22)60592-4
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289
electroreduction to HCOOH by virtue of their advantages of
unlimited sources, controllable morphology, large specific
surface area and high stability, indicative of superiority and
well development potential.
In this review, the recent advances of carbon-based
electrocatalytic materials in electrochemical CO2 reduction to
HCOOH is summarized. Firstly, the physical and chemical
properties of CO2 molecule are introduced. The reaction
mechanism for electroreduction of CO2 to HCOOH and
common carbon-based catalysts are reviewed and discussed.
Furthermore, the design and optimization strategy of reactors
for HCOOH production was summarized and commented.
Then the hybrid CO2 electrolysis technology was analyzed by
taking the CO2 electroreduction coupled methanol
electrooxidation reaction as an example. Finally, the current
challenges and future industrial prospects for CO2
electroreduction to HCOOH are discussed and proposed.
2 Mechanism of CO2 electroreduction to HCOOH
As for CO2 molecule, the outermost four electrons of C
atom are configurated by sp hybridization, which are filled in
the form of two sp hybrid orbitals and 2 unhybridized orbitals
(px and py). The two sp orbitals of C atom overlap with the 2p
orbitals of O atoms to form σ bonds. While the two
unhybridized p orbitals overlap in parallel with the p orbitals
provided by each of the two O atoms to form large π bonds,
respectively. Therefore, the molecular linearity of CO2 is
stabilized by the unique π-conjugated system of three centers
with four electrons. On the basis of unique stability, the
activation of CO2 molecule is a critical step during CO2 RR
process. In view of this, it is necessary to input electrons to
activate CO2 into excited state of CO∗− 2 , and further achieve
the CO2 electroreduction. Various products are produced,
being dependent on the different reduction reaction
mechanisms derived from the multiple electron transfer.
Electroreduction of CO2 to HCOOH is a two-electron transfer
reaction which can be divided into the two reaction
mechanisms. The first reaction mechanism is schemed as
follows:
Fig. 1 Two possible mechanisms for electroreduction of CO2 to HCOO−, where the C, O, H atoms and catalyst are represented by red, gray, blue,
yellow colors.
CO2 + e− +∗→ CO∗−
2 (1)
CO∗−
2
−
+ e + H → COOH + ∗−
(2)
∗− −
COOH → HCOO +∗ (3)
The CO2 is adsorbed on the active site of the catalyst at
first, and the C atom of CO2 molecule is bonded with active site.
As a result, the CO2 molecule is activated into excited state of
CO∗−2 . Subsequently, a proton-coupled electron process occurs,
*− *−
which transforms CO∗− 2 into COOH . Finally, the COOH
intermediate is desorbed from the surface of catalyst, and the
HCOO− is generated (Fig. 1a).
In the case of the second reaction mechanism, the
adsorption and activation processes of CO2 are similar to the
first mechanism, as schemed as follows:
CO2 + e− +∗→ CO∗−
2 (4)
CO∗−
2
−
+ e + H → OCHO + ∗−
(5)
OCHO ∗− −
→ HCOO +∗ (6)
However, the O atom of CO2 molecule is bonded with
active site, which is different from that of the first reaction
pathway. Also, the excited state of CO∗−
2 is transformed into
the OCHO*− instead of COOH*− intermediate, finally
generating the product HCOO− (Fig. 1b).
In general, the presented mechanisms involve several
processes, including CO2 adsorption, activation, reaction on
the catalyst surface and desorption of the intermediates from
the surface of catalyst. The active sites will bond with the C or
O atoms of CO2 molecule, which depends on the properties of
adopted and developed catalyst. Finally, the two reaction
intermediates (COOH*−, OCHO*−) follow the different
reaction pathways to proceed the CO2 electroreduction.
