Electrochemical Reduction of Carbon Dioxide To Formic Acid

CHEMELECTROCHEM
REVIEWS
DOI: 10.1002/celc.201300206
Electrochemical Reduction of Carbon Dioxide to Formic

Acid
Xu Lu,[a] Dennis Y. C. Leung,*[a] Huizhi Wang,[a] Michael K. H. Leung,[c] and Jin Xuan*[a, b]
2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemElectroChem 2014, 1, 836 – 849 836
21960216, 2014, 5, Downloaded from https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/celc.201300206 by Kwame Nkrumah Univ of Sci & Te, Wiley Online Library on [21/07/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
CHEMELECTROCHEM
REVIEWS www.chemelectrochem.org
This Review provides an overview of electrochemical tech- alleviating restrictions of the current CO2 electrochemical re-
niques that are implemented in addressing gaseous CO2 to- duction system are summarized, including low reactant-trans-
wards the synthesis of a particular fuel (i.e. formic acid). The fer rate, high reaction overpotential, and low product selectivi-
electrochemical reaction mechanism, as well as the advance- ty. The use of microfluidic techniques to build microscale elec-
ment of electrodes, catalyst materials, and reactor designs are trochemical reactors is identified to be highly promising to
reviewed and discussed. To date, the electrolytic cell is the largely increase the electrochemical performance. Finally,
dominant reaction site and, based on which, various catalysts future challenges and opportunities of electrochemical reduc-
have been proposed and researched. In addition, relevant tion of CO2 are discussed.
work regarding reactor design optimization for the purpose of
1. Introduction
As the fourth most abundant element, carbon plays a funda-

mental role in the ecosphere. Carbon and its associated prod-
ucts are mostly stored in the lithosphere and fossils, from
which they can be exchanged through the atmosphere, hydro-
sphere, and biosphere.
The equilibrium state of the carbon cycle provides the habi-
tat for all residents on earth. However, human activities have
broken the balance and altered the carbon cycle since the in-
dustrial revolution. Issues related to CO2, which is universally
believed to be the primary greenhouse gas, have become the
focus of global attention, because of its substantial emission
and consequent adverse effect on climate. It has now become
a consensus that immediate measures must be carried out to
intensively reduce carbon emission from energy generation.
Towards achieving this aim, carbon capture and sequestration
(CCS) has been proposed, and has demonstrated the capability
to capture CO2 from centralized sources such as coal-fired
power plants. In CCS, the captured CO2 is sequestered and Scheme 1. Schematic diagram of CCS for various combustion systems.
stored in underground geological structures, in deep-ocean, or
pumped into depleted oil fields for oil recovery, as can be seen
in Scheme 1. age medium for renewable energy (e.g. photochemical and
Despite its potential in the mass reduction of CO2, the last electrochemical conversion), and a feedstock for chemicals
step of CCS, that is, sequestration and storage, is still under (natural gas to liquid, coal to liquid, chemical and biochemical
debate; it is thought to neither provide a permanent solution, conversion, and bio CCS algal synthesis).[15] Among these tech-
owing to potential leakage, nor help satisfy future energy nologies, converting CO2 into useful fuels offers a more sus-
needs.[13] Therefore, the concept of CO2 utilization, instead, has tainable prospect. On one hand, by recycling CO2 into usable
attracted increasing interests in recent years. CO2 can perform forms, a carbon neutral cycle could be created to provide
as a solvent or a working fluid (e.g. physical storage),[14] a stor- energy without increasing environmental CO2 concentration.
On the other hand, it has the potential to achieve mass reduc-
tion of CO2 while the contributions to global CO2 reduction
[a] X. Lu, Prof. D. Y. C. Leung, Dr. H. Wang, Dr. J. Xuan
from other utilization methods are largely limited.
Department of Mechanical Engineering
The University of Hong Kong CO2-to-fuel conversion can be conducted in a thermochemi-
Pok Fu Lam, Hong Kong (China) cal, photochemical, or electrochemical manner. With regard to
E-mail: ycleung@hku.hk the operation conditions required, electrochemical conversion
[b] Dr. J. Xuan can be performed at room temperature and ambient pressure,
State-Key Laboratory of Chemical Engineering
thereby bringing higher feasibility of reducing atmospheric
School of Mechanical and Power Engineering
East China University of Science and Technology CO2. Furthermore, the electrochemical process is highly con-
Meilong Road 130, Shanghai, Shanghai (China) trollable and can achieve much higher conversion efficiency,
E-mail: jxuan@ecust.edu.cn making it advantageous with respect to practicability and in-
[c] Dr. M. K. H. Leung dustrial prospect. This Review has particular emphasis on the
Ability R&D Energy Research Centre
electrochemical reduction of CO2, which enables the produc-
School of Energy and Environment
City University of Hong Kong tion of fuels and leveling of renewable electricity generated
Tat Chee Avenue, Kowloon, Hong Kong (China) from intermittent sources (e.g. solar, wind, and tidal). Table 1
CHEMELECTROCHEM
summarizes the fuels that have the potential to be obtained

Table 1. Possible products from the conversion of CO2 into fuels.
through conversion of CO2 by using different methods, indicat-
ing that the range of products from electrochemical method is Technology Product Ref.
wider. photochemical conversion formate [1]
Electrochemical reduction of CO2 can be categorized accord- formic acid [2]
ing to the products formed. Several researchers have achieved carbon monoxide [3]
methanol [4]
selective conversion of CO2 into CO at high reaction rates.[16]
electrochemical conversion formic acid esters [5]
Additionally, conversion mechanisms of CO2 and its derivatives formamides [6]
to formic acid can be found in many literature papers.[17] carbon monoxide [7]
It should be noted that under proper conditions, formic acid methane [8]
methanol [9]
can be formed in neutral or acidic solution, whereas formate
formic acid [6, 10]
ions are the main product in weak alkaline conditions, both of dimethyl carbonate [11]
which have similar chemical characteristics and will be includ- polycarbonate [12]
ed within the scope of this Review paper. CO2 could also be alkylene carbonates [6]
carbamic acid esters [5]
converted to oxalates C2 O2 4 at low applied potentials.[18]
lactones [5]
aliphatic polycarbonates [5]
Prof. Dennis Y. C. Leung received his