At present, the development of efficient and stable
electrocatalysts is one of the keys to realize the CO 2
electroreduction to HCOOH. Carbon-based electrocatalysts
are highly concerned due to the low cost and adjustable
structure stability. Of course, metal-free carbon materials can
not only be directly used as electrocatalysts for CO 2
electroreduction, but also can be adopted as suitable supports
to construct the high-performance electrocatalysts via
coupling with other active components.
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289

3 Metal-free carbon catalyst as-made metal-free carbon material as the electrocatalyst

exhibited a FEHCOOH of 87% with a current density of 9.5 mA
The carbon materials have been ideal electrocatalysts for cm−2 for CO2 electroreduction to HCOOH. As a cocatalyst, the
CO2RR because of superior conductivity and high stability coated polyethyleneimine and doped nitrogen species in
under electrochemical conditions. Moreover, the active sites carbon nanotubes resulted in the formation of a favorable
can be constructed easily by virtue of the characteristics of microenvironment, promoting the enrichment of CO 2 on the
adjustable defect sites, surface chemistry and electronic electrode surface, contributing to the adsorption and activation
structure of carbon materials, resulting in the improvement of of CO2, and improving the production rate of HCOOH.
performance of metal-free carbon catalysts. For
electroreduction of CO2 to HCOOH, Xu et al.[31] prepared a 4 Carbon-supported catalysts
series of monolayer graphene nanodisks (GNDs) with
Besides as electrocatalysts for CO2 electroreduction
abundant oxygen functional groups by a simple hydrothermal
directly, the carbon materials are also used as the low-cost and
reaction under different temperatures, where graphene oxide
scalable supports for catalyst for CO2RR, including
and nitric acid were used as the raw materials. The GNDs-160
zero-dimensional carbon quantum dots, one-dimensional
can realize a supreme current density and Faradaic efficiency
carbon nanotubes, two-dimensional graphene etc. Various
(FE) (Fig. 2a, b). The density functional theory (DFT)
metal or metal oxides are supported or anchored on the
revealed that the synergetic effects between carboxyl groups
various carbon matrix, producing a series of electrocatalysts
on graphene surface and other adjacent oxygen-containing
such as carbon-supported metal catalysts, heteroatom-doped
groups (hydroxyl, carbonyl, epoxy, etc.) on the surface of
carbon-supported metal catalysts, MOF-derived carbon-based
GNDs were responsible for the high performance, which
catalyst. As a result, the electronic structure, the Lewis
could significantly reduce the energy barriers for CO 2 to
* acidity/alkalinity of catalyst surface, Fermi level etc. can be
COOH (Fig. 2c, d). Meyer et al.[32] firstly synthesized
regulated, finally resulting in the improved CO2 adsorption
N-doped carbon nanotubes by treating the carbon nanotubes in
and activation, accompanied by the decreased reaction energy
an ammonia plasma atmosphere. Then polyethylenimine
barrier and the promotion of activity and selectivity of the
modified N-doped carbon nanotubes were prepared by an
catalysts for electroreduction of CO2 to HCOOH.
impregnation method, where the N-doped carbon nanotubes
were immersed into polyethylenimine aqueous solution. The

Fig. 2 (a) Linear sweep voltammetry curves over different GNDs catalysts for CO 2RR. (b) FEHCOO− over different GNDs catalysts for CO2RR.
(c) Models of carbon catalysts with different configurations containing oxygen functional groups. (d) Gibbs free energy of CO 2RR and HER over
carbon catalysts with different configurations of oxygen-containing functional groups[31]. Reprinted with permission by American Chemical
Society.