B.Sc. (Eng.) in 1982 and PhD in 1988,
Other electrochemical reduction products, including long-
both from the Department of Mechan-
chain hydrocarbon fuels[18a, 19] and alcohols (e.g. methanol),[20]
ical Engineering at the University of
have been also reported.
Hong Kong. He joined the same de-
Amongst all of these routes, the conversion of CO2 to formic
partment in 1993 and is now a Full
acid is favored for many reasons. Firstly, commercialization of
Professor, specializing in renewable
CO2-to-formic acid conversion is considered to be feasible,
energy and energy conservation. He
owing to the broad market and wide application range. Value
serves as an Editorial Board member of
analyses conducted by some industrial bodies have also con-
several journals and chairman of many
cluded that this process is most likely to be profitable com-
government and non-government
pared to its competitors that produce methanol, CO, and long-
committees. In 2008, Prof. Leung re-
chain hydrocarbons.[21] Besides, formic acid is becoming an in-
ceived the Outstanding Earth Champion Hong Kong award in rec-
ognizing his contributions in protecting the environment.
Dr. Huizhi Wang obtained her PhD in
Dr. Jin Xuan obtained his PhD in Me- Mechanical Engineering from The Uni-
chanical Engineering from The Univer- versity of Hong Kong in 2011. She is
sity of Hong Kong in 2011. He then currently a Postdoctoral Fellow in the
took an academic position at East Department of Mechanical Engineer-
China University of Science and Tech- ing, The University of Hong Kong. Her
nology. He is currently a Visiting research interests focus on electro-
Fellow at the School of Energy and En- chemistry for energy and carbon con-
vironment, City University of Hong version.
Kong. His research interests include
microscale process intensification and
control, microfluidic reaction systems
for energy and carbon conversion, and Dr. Michael K. H. Leung is Associate
process simulation and theory. Dean and Associate Professor of the
School of Energy and Environment
Lu Xu was born in 1989 in Fujian Prov- and Director of the Ability R&D Energy
ince, China. He obtained BEng and Research Centre at the City University
MSc degrees in Mechanical Engineer- of Hong Kong. He was previously the
ing from the University of Hong Kong. Chairman of the Energy Institute
He is currently a PhD student under (Hong Kong Branch), and is currently
the supervision of Prof. Dennis Y. C. a member of the HKSAR Energy Advi-
Leung. His research interests cover sory Committee, a chartered engineer,
electrochemical reduction of CO2, mi- and a registered professional engineer.
crofluidic reactors, and interphase His main research interests are carbon
modelling. management and reduction, solar photocatalysis, fuel-cell electro-
chemistry, and advanced refrigeration.
CHEMELECTROCHEM
creasingly popular fuel. For instance, Rice et al.[22] described

Table 2. Theoretical equilibrium potentials of common CO2 reduction
formic acid as an excellent fuel for a fuel cell and Loges et al. routes, adapted from Ref. [29c].
[23]
stated that liquid fuels, such as methanol, ethanol, and
formic acid, can be directly converted in direct fuel cells. Route Chemical reaction Equilibrium potential
[V vs. NHE]
By using the fuel cell platform, formic acid can be used to gen-
erate electricity and form a clean energy-conversion chain.[22, 24] (2), (6) CO2 + 2 H + + 2 e !HCOOH 0.199
(3) 2 CO2 + 2 H + + 2 e !H2C2O4 0.475
Secondly, formic acid is a useful energy-storage medium,
(7) CO2 + 4 H + + 4 e !HCHO + H2O 0.071
storing 4.35 wt % hydrogen. Also, formate, the anion derived (8) CO2 + 6 H + + 6 e !CH3OH + H2O +0.030
from formic acid, can be oxidized at similar potentials to hy- (9), (12) CO2 + 2 H + + 2 e !CO + H2O 0.109
drogen, indicating itself as a viable energy source.[25] . (11) CO2 + 8 H + + 8 e !CH4 + 2H2O +0.169
Thirdly, extensive energy input is required to overcome ki-
netic barriers of activating multi-electron transfer. Furthermore,
most catalysts for multi-electron transport suffer from poor because of the high-energy barrier of multi-electron transfer,
thermal stability and bond cleavage.[26] Although efforts have higher order hydrocarbon products (e.g. H2C2O4) of CO2 elec-
been made to fabricate electrocatalysts that contain multiple trochemical reduction require high potentials, corroborating
metal centers to facilitate multi-electron transfers, higher order the advantage of the CO2-to-formic acid pathway in terms of
CO2 reduction products are rarely observed[20b, 27] and most energy consumption. As indicated in Scheme 2 and Table 2,
studies involve no more than 2e reduction processes. conversion of CO2 to formic acid can be achieved via
The above statements lead to the conclusion that formic Routes (2) or (6). It should be noted that, because of intermedi-
acid converted from CO2 through electroreduction may serve ate species, the actual reactions would be affected by large
as both an energy-storage medium and a useful fuel with high overpotentials, which are highly dependent on the particular
technical feasibility and promising commercial potential. system involved (e.g. electrode, catalyst, and reaction condi-
So far, relevant reviews of CO2 electroreduction can be tions).
found on topics such as reaction theory and mechanism,[19b, 28] General reactions at cathode and anode for electrochemical
possible reaction pathways,[29] and the effect of one particular reduction of CO2 are [Eqs. (1) and (2)]:
constituent or condition (e.g. metallic electrodes, transition-
metal complexes as catalysts, or pH value).[29b, 30, 31] Neverthe- Cathode : 2 CO2 þ 4 Hþ þ 4 e ! 2 HCOOH ð1Þ
less, an overview of the overall electrochemical process can
rarely be found. Therefore, of special interest in this Review is Anode : 2 H2 O ! O2 þ 4 e þ 4 Hþ ð2Þ
a comprehensive discussion on the electrochemical aspects
and essential factors of electrolytic cell system for CO2-to- Actual electrode reactions are much more complicated and
formic acid conversion, including electrode structure, catalyst, the cathode reaction can be divided into two steps: 1) forma-
electrolyte, reactor design, and
operation conditions.
2. CO2 Electrochemical
Reduction Routes
There are several routes that
enable CO2 to be electrochemi-
cally converted into usable
carbon-based compounds such
as methanol, ethanol, aldehydes,
methane, ethylene, formic acid,
oxalic acids, CO, H2 syngas, and
so forth. These routes are sum-
marized in Scheme 2,[16c, 17b, 29c] in
which the corresponding cata-
lysts for different reaction path-
ways of CO2 electroreduction are
also listed. Besides, equilibrium
potentials, against the normal
hydrogen electrode (NHE), of
common CO2 reduction reac-
tions have been summarized by
Chaplin et al., [29c] as shown in
Table 2. It can be observed that, Scheme 2. Pathways of electrochemical CO2 reduction; see Refs. [16c, 17c, 29c].
CHEMELECTROCHEM
tion of an intermediate COOH radical (ad) and 2) final produc-

tion of HCOOH. Scheme 3 demonstrates several possible se-
quences of Step (1) and likely alternatives to Step (2).[29b, c]
In general, electrochemical reduction of CO2 is accomplished
in an electrolytic cell, most of which have a common structure
consisting of a pair of electrodes (i.e. anode and cathode), cat-
alyst(s) coated on electrode surface, and electrolyte(s) transfer-
ring ions between electrodes. A schematic diagram of the
basic configuration of a CO2-electroreduction electrolytic cell is
presented in Figure 1. At the positively charged electrode (i.e.
Figure 2. Mechanism of electrochemical CO2 reduction on an electrolytic cell

cathode: a) yield of adsorbed CO2 from electronation, b) evolution of ad-
sorbed HCO2 from the reaction of adsorbed CO2 and H2O, c) yield of for-
mate ions HCO2 from further electronation, and d) isolation of HCO2 from
the electrode surface.[29b]
Major steps involved in the CO2 electrochemical reduction

process (e.g. CO2 absorption, three-phase interface formation,
CO2 reduction, HCOOH evolution etc.) occur on the cathode
and the adjacent active site, whereas the function of the
anode is similar to that implemented in conventional hydroly-
sis cell (e.g. catalysis of oxidation reaction, removal of prod-
Scheme 3. Alternative pathways of HCOOH formation; see Refs. [29b, c]. ucts), which have been well-investigated and are available else-
where.[33] Therefore, in the following sections, electrode discus-
sions will specifically focus on the cathode.
3. Electrode Structure
In general, an electrode of an electrolytic cell comprises a sub-
strate and a catalyst layer (CL), serving multiple functions in
electrochemical reduction of CO2 to formic acid, such as:
· absorb gaseous CO2
· transport gaseous CO2 from substrate to the CL
· provide an active reaction site for catalyst(s) adhered on its
surface
Figure 1. Basic structure of CO2 electroreduction electrolytic cell. · deliver formic acid from the CL into the electrolyte
· conduct protons and electrons with low resistance
anode), oxidation products from reaction sites are transported At an early stage, substantial attempts to develop electrodes
and discharged through its pores; at the negatively charged with planar and mesh structures[34] were conducted, but out-
electrode (i.e. cathode, where electrons enter the electrolyte), comes were mostly unsatisfactory. Recently, gas diffusion elec-
CO2 passes through its surface to reaction sites and electrons trodes (GDEs), which create effective three-phase interfaces for
are transported from the current collector to the reaction sites gaseous reactants, electrodes, and electrolytes, have developed
through electron-conducting particles. rapidly and are regarded as an effective solution towards low
The mechanism of CO2 electrochemical reduction has been CO2-transfer rate and poor cell performance. A GDE usually
suggested by many researchers,[17a, 32] and a commonly accept- comprises a conventional catalyst layer, where carbon black is
ed mechanism[29b] is shown in Figure 2. After gaseous CO2 is usually utilized to support catalyst particles, and a gas diffusion
absorbed as ·CO2 (ad), it undergoes electron addition (electro- layer (GDL).[35] The GDL is usually made from porous materials
nation) to yield ·CO2 (ad). Subsequent reactions of ·CO2 (ad) and a dense array of carbon fibers. Two common examples are
and H2O form released OH ions and adsorbed HCO2, the latter non-woven carbon paper and woven fabric carbon cloth.
undergoes further electronation to yield formate ions, HCO2 . In addition to providing mechanical support and protection
As electrons are paired after electronation, the HCO2 species from corrosion or erosion, GDEs also perform other multiple
are desorbed from the electrode surface. roles including:
CHEMELECTROCHEM
· pathway of CO2 and electrolyte diffusion In our discussion, sp metals include principal group metals in
the periodic table and transition metals whose d orbitals are
· intermediary of proton and electron transfer
fully filled;[29b, c, 44] d metals refer to other transition metals in
· passage for by-product removal for the purpose of prevent- the d block of the periodic table. Based on these definitions
ing cathode flooding and the phases of partnered electrolytes, metal catalysts could
be categorized into four groups: sp metals in aqueous electro-
· medium of heat transfer
lyte, sp metals in nonaqueous electrolyte, d metals in aqueous
Studies of GDEs in CO2-to-formic acid conversion cells have electrolyte, and d metals in nonaqueous electrolyte.
been conducted by researchers. Experiments with Pb-coated Scheme 4 illustrates the above-mentioned categorization
GDEs show a high reaction rate, high current density and corresponding routes towards the formation of HCOOH.
(115 mA cm2), high Faradaic efficiency (ca. 100 %), and reason-
able applied potential [ca. 1.8 V vs. saturated calomel elec-
trode (SCE)].[36] Another high performance catalyst, Ru–Pd alloy
particles, has also been incorporated into a GDE,[37] and the
competitiveness of this electrode was revealed by a 90 % cur-
rent efficiency at 1.1 V (vs. SCE) and 80 mA cm2. Cu- and Zn-
phthalocyanines have also been coated and tested on GDEs,
yielding formic acid at high current densities (100 mA cm2).[38]
In order to achieve a more effective three-phase region and
higher porosity, nanotechnology has been incorporated into
the development of GDEs. On basis of electrochemical investi-
gations of micro- or mesoporous materials, nanostructured car-
bons give researchers new visions in electrode development Scheme 4. CO2-to-HCOOH conversion under catalysis of sp metals and d
metals in aqueous and nonaqueous electrolytes.
for CO2 electroreduction.
A popular example is carbon nanotubes (CNTs). With a cylin-
drical nanostructure and a large length-to-diameter ratio, CNTs In addition, Table 3 summarizes Faradaic efficiencies, selectivity,
show higher mass-transfer rates, more structured three-phase applied voltages, and current densities that have been report-
boundaries, and better confinement effects.[39] Gangeri et al.[40] ed with some of the foregoing metal catalysts. As indicated in
reported improved stability and productivity of CO2-to-liquid Table 3, high catalytic activity can be achieved on some sp
fuels conversion on Pt/CNT and Fe/CNT electrodes. Similar ach- metals in aqueous electrolytes including In, Bi, Hg, and
ievements can be observed on N-doped CNTs.[41] More specifi- Pb,[17b, 45] and Faradaic efficiencies are mostly above 80 % at rel-
cally, experiments on multiwalled CNTs and cobalt tetra-amino- atively high current densities. Besides, In is reported to depress
phthalocyanine composite-modified electrodes have revealed a major competitive reaction, that is, hydrogen generation.
considerable improvements in CO2-to-formic acid electrocata- On other sp metals, such as Zn, Cu, and Cd, formic acid could
lytic conversion. The current density is increased by 20 %, the also be produced, but the Faradaic efficiencies and current
HCOOH production rate is improved by 100 %, and the cath- densities are not satisfactory.
ode potential of CO2 reduction is recorded to be 0.5 V (vs. Fewer d-group metals are reported to show high per-
Ag/AgCl).[42] It is believed that CNT-based electrodes will bring formance in CO2-to-formic acid conversion. Currently, Pd is the
significant advancements to CO2 reduction and conversion. most commonly used d metal, with recorded Faradaic efficien-
cies up to 100 %[48] at high current densities.[20a] Rh and Ir elec-
trodes have also been studied; however, their selectivity to-
4. Electrode Catalyst
wards formic acid is not high and the products are dominated
As can be seen in Scheme 2, CO2-to-formic acid conversion can by H2 and CO.[49]
only be achieved with certain catalysts. With the appropriate In summary, high Faradaic efficiencies can be achieved on
selection of the catalyst, some intermediate species, resulting most metal catalysts, whereas the current densities vary with
in high overpotentials, can be suppressed and cell per- different type. It is also realized that the utilization of GDEs
formance can be improved. In this section, catalysts that cata- and elevating the pressure, usually in partnership with aque-
lyze the CO2-to-formic acid reaction are classified into three ous electrolytes, gives better cell performances.
categories for discussion: metal catalysts, metal-complex cata-
lysts, and biocatalysts.
4.2. Metal-Complex Catalysts
Although electrochemical methods provide a promising solu-
4.1. Metal Catalysts
tion to CO2 conversion, large negative applied potentials are
Conventional catalysts for the electroreduction of CO2 to required when applying conventional metal catalysts, because
formic acid include metals such as Pb, Ru–Pd, Sn, Hg, In, and of the formation of intermediate species such as ·CO2 .
Cd. As is known, a standard 18-column periodic table could be In recent decades, metal complexes have been developed to
deconstructed into four blocks, that is, s, p, d, and f blocks.[43] alleviate this barrier, most of which are transition-metal com-
CHEMELECTROCHEM
Table 3. Efficiencies, applied potentials, and current densities under various combinations of catalyst and electrolyte.
Metal Electrolyte Catalyst Selectivity Electrolyte Faradaic Potential Current Ref.