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289

4.1 Carbon-supported metal catalysts
For carbon-supported metal catalysts, Kang et al.
synthesized a carbon black-supported diethano-
lamine-modified tin oxide catalyst by using carbon black,
SnCl2 and diethanolamine as raw materials (Fig. 3a). The
catalyst exhibited an excellent performance with a FE of 84.2%
for HCOOH at a potential of −0.75 V vs. RHE. The surface
amine functional groups on the catalyst were beneficial to
capture and collect the CO2 molecule, and accelerate the
formation of HCOO−, thereby regulating the distribution of
products (Fig. 3b). Our group designed a monolithic carbon
foam-supported SnOx nanosheet with rich oxygen
vacancies(Fig. 3c)[34], which achieved a maximum FEHCOOH of
86% for CO2RR. It can be observed from the scanning
electron microscopy (SEM) images that the three-dimensional
porous carbon foam catalyst featured the abundant
interconnected channels (Fig. 3d, e), which greatly accelerated
the mass transfer in the reaction. While the excellent electrical
conductivity was in favor of the electron transfer, as expected.
The oxygen vacancies of SnOx were conducive to adsorb the
CO2 molecules and provided the more opportunities for
exposure of active sites as well as enhancement of the
electrocatalytic performance. Deng et al.[35] prepared a Cu@C
catalyst with uniformly distributed copper nanoparticles
embedded in a carbon substrate by using a simple and fast ball
milling method. The DFT results indicated that the high
activity of catalyst derived from the synergistic effects
between the abundantly exposed Cu (111) surface and the
carbon substrate. The charge transfer from Cu to the carbon
[33] substrate induced the formation of a charge-rich local
microenvironment, which enhanced the adsorption of *OCHO
intermediates and promoted the formation of HCOOH (Fig.
3f). At a potential of -1.0 V vs. RHE, the FE of the Cu@C
catalyst reached up to 78% and the yield of HCOOH can be
up to 82.8 µmol h−1 cm−2 at -1.2 V vs. RHE (Fig. 3g).
4.2 Heteroatom-doped carbon-supported metal catalysts
Heteroatom doping is an effective strategy to regulate the
intrinsic electronic structure of the carbon substrates and
further improve their catalysis activity. Further, the
introduction of heteroatoms can alter the electronic structure
between metal and carbon substrates, adjust the Fermi level of
the electrocatalyst as well as change Lewis acidity and
alkalinity. Moreover, these heteroatoms can enhance the
adsorption and activation of CO2 molecules on the active
centers and promote the formation of the target products. Luo
et al.[36] synthesized S-doped Bi2O3-CNT composite material
(Fig. 4a). The as-synthesized S-Bi2O3-CNT catalyst can
achieve a HCOOH FE of 97.06% (Fig. 4b). The S doping can
realize the electron delocalization of Bi atoms and enhance the
adsorption of CO2 on the Bi sites, as well as stabilize the
intermediates of CO2* and HCOO*− and hinder the HER.
Therefore, the ability of CO2 electroreduction to HCOOH was
enhanced and the HER was inhibited (Fig. 4c). Hu et al.[37]
prepared N,S co-doped SnO2/NSC composites using
mesoporous carbon as substrate (Fig. 4d). The introduction of

Fig. 3 (a) Fabrication of DEA-SnOx/C catalyst. (b) Mechanism diagram of electrochemical CO2RR to HCOO-[33]. Reprinted with permission by
American Chemical Society. (c) Schematic illustration of the preparation of VO-SnOx/CF catalyst. (d, e) SEM images of VO-SnOx/CF[34].
Reprinted with permission by Royal Society of Chemistry. (f) Schematic diagram of electrochemical CO2RR on Cu@C catalyst.
(g) Electrochemical performance over the Cu@C catalyst covering FE HCOOH and HCOOH formation rate[35]. Reprinted with permission by
Elsevier.
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289

N and S species can effectively enhance the metal-support
interaction and promote the rapid transfer of electrons from
the support to the SnO2 nanoparticles. This endowed the
surface of SnO2 with negative charge and promoted the
adsorption of CO2, thus enhancing the activity of CO2. The
experimental results showed that the maximum FE of
SnO2/NSC for HCOOH can reach up to 94.4% with a current
density of 56 mA cm−2. Zhang et al.[38] synthesized an
atomically dispersed indium-nitrogen-carbon catalyst (In-N-C,
Fig. 4e). The strong interaction between atomically dispersed
indium and adjacent N atoms on the carbon skeletons can
improve the performance of the electrocatalyst for CO 2RR.