group type [%] efficiency [%] [V vs. NHE] density [mA cm2]
sp aqueous Pb – 50 g L1 NaSO4 100 1.6 115 [26]
80 – 78.9 2.2 – [17b]
Sn – 0.1 m KHCO3 88.4 1.5 5.0 [17e]
In – 0.1 m KHCO3 94.9 1.6 5.0 [17e]
92.8 – 87.6 1.8 – [17b]
Zn 60 – 53.4 2.2 – [17b]
– 0.1 m KHCO3 20 1.4 0.6 [45]
Cu – Na2CO3/Na2SO4 81.5 3.3 20 [17a]
– 0.5 m K2SO4 5.9 1.3 19 [46]
Hg – 0.1 m KHCO3 99.5 1.5 0.5 [34a]
Cd – 0.1 m KHCO3 78.4 1.6 5.0 [17e]
– 0.1 m KHCO3 39 1.4 0.8 [45]
Au – 0.1 m KHCO3 6 1.4 41.3 [45]
nonaqueous Pb – 0.3 m KOH–methanol 77 1.8 ~ 5.0 [17d]
Ag – 0.1 m KOH–methanol 8 2.8 ~ 0.9 [47]
d aqueous Ru–Pd – 0.5 m KHCO3 90 1.1 80 [37]
- Pd 100 1 m KHCO3 – 0.1 0.01 [48]
nonaqueous Ti – 0.1 m KHCO3 95.1 1.6 5.0 [17e]
plexes. Highly active metal-complex catalysts for CO2-to-formic

acid conversion are usually hydrides or halides, with phos-
phines as natural ligands.
In the 1970s, Rh(diphos)2Cl [diphos = 1,2-bis(diphenylphos-
phino)ethane] was proposed.[50] Experiments show that sub-
stantial amounts of formate are produced, and a likely interme-
diacy of the rhodium hydride is observed. In terms of cell per-
formance, current efficiencies range from 42 % for shorter elec-
trolysis times to 22 % for longer duration. Meanwhile, a small
proportion of cyanoacetate is detected in the product, and im-
provements of current efficiencies as well as the system life-
time are believed to be necessary.[50]
Continuous development of Rh complexes was carried out
in the late 1980s. Controlled-potential electrolysis has been
performed with cis-[Rh(bpy)2X2] + (X = Cl or the trifluorome-
thane sulfonate anion) as the catalyst and 0.1 m tetra-n-butyl-
ammonium hexafluorophosphate in acetonitrile (MeCN) as the Figure 3. Catalytic cycle of CO2 reduction catalyzed by an Ir complex, as pro-
posed by Kang et al.: modified from Ref. [52].
electrolyte solution. Formate, hydrogen, butylamine, and
butene could be detected as the dominant products. Control
experiments, comparing electrolysis with the presence and ab-
sence of metal complex and CO2, have demonstrated that this peak at approximately 4 %. Concerns might be raised that the
metal complex is an effective catalyst, and formate products competitive background evolution of hydrogen, which is one
are indeed derived from CO2.[51] of the major hindrances in CO2 electrochemical reduction,
Besides Rh complexes, Ir complexes are also eligible for cata- would be caused by the addition of water; however, solid evi-
lyzing CO2-to-formic acid electroreduction. A five-coordinate dence is reported to show that added water provides protons
16-electron IrIII pincer dihydride complex has been proposed as to generate hydroxide, which further reacts with CO2 to form
a catalyst for the electrochemical reduction of CO2, as shown HCO3 and minimizes hydrogen generation from protons.
in Figure 3. Experimental results indicate that the selectivity of Furthermore, through a nuclear magnetic resonance investiga-
this five-coordinate 16-electron IrIII pincer dihydride complex is tion, it was observed that added water promotes the forma-
high on a glassy carbon electrode at 1.45 V.[52] Neither hydro- tion of a cationic complex and subsequent release of formate
gen gas, which is supposed to be one of the side products, anions, as denoted in Figure 3. As the reduction potential of
nor carbon monoxide is found in a significant quantity.[52] this cationic complex is much lower than the neutral Ir com-
Another contribution of this study is the role of water, which plex, the overall electroreduction potential is significantly
can also be found elsewhere.[30b, 53] It is pointed out that added reduced.[52]
water would favor the reaction rate, specifically for the electro- Much effort has also been devoted to using other types of
reduction of CO2 to formate/formic acid, and it reaches the complexes to improve reaction rates, reduce high overpoten-
CHEMELECTROCHEM
tials, and enhance the overall efficiency. For instance, the [(h5-
Me5C5)M(L)Cl] + (L = 2,2’-bipyridine ligands; M = RhIII and IrIII)
catalyst[56] was reported to yield a 2:1 formate/H2 mixture in
5 % water/MeCN. It turns out that the RhIII complex, with a cur-
rent efficiency reaching 50 %, performs better than the IrIII com-
plex. The study also reveals that as the hydrido complex would
be formed at early stage, immobilization of catalysts by func-
tionalized polypyrrole films would result in lower efficiency of
CO2 insertion into the metal-hydride bond.
High catalytic activity is also found to be achieved with Ru
complexes. Based on research on Rh(1,2-bis(diphenylphosphi-
no)ethane)2Cl, as mentioned previously, Ishida et al.[57] have re- Figure 4. Schematic diagram of CO2-to-formate conversion catalyzed by
FDH1: modified from Ref. [25a].
ported large amounts of formate produced in the presence of
[Ru(bpy)2(CO)2]2 + (bpy = 2,2’-bipyridine), accompanying the uti-
lization of Me2NH·HCl or PhOH as a proton source in MeCN.
Experimental results suggested that the higher the pKa value that the structure of Desulfovibrio gigas might provide clues
of the proton source, the higher its selectivity for formate of the proper description of its actual structure.[62]
formation.
Another example is the tetranuclear iron–sulfur cluster
[Fe4S4(SR)4]2,[58] which significantly reduces the overpotentials 5. Electrolyte
by 0.7 V in the current range from 5 to 20 mA and shifts preva-
The electrolyte has a significant role in electrochemical reduc-
lent products from oxalate to formate, with water being the
tion of CO2. As the charge-transfer medium between the elec-
proton donor.
trodes and the co-catalyst during chemical reactions, the elec-
trolyte adds complexity to the process; on one hand, it might
4.3. Biocatalysts cause unpredictability, and on the other hand, proper selection
and utilization could contribute to system stabilization.
As emphasized previously, it is crucial to improve the selectivi-
Hydrogen evolution reaction (HER) is known as an undesira-
ty of CO2 electroreduction to valuable products. To this aim,
ble competing reaction in CO2 electrochemical reduction and
proton-assisted multi-electron transfer is highly favorable,
suppression of it can be achieved not only by appropriate cat-
whereas the single-electron reduction of CO2 to form the inter-
alysts, but also electrolytes with high overpotentials for hydro-
mediate species ·CO2 is unwanted.[59] Many attempts and ef-
gen evolution. Additionally, despite likely advantages, includ-
forts have been made to develop catalysts that can yield
ing high stability, mature preparation technology, and com-
formic acid as the only predominant product; however, few of
mercial availability, some catalysts might not give the optimal
them are highly satisfactory. Biocatalysts, composed of natural
catalytic activity for CO2-to-formic acid conversion; however,
materials and famous for their high catalytic activity and selec-
the possibility of utilizing such catalysts can be realized by em-
tivity, offer an alternative to CO2 electroreduction catalyst de-
ploying electrolytes that have a shift effect.
velopment and have become a popular subject lately.[60]
The impact of electrolytes on electrode performance has
A typical example is the tungsten-containing formate dehy-
been mentioned in the previous section. Conventionally, elec-
drogenase enzyme (FDH1).[25a, 61] Being adsorbed to the elec-
trolytes implemented in electrochemistry are categorized by
trode surface, FDH1 performs outstandingly with respect to
their phases, aqueous and nonaqueous, which are discussed
overpotential, catalytic activity, and selectivity. The reaction
below.
overpotential appears to be small, the catalytic rate reaches
more than two orders of magnitude higher than most other
catalysts for CO2-to-formate conversion, and formate is the
5.1. Aqueous Electrolytes
only product under mild reaction conditions. Moreover, experi-
mental results show that Faradaic efficiency reaches around An aqueous electrolyte is usually a solution in which the ions
100 % and the thermodynamic efficiency is recorded to be are dissolved in a hydrosolvent, based on which most studies
97 % at an overpotential of 0.45 V, corroborating the catalytic of CO2-to-formic acid conversion are conducted. Despite the
ability of FDH1 for CO2 and HCOO conversion.[25a] Figure 4 argument on whether ions, such as HCO3 and CO2 3 , would
demonstrates the catalytic process of CO2 electrochemical re- possibly act as the source of formate,[17a, 63] solid evidence has
duction to HCOO catalyzed by FDH1. been provided to show that these ions indeed enhance the
Although FDH1 shows great potential and is regarded as electrochemical reduction of CO2.[17d, 29c, 30b, 64] In addition to
the indicator of development direction, viability of commercial- HCO3 and CO2 + +
3 , ions including Na , Li , and K
+
are attested
izing FDH1 is still not feasible in the near future, because it is to favor CO2 reduction.
vulnerable to oxygen poisoning. Also, the structure of FDH1 KHCO3 solution is one of the most representative aqueous
has not been clarified yet and researches can only suggest electrolytes. In addition to the experiments shown in Table 3,
that it contains at least nine iron–sulfur clusters. It is believed many other studies have been conducted with KHCO3 electro-
CHEMELECTROCHEM
lyte to assess, for example, Cu electrodes,[46, 65] GDE struc- ganic solvent with high dielectric constants and high dipole
tures,[37, 66] Pd wire electrodes,[67] and so forth. moments, such as MeCN.
In general, the stable electroconductivity and convenience Another type of electrolyte that draws more and more at-
of concentration adjustment of common aqueous electrolytes tention is ionic liquids.[73] Different from the electrolytes dis-
enables researchers to perform control experiments on various cussed above, ionic liquids are salts in a liquid phase instead
electrode catalysts and structures. of electrically neutral molecules dissolved in solvents. Ionic liq-
uids are highly electrically conductive and, hence, have been
treated as a new direction of electrolyte development for CO2
5.2. Nonaqueous Electrolytes
electrochemical reduction.
Generally speaking, nonaqueous electrolytes enhance CO2 sol- As is well known, most salts have a rather high melting
ubility and suppress the HER. Common substances include points, owing to strong ionic bonds; however, liquid states
KOH/methanol (i.e. KOH/CH3OH), tetraethylammonium perchlo- would still exist for substances based on 1-alkyl-3-methylimida-
rate (TEAP), and MeCN. Back in the 1980s, CH3OH was found to zolium, N-methyl-N-alkylpyrrolidinium, 1-ethyl-3-methylimida-
have a CO2 solubility five times that of water, and it has already zolium (EMIM), 1-butyl-3-methylimidazolium (BMIM), and fluo-
been applied in industry as a CO2 absorber.[55, 68] Moreover, rosulfonyl-trifluoromethanesulfonylimide (FTFSI).[74] Through
Mizuno et al. pointed out that formation of favorable K + and synthesis and metathesis reactions, common ionic-liquid com-
HCO3 ions would occur with KOH in CH3OH.[55] pounds, such as BMIM-Br, BMIM-BF4, BMIM-PF6, BMIM-CL, and
HER suppression is another feature of the KOH/CH3OH elec- EMIM-dicyanamide could be prepared.[11, 75] Additionally, the
trolyte. As indicated by the comparison between benzalkoni- solubility of CO2 in ionic liquids, especially BMIM-BF4 and
um/CH3OH and KOH/CH3OH electrolytes in Table 4, KOH/ BMIM-PF6, has been studied and improved to a great extent in
recent years.[76] BMIM-PF6, as an example, demonstrates high
CO2 solubility, according to experiments conducted by Prez-
Table 4. Comparison between benzalkonium/CH3OH and KOH/CH3OH Salado et al. at temperatures from 20 to 120 8C and pressures
electrolytes in terms of HER suppression on different electrode materials. below 10 MPa.[76b] Furthermore, with biological enzyme re-
Electrode Current efficiencies for H2 evolution [%] Ref. search blooming recently, studies on biocatalysts such as the
benzalkonium/CH3OH KOH/CH3OH NAD redox couple show that ionic liquids are a suitable elec-
Au 10–16 1.4–49.7 [17d]
trolyte,[77] promoting its popularity in researches of biocatalysts
Cu 54 3–21 [54] for CO2 electroreduction.
Pd – 2–85 [17d]
Ti 114 40–100 [55]
6. Operation and Design of the Electrolytic