The In-N-C catalyst can achieve a FE of 80% for HCOOH
with a high TOF value (26 771 h−1).
4.3 MOF-derived carbon-based catalysts
MOFs made of metal nodes and functional molecular
building blocks are widely used as precursors or templates to
synthesize the morphologically and dimensionally controllable
catalysts[39]. In addition, the inherent pore structure of the
MOFs materials is also helpful for forming the carbon with
large specific surface areas and abundant pore channels, which
will facilitate the adsorption and uniform distribution of CO 2
on active sites. Xia et al.[40] prepared a carbon-coated rodlike
Bi2O3 composite (Bi2O3@C) by high temperature
carbonization with Bi-MOF as the precursor (Fig. 5a). The
transmission electron microscopy (TEM) image exhibited that
the Bi2O3 species uniformly dispersed within the carbon
matrix (Fig. 5b). The synthesized Bi2O3 had excellent
electrocatalytic performance, suggesting that carbon matrix
contributed to improve the activity and current density, and
the bismuth oxide in composites contributed to improve the
reaction kinetics and selectivity. For CO2RR, the catalyst had
an initial potential of -0.28 V vs. RHE, and can achieve a
maximum FE of 93% for HCOOH with the HCOOH partial

Fig. 4 (a) Schematic fabrication process for S-doped Bi2O3-CNT. (b) FEHCOOH over a series of catalysts at different applied voltages.
(c) Schematic diagram of the S species-promoted effects on CO2RR to HCOOH[36]. Reprinted with permission by American Chemical Society.
(d) Mechanism diagram for CO2RR to HCOOH over N, S-doped SnO2/NSC[37]. Reprinted with permission by American Chemical Society.
(e) Schematic fabrication process for In-N-C[38]. Reprinted with permission by American Chemical Society.

Fig. 5 (a) Preparation diagram of carbon nanorods-encapsulated Bi2O3 (Bi2O3@C). (b) TEM image of Bi2O3@C. (c) FEHCOOH over catalyst at
different potentials vs. RHE[40]. Reprinted with permission by WILEY-VCH. (d) Schematic fabrication process for CuBi-C. (e) FEHCOOH over
different catalysts under various voltages[41]. Reprinted with permission by Elsevier.
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289
current density greater than 200 mA cm−2 (Fig. 5c). Wu et
al.[41] synthesized carbon-supported CuBi bimetal catalyst by
carbonizing the CuBi-MOF precursor (Fig. 5d). The catalyst
showed an excellent CO2RR performance, with the FE
remaining above 93.7% in a wide potential window range of
900 mV for HCOOH, achieving 100% FE of HCOOH at -0.77
V vs. RHE (Fig. 5e).
5 Reactor design and optimization
In the conventional H-type reactor, CO2 gas is directly
injected into the electrolyte. The CO2 molecules firstly
dissolve in the electrolyte and then take part in reduction
reaction at the interface of catalyst. Due to simple equipment
and easy operation, H-type reactor is widely used in
CO2RR[42]. However, the solubility of CO2 in the electrolyte
will affect the rate of CO2RR, resulting in limited mass
transfer in the whole system, which further hinders the current
density boosting for the industrial application of CO 2
electroreduction. Moreover, it is more difficult to understand
the CO2RR system, involving the complex three-phase
reaction interface. HCOOH, as a liquid product, will be
dissolved in the electrolyte, which will undoubtedly bring
about a series of problems, such as product collection,
separation and recovery. In this way, the cost of HCOOH
production via electrochemical CO2RR technology would
greatly increase, which further hinders the industrial
development of HCOOH production. Moreover, to realize the
industrialization of HCOOH production, the current density
should reach up to industrial level (>200 mA cm−2) at first,
which is hard to be achieved in the traditional H-type reactor.