Cell
CH3OH electrolyte generally depresses the HER rate to no
more than half of that in benzalkonium/CH3OH, and the lowest In addition to the aforementioned factors, in order to achieve
HER current efficiencies have been recorded to approach zero. optimal reaction efficiency and selectivity of CO2 electrochemi-
Additionally, the combination with a Pb wire electrode is re- cal reduction, significant impacts of pH values, temperatures,
ported to yield formic acid and depress HER to < 3.5 % at po- reactor design, and gaseous bubbles have been realized and
tentials between 1.8 and 2.5 V (vs. Ag/AgCl). In the pres- investigated.
ence of KOH/CH3OH, HCOOH can also be observed on Au, Cu, The pH conditions in the reactor directly influence the reac-
Pd, Pb, and Ti electrodes.[17d, 47, 54, 55, 69] Thus, KOH/CH3OH electro- tion rate of CO2 reduction. In general, on sp-metal electrodes
lyte has shown satisfactory performance. in aqueous electrolytes, neutral solution favors formic acid for-
Another type of nonaqueous electrolyte is organic electro- mation and formate ions would be the main product in weak
lytes, in which solutes are dissolved in organic solvents such as alkaline solution.[29b] Different CO2 electroreduction routes can
dimethylfomamide (DMF), MeCN, or dimercaptosuccinic acid be found in Scheme 2 and the respective impacts of pH values
(DMSA). Similar to KOH/CH3OH, organic electrolytes are report- are summarized in Table 5. More specifically, three representa-
ed to have a high solubility of CO2[70] and effectively depress tive pH values (i.e. pH 4, 7, and 10) have been compared,[33a] as
the HER, because of their aprotic nature. summarized in Table 6. In addition, the relationship between
Tetraethylammonium salt (TEA, molecular formula: C8H20N + ) pH values and potentials of CO2 as well as other related sub-
is a representative organic electrolyte in virtue of its high in- stances are presented in Figure 5, based on the Pourbaix dia-
volvement in phase-transfer catalysis, where ionic reactants are gram by Hori.[30a] It is revealed that in order to obtain formate
solubilized into an organic phase. TEA salts are more common- or formic acid, that is, Routes (2) and (6) in Scheme 2, medium
ly used than TEA, because the four small ethyl groups in the potentials are required and an acidic environment is desirable
molecular structure of TEA are not competent for effective regarding current density, selectivity, and overpotential. Yet,
inter-phase ion transfer, whereas this demerit is not found for low pH values would conversely hinder or even block the
TEA salts. Examples of TEA salts are tetraethylammonium tetra- transport of CO2 ; moreover, the competitive HER would be
fluoroborate (TEABF4)[71] and TEAP.[72] In laboratory electro- strengthened to a large extent and instability of catalysts (es-
chemical reduction of CO2, TEA salts are usually dissolved in or- pecially Sn) would likely occur at low pH conditions.[29b, c, 33a]
CHEMELECTROCHEM
Table 5. Impact of the pH value on each CO2 reduction pathway.
Route pH impact Ref.

(2), (3) in Scheme 2 blocked by very low pH [29c]
(1), (4), (5), (6), (7), (8), (9), (10), (11) in Scheme 2 promoted by acidic condition [20a, 29b, c, 46, 63]
transport of CO2 to the electrode surface possibly catalyzed by high pH values [29c]
yield of HCOOH from Hg and In in aqueous solution optimal pH value is 5–6 [29c, 63]
yield of HCOOH on Cu electrode in KHCO3 solution or d group metals favored by high pH values [29c, 46]
Table 6. Comparison of pH values at pH 4, 7, and 10, based on data ex-

tracted from Ref. [33a].
pH Partial current Selectivity of Energetic Cell

value density the catalyst efficiency potential
4 largest largest largest lowest
7 medium medium medium medium
10 lowest lowest lowest highest
In addition to an optimal pH value, the merit of elevating

pressure in CO2-to-formic acid conversion has also been realiz-
ed. Relevant studies and experimental results are summarized Figure 5. Potential versus pH value of CO2 and related substances: modified
in Table 7. As can be seen, HCOOH formation and current den- from Ref. [30a] with permission.
sity would be promoted at reasonably high CO2 partial pres-

sures. Potential shifts and HER suppression could also be ach- cades, rectangular-type reactors have been reported, which
ieved on certain metals[78] and, therefore, pressurized electro- can extend the electrode surface as much as possible within
lytic cells draw more and more attention. a small cell volume.[7b] Although formic acid was not observed
Further improvements of cell performance, especially current as a product and this type of reactor did not involve liquids,
densities, can be achieved by optimizing the reactor design. the design idea was referenced for subsequent development.
In early studies, the H-cells shown in Figure 6 a with metal With similar purposes as rectangular-type reactors, bench-scale
plate electrodes were widely utilized. However, drawbacks continuous reactors were proposed for the electrochemical re-
soon emerged, including limited electrode surface, large inter- duction of CO2 to formate, as demonstrated in Figure 6 b.
electrode distance, and poor cell performance. In recent de- By using a mesh tinned-copper cathode, co-current reactant
Table 7. Relevant studies of elevated pressure in CO2 electroreduction.
Pressure Electrode material Observations and findings Ref.

[atm]
10 Cu Faradaic efficiency of HCOOH formation at 3.0 V (vs. Ag quasi-reference electrode) reaches 15 % [79]
20 Co, Rh, Pd, Pt, Ag At current density 300 mA cm2 and cathode potentials of 1.56, 1.34, 1.33, 1.38, 1.22 V [80]
(vs. Ag/AgCl), Faradaic efficiencies of HCOO formation are recorded to be 0.6, 3.6, 2.3, 0.2, 1.8 %,
respectively
Ni At current density 600 mA cm2 and cathode potential of 1.88 V (vs. Ag/AgCl), Faradaic efficiency
of HCOO formation is recorded to be 0.9 %
Cu At current density 900 mA cm2 and cathode potential of 1.27 V (vs. Ag/AgCl), Faradaic efficiency
of HCOO formation is recorded to be 27.8 %
29.6 Sn, Pb > 90 % HCOOH yield [66]
Cu, Bi > 50 % HCOOH yield
30 Rh, Ag, Pd Maximum partial current densities of CO2 electroreduction reach 237, 383, and 397 mA cm2, [29b, 49b]
respectively
Pb, Sn, In, Bi Faradaic efficiencies of HCOOH formation reach 95.5, 92.3, 90.1, and 82.7 %, respectively
Cr, Ti, Zr, Nb, Ta, Mn < 10 % HCOOH yield
< 50 Pt Faradaic efficiency of CO2 electroreduction reaches 46 % and current density reaches 900 mA cm2 [78]
50 Ag Current densities increase with higher CO2 partial pressures [80]
Ni Current densities decrease as CO2 partial pressure increases
Pd Current densities are not increased significantly
50–60 Fe, Co, Ni, Pd, Pt Current efficiencies are recorded up to 62 % [29c, 81]
60 In Current density of HCOOH formation rises from ~ 200 to 560 mA cm2 [66]
high pressure In, Sn, Pb Faradaic efficiencies of CO2 to HCOOH conversion reach 100 at 20–60 8C, 99.2 at 20 8C, and 91.2 % [82]
at 60 8C
CHEMELECTROCHEM
Figure 6. Schematic diagram of electrolytic cell design: a) conventional H-cell, b) bench-scale continuous reactor (modified from Ref. [83], c) undivided fixed-
bed reactor (modified from Ref. [64], and d) microfluidic reactor.
gas and catholyte could flow through and this mechanism ducted numerical modeling on a microfluidic reactor for CO2
could help alleviate the CO2 solubility constraint.[83] Formate electrochemical reduction and have performed parametric
turns out to be the primary product; however, unsatisfactory analysis towards the optimization of cell operation.[86]
overpotential is also observed, driving the evolution of other Based on microfluidic reactors, the generation and dissolu-
designs. tion of small CO2 bubbles at the mesoscopic scale have been
In 2003, undivided fixed-bed reactors,[64] with the advantag- studied.[87] Conclusions are drawn that the flow rate of the con-
es of relatively large geometric surface area, small electrode tinuous aqueous phase and the acid–based equilibria are the
gap, and high Faradaic efficiency, were proposed by Kçleli determinants of the final size of the bubbles. Control strategies
et al., as presented in Figure 6 c.[64] High selectivity is observed have also been investigated, and temperature-mediated con-
and formic acid is the only detectable product with Pb as the trol of CO2 is reported to mediate CO2 interactions with the
electrode material and 0.5 m KHCO3 as the electrolyte. electrolyte and solve the problem of unwanted bubble-size in-
All of the abovementioned reactors were designed on the congruence through a narrow size distribution.
basis of fuel cells, most of which utilize a polymer electrolyte
membrane as the electrode separator. More recently, a state-
7. Industrial Applications
of-the-art concept of microfluidic electrolytic cells for CO2 re-
duction[84] has been reported, using a flowing electrolyte Owing to commercial prospects such as renewable-energy stor-
stream to separate cathodes and anodes. Microfluidics refers age and chemical feedstock production, promising technology
to fluid flowing in a microchannel that can perform distinctive for CO2-to-formic acid conversion has bred new industrial efforts
behaviors and have unique properties in contrast to the fluid (Figure 7). Supported by theoretical modeling results of the op-
at the macroscale. Microfluidics is a powerful technique to en- eration conditions and reactor design, DNV GL constructed
hance reaction systems, because it offers a high surface-to- a small-scale reactor powered by solar panels[21a] in 2011, report-
volume ratio and efficient heat and mass-transfer rates. It has ing the capability of reducing around 1 kg of CO2 per day. This
been proven that microfluidic reactors, as demonstrated in Fig- pilot device not only demonstrated the function of formic acid
ure 6 d, may address some limitations of macroscale devices, as a renewable-energy storage medium, but also the commer-
such as minimizing water management, salting-out issues, and cial viability of achieving a high overall system performance.
ohmic loss. Therefore, leveraging the benefits of microfluidics Siemens also initiated a project called CO2RRECT,[88] aiming
to address today’s most pressing energy and environmental at leveling renewable resources and converting atmospheric
challenges would be promising and significant. CO2 into useful chemicals including formic acid. Their research
In addition to experimental studies and prototype develop- is carried out at a coal-fired power plant, investigating the pos-
ment on general microfluidic reactors,[85] Wang et al. have con- sibility of industrial-scale development.
CHEMELECTROCHEM
At the same time, despite the difficulties of hydrogen stor-