Therefore, the new reactors are urgent to be designed and
optimized for achieving an industrial-grade current density
and high energy conversion efficiency. This section mainly
Fig. 6 Scheme and comparison of four different reactors for producing HCOOH via CO 2RR.
outlines and introduces the flow reactor[43,44], including
membrane electrode reactor (MEA)[45-47] and all-solid-state
reactor[48]. There are several new and enlightened
reactors/devices for the production of HCOOH via CO2RR, as
schemed in Fig. 6. The H-type reactor as the traditional and
most commonly applied reaction device, has been studied in
most of review papers. Therefore, the H-type reactor will not
be introduced in the follow section.
5.1 Flow reactor
In order to achieve the high current density and energy
conversion efficiency, the flow reactors without mass transport
limitations have been widely concerned and applied in CO 2RR.
The flow reactor is a three-electrode reaction system, in which
the gas diffusion electrode (GDE) is coated with catalyst on
one side as cathode. The side of GDE coated by catalyst
directly contacts with the catholyte, while CO2 is directly
introduced from the back of GDE to participate in the reaction.
Moreover, the anode and cathode are separated by an ion
exchange membrane, including anion/cation exchange
membrane. The CO2 and electrolyte contacts with the catalyst
from different sides in the flow cell reactor, respectively, thus
avoiding the mass transfer limitation caused by the low
solubility of CO2 in the electrolyte. Therefore, the overall
current density of CO2RR can be significantly enhanced in the
flow reactor and meet the requirements of industrialization. At
the same time, the catholyte and anolyte are continuously
circulating in the flow reactor. Thus, the liquid product can be
taken away from surface of the catalyst to ensure the full
exposure of active sites. Furthermore, the continuous flow of
the electrolyte is also conducive to the desorption and release
of the gas phase products, finally ensuring the stability of the
system.
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289
Wu et al.[49] constructed a MOF-derived leaf-shaped
bismuth nanosheet with a hybridized Bi/Bi-O interface by an
in-situ electroreduction method. DFT results revealed that the
existence of O atoms at the Bi/Bi-O interface can beneficial to
reduce the free energy barrier of CO2RR. The catalyst was
assembled in a flow reactor to evaluate the CO2
electroreduction activity. At a current density of >200 mA
cm−2, the bismuth nanosheets can achieve HCOOH FE of
more than 90% and stably run for more than 10 h, showing an
excellent activity and stability. Li et al.[50] synthesized the
highly dispersed In2O3 nanoparticles loaded on carbon
nanorods. The catalyst exhibited an excellent activity for CO 2
electroreduction in a flow reactor with a FEHCOOH of 90% and
a current density of 300 mA cm−2. Zhu et al.[51] evaluated and
compared the CO2 electroreduction performance of a
bismuthene catalyst in the H-type and flow reactors,
respectively. In H-type reactor, the catalyst exhibited a current
density of 130 mA cm−2 at -1.17 V vs. RHE. The
corresponding current density reached to 560 mA cm−2 in the
flow reactor, which is five times higher than that in H-type
reactor. This showed that the problems of CO2 diffusion and
mass transport limitation would be well solved in a flow cell,
and the activity of catalyst would also be significantly
improved.
5.2 MEA reactor
In order to achieve a high current density and high
energy conversion efficiency in an industrial-scale, MEA
reactor is also designed and applied to electrochemical
CO2RR. In the MEA reactor, the cathode, anode and the ion
exchange membrane are pressed together, which greatly
reduce the resistance of the reactor and improve the energy
efficiency of the overall device. At the same time, CO2 is
introduced into the reactor accompanied by water vapor to
participate in the reaction, which is beneficial to enhance the
mass transport and improve the current density. Zhong et al. [52]
assembled the as-prepared BiSn catalyst into a MEA reactor.