age and transport, water electrolysis for hydrogen production
is still an alternative for electricity storage. Thus, only if the cur-
rent density of the CO2 reduction process is further increased
to close to or even exceed that of water electrolysis, the com-
petitiveness of CO2-to-formic acid conversion can be enhanced.
In addition, owing to low solubility, the rate of CO2 mass trans-
port to active sites significantly constrains cell performance.
Overpotential is another major restriction that is imperative
to be alleviated. In fact, electrochemical CO2 reduction does
not have a high negative equilibrium potential [0.43 V vs.
standard hydrogen electrode (SHE)] compared with that of the
HER (0.414 V vs. SHE) in aqueous electrolyte solutions.
However, the hindrance for advancing CO2 reduction is the
high overpotential caused by the formation of the radical
anion intermediate species ·CO2 .[3, 29c, 30a] As a consequence, the
actual electrolysis potentials for CO2 reduction become much
more negative than the equilibrium ones and should be im-
proved through intermediate stabilization.
Last but not least, because microfluidic electrochemistry is
a relatively new research area and the development of micro-
fluidic CO2 electrolyzers is still at an early stage, many unre-
solved problems still exist. From a device-level viewpoint, the
microfluidic system performance is generally lower than its
conventional counterparts. Thus, in order to exploit microflui-
dics as a powerful technique to enhance CO2-electrolyzer per-
formance, particular focus should be put on the fundamental
understandings of transfer and reaction mechanisms.
9. Summary and Outlook

This paper presents a comprehensive review on the engineer-
Figure 7. Industrial application of electrochemical reduction of CO2 to for- ing aspects and essential constituents of electrochemical
mates: a) pilot reactor built and assembled by DNV GL (reproduced from system for CO2-to-formic acid conversion, including electrode
Ref. [21a] with permission) and (b) project CO2RRECT conducted by Siemens structure, catalyst, electrolyte, reactor design, and operation
AG (reproduced from Ref. [88] with permission).
conditions. Recent research shows the prospect of electro-
chemical reduction of CO2 to formic acid for purposes of
greenhouse-gas reduction and energy conversion. Investiga-
8. Challenges and Opportunities
tions on metal complexes and biological catalysts, as well as
The efficiency of an electrochemical process is evaluated by state-of-the-art organic electrolytes and ionic liquids, have sig-
how high the selectivity for the desired products is and to nificantly promoted the development of CO2 electroreduction
what extent can the need for a high driving force be avoided. technology. Great efforts have also been put into the optimiza-
Also, the amount of energy that can be converted and stored tion of operation conditions and, hence, the overall system
in the desired products, which is measured as the Faradaic effi- performance.
ciency and energy efficiency, is also a vital benchmark and de- There remains room for improvement in many areas, includ-
termines the reactor size, and thus the capital cost. ing ameliorating reactor designs, improving catalyst activity
To date, researchers have reported high Faradaic efficiency and selectivity, advancing simulations of the three-phase inter-
for CO2-to-formic acid conversion. Moderate-to-high current face, and introducing brand-new electrode designs. There is
densities (exceeding 600 mA cm2) have also been achieved by also great potential for studies on the interactions between mi-
using catalyst-deposited GDEs.[31, 78] However, the problem of crofluidic mechanics and electrochemical kinetics. At the same
GDE corrosion and exfoliation still exists at high cell potentials time, the integration of electrolytic cells into a microfluidic
on common carbon diaphragms, which result from gaseous platform shows a cutting-edge interdisciplinary research area
bubbles invading into the porous structure. of electrochemical CO2 reduction.
CHEMELECTROCHEM
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Electrochemical Reduction of Carbon Dioxide To Formic Acid

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CHEMELECTROCHEM

Electrochemical Reduction of Carbon Dioxide to Formic

As the fourth most abundant element, carbon plays a funda-

summarizes the fuels that have the potential to be obtained

Prof. Dennis Y. C. Leung received his

creasingly popular fuel. For instance, Rice et al.[22] described

tion of an intermediate COOH radical (ad) and 2) final produc-

Figure 2. Mechanism of electrochemical CO2 reduction on an electrolytic cell

Major steps involved in the CO2 electrochemical reduction

Metal Electrolyte Catalyst Selectivity Electrolyte Faradaic Potential Current Ref.

plexes. Highly active metal-complex catalysts for CO2-to-formic

6. Operation and Design of the Electrolytic

Table 5. Impact of the pH value on each CO2 reduction pathway.

Route pH impact Ref.

Table 6. Comparison of pH values at pH 4, 7, and 10, based on data ex-

pH Partial current Selectivity of Energetic Cell

In addition to an optimal pH value, the merit of elevating

sity would be promoted at reasonably high CO2 partial pres-

Table 7. Relevant studies of elevated pressure in CO2 electroreduction.

Pressure Electrode material Observations and findings Ref.

At the same time, despite the difficulties of hydrogen stor-

9. Summary and Outlook

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