At a current density of 120 mA cm−2, the FEHCOOH was as high
as 97.8% at a cell voltage of 3.6 V, and the energy efficiency
can reach up to 36%. Xia et al.[53] constructed an
amino-functionalized indium-organic framework material.
The catalyst can achieve a commercial current density of 800
mA cm−2 at a cell voltage of 3.4 V in a MEA reactor.
5.3 All-solid-state reactor
The as-obtained liquid product of HCOOH in the
above-mentioned reactors will dissolve in the electrolyte.
Notably, the final product exists in the form of formate in the
alkaline electrolyte rather than the target product of HCOOH.
Therefore, to obtain the pure HCOOH, the downstream
processes of separation and recovery steps are required, which
will inevitably increase the cost of industrial applications, and
these downstream processes are energy-intensive and require
the complicate production infrastructures. Wang et al.[54]
designed an all-solid-state reactor with a porous solid
electrolyte layer instead of the traditional liquid electrolyte.
During the CO2RR test, the humid CO2 gas was supplied to
the cathode side. On the anode side, hydrogen oxidation
reaction was used to replace the water oxidation reaction. The
H2 gas was passed into the anode side to realize the hydrogen
oxidation reaction on the anode catalyst to generate the
protons. The generated protons transfer to the cathode through
the anion and cation exchange and react with the generated
HCOO− on cathode was reacted with the protons from anode,
which had passed, respectively under the driving of an electric
field, finally producing the pure HCOOH. In addition, N 2 was
used to bring the pure HCOOH vapor out of the reactor, which
can avoid the accumulation of HCOOH on the surface of the
catalyst and facilitate to maintain the process stability. Finally,
a high-concentration pure HCOOH solution was obtained, and
N2 can be recycled and continue to enter the reactor. In the
all-solid-state reactor, the bismuth-based catalyst can achieve
a current density of >440 mA cm−2 with a FE of >97% and a
stability of >100 h for producing HCOOH. At the same time,
the generated HCOOH reached a concentration close to 100
wt.%. The all-solid-state reactor simultaneously is fed CO2
and H2 as gas feedstocks to produce the pure HCOOH, which
will have a great application prospect in safe hydrogen storage
technology.
6 Hybrid CO2 electrolysis systems
In the section of all-solid-state reactor, it has been
mentioned that the valuable products can be obtained by
coupling the products from the anode and cathode. Meanwhile,
the energy consumption of the entire reaction system can be
reduced and the energy conversion efficiency can be improved
by using hydrogen oxidation reaction instead of water
oxidation reaction at the anode. Recently, a lot of work has
been devoted to hybrid CO2 electrolysis. Other anodic
oxidation reactions are replaced by water oxidation reactions,
and valuable chemicals can be produced on the anode side [55].
Hybrid CO2 electrolysis is also concerned, which can
significantly improve the economic benefits of the CO 2RR
system and promote the industrial development of CO 2
electroreduction technology. Zhu et al.[16] designed a new
hybrid CO2 electrolysis system, in which the CO2
electroreduction reaction and the methanol oxidation reaction
(MOR) are coupled. In this reaction system, the voltage of the
overall reaction can be greatly reduced, and the HCOOH
product was simultaneously produced at both anode and
cathode (Fig. 7a). By using methanol oxidation to replace the
water oxidation reaction, the cell voltage of the entire device
was declined to 213 mV when the current density reached to
10 mA cm−2. This proved that this strategy can effectively
reduce the power consumption of the overall reaction and
improve the overall energy conversion efficiency (Fig. 7b).
The as-designed Ni-MOF nanosheet arrays (Ni-NF-Af) and
bismuthenes (Bi-ene) electrocatalysts were applied in the
cathode and anode, respectively, to configure hybrid CO 2
electrolysis reactor, which can efficiently produce the
HCOOH in a wide voltage range (FEs of the both cathode and
anode are close to 100%, Fig. 7c). This work provides an
 Wen-bin Li et al. / New Carbon Materials, 2022, 37(2): 277-289
Fig. 7 (a) Schematic of CO2RR and MOR. (b) LSV curves of
CO2RR and MOR. (c) FEformate of CO2RR and MOR[16]. Reprinted
with permission by WILEY-VCH.
inspired idea to reduce energy input and improve production
efficiency for realizing the co-production of HCOOH at both
cathode and anode.
7 Conclusions and perspectives
In general, HCOOH, as a stable liquid product, is
valuable and promising, which can be produced on the basis
of CO2 electroreduction technique. In addition, the HCOOH is
expected to be widely used as a safe and reliable hydrogen
storage material. Consequently, electroreduction technique of
CO2 to HCOOH is very significant and needs to be explored
and developed, which is full of opportunities and challenges.
Of course, some problems/issues and challenges that will be
faced and solved, still exist in such a novel system.
(1) Electrocatalytic CO2 reduction to HCOOH is
dependent on the design and development of electrocatalyst
with high activity, selectivity, stability. Therefore, rational
design and construction of carbon-based electrocatalyst is still
one of the main focuses in future research. For efficiently and
stably electrochemical reducing CO2, it is one of the keys to
give full play to the advantages of carbon-based materials,
such as high conductivity, high specific surface area and acid
and alkali resistance. Further, these carbon materials need to
be coupled with other active components to construct the
advanced carbon-based composite catalysts. In addition, the
gradually decreased pH value in the system derived from the
produced HCOOH changes the local microenvironment and
has an important influence on the finally reaction rate and
selectivity of CO2 reduction to HCOOH. As a result, the
electrolyte and the separation of HCOOH from the system are
also needed to be considered. As for the most popular alkaline
electrolyte, high solubility of CO2 leads to a good mass
transfer capability and fast reaction rate. Nonetheless,
reduction product is in the form of formate rather than
HCOOH in the alkaline electrolyte. While as for the acid
electrolyte, the HCOOH can be directly produced and avoid
the formation of formate. However, the competitive HER is a
tough challenge for CO2 reduction to HCOOH. Besides,
organic electrolyte, the emerging seawater electrolyte and
solid-state electrolyte, as well as external ingredients in
electrolyte have been employed in CO2RR system and are of
great potential, which need to be further explored and
optimized.
(2) The reaction mechanism of CO2RR over
carbon-based materials remains to be further explored and
detected. The tunable intrinsic structure of carbon-based
materials such as multiple heteroatoms-doped
rich-defective-electron effects, abundant pore channels and
functional groups, as well as multi-dimensional characteristics
should be correlated with their electrochemical performance
towards CO2. The adsorption, activation and reduction
processes of CO2 on the surface of catalysts should be
monitored at molecular scale by the advanced in-situ
characterization methods. In addition, DFT is also used to
simulate the catalyst structure and catalytic process in the
atomic scale, so as to clarify the real active site of the reaction,
which helps us to understand the reaction mechanism deeply
and design the efficient carbon-based electrocatalyst
accurately.
(3) Various obstacles/issues still exist and hinder the
industrial application of electroreduction CO2 to HCOOH.
Although the current density has reached the industrial level
through the design of new devices such as flow reactor and
MEA reactor, the reaction overpotential and energy
conversion efficiency of the device still need to be further
improved, and the utilization rate of CO2 is still very low.
Future development needs to focus on innovative catalyst
engineering and gas diffusion electrode design, optimization
of reaction device, coupling other anode reactions to prepare
value-added chemicals, and further exploration the industrial
development route of CO2 conversion technology.
Acknowledgements
This work was partly supported by the National Natural
Science Foundation of China (51872035, 22078052) and
Innovation Program of Dalian City of Liaoning Province
(2019RJ03).
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