Chem Soc Rev

View Article Online

TUTORIAL REVIEW View Journal

Electrocatalytic reduction of CO2 and CO to

Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.

multi-carbon compounds over Cu-based catalysts

Cite this: DOI: 10.1039/d1cs00535a

Wenchao Ma, Xiaoyang He, Wei Wang, Shunji Xie, * Qinghong Zhang and
Ye Wang *

Received 11th June 2021
DOI: 10.1039/d1cs00535a
rsc.li/chem-soc-rev
The electrocatalytic reduction of CO2 with H2O to multi-carbon (C2+) compounds, in particular, C2+
olefins and oxygenates, which have versatile applications in the chemical and energy industries, holds
great potential to mitigate the depletion of fossil resources and abate carbon emissions. There are two
major routes for the electrocatalytic CO2 reduction to C2+ compounds, i.e., the direct route and the
indirect route via CO. The electrocatalytic CO2 reduction to CO has been commercialised with solid
oxide electrolysers, making the indirect route via CO to C2+ compounds also a promising alternative.
This tutorial review focuses on the similarities and differences in the electrocatalytic CO2 and CO
reduction reactions (CO2RR and CORR) into C2+ compounds, including C2H4, C2H5OH, CH3COO and
n-C3H7OH, over Cu-based catalysts. First, we introduce the fundamental aspects of the two
electrocatalytic reactions, including the cathode and anode reactions, electrocatalytic reactors and
crucial performance parameters. Next, the reaction mechanisms, in particular, the C–C coupling mecha-
nism, are discussed. Then, efficient catalysts and systems for these two reactions are critically reviewed.
We analyse the key factors that determine the selectivity, activity and stability for the electrocatalytic
CO2RR and CORR. Finally, the opportunities, challenges and future trends in the electrocatalytic CO2RR
and CORR are proposed. These insights will offer guidance for the design of industrial-relevant catalysts
and systems for the synthesis of C2+ olefins and oxygenates.

Key learning points

(1) Key breakthroughs and the state-of-the-art in the electrocatalytic CO2/CO reduction to C2+ compounds.
(2) Similarities and differences between the electrocatalytic CO2 and CO reduction reactions.
(3) The mechanism of C–C coupling in the electrocatalytic reduction of CO2/CO.
(4) Challenges, opportunities and future trends for the electrocatalytic CO2/CO reduction.

1. Introduction under ambient conditions and the precise control of C–C

The growing CO2 emissions and the increasing demand for
carbon feedstocks have evoked a lot of research activities on the
upgrading of CO2 into building-block chemicals and liquid
fuels, in particular multi-carbon (C2+) olefins and oxygenates,
which are playing crucial roles in the current supply of energy
and chemicals such as fuel additives, plastics, disinfectants and
pharmaceuticals.1 The activation of stable CO2 molecules
State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative
Innovation Center of Chemistry for Energy Materials, National Engineering
Laboratory for Green Chemical Productions of Alcohols, Ethers and Esters,
Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian
Province (IKKEM), College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China. E-mail: shunji_xie@xmu.edu.cn,
wangye@xmu.edu.cn
coupling are two of the biggest challenges in chemistry for CO2
transformations.2 The thermocatalytic hydrogenation of CO2
with H2 over modified Fischer–Tropsch catalysts or bifunc-
tional catalysts composed of a metal oxide and a zeolite affords
C2+ compounds at high temperatures and pressures.3 However,
the selectivity of a specific C2+ compound is limited due to the
limitation by the Anderson–Schulz–Flory distribution over the
modified Fischer–Tropsch synthesis or the formation of CO
over bifunctional catalysts.3 In the past decade, the electro-
catalytic CO2 reduction reaction (CO2RR) with H2O to C2+
compounds (Fig. 1a) has become a hot research area mainly
because of the following reasons.4–6 First, electricity can be
generated from renewable energy sources such as solar and
wind energies, and the cost of the renewable electricity has
been decreasing. The combination of renewable electricity and

This journal is © The Royal Society of Chemistry 2021 Chem. Soc. Rev.

Tutorial Review
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
Fig. 1 (a) Direct route for the electrocatalytic CO2RR to C2+ compounds. (b) Indirect route for the electrocatalytic CO2RR to C2+ compounds via CO.
the electrocatalytic CO2RR would contribute to establishing
carbon-neutral processes. Second, the electrocatalytic CO2RR
to high-energy molecules enables to store electric energy in the
form of chemical energy. Third, recent studies have demon-
strated that the high selectivity of C2+ olefins and oxygenates
can be achieved by the electrocatalytic CO2RR under ambient
conditions. It is also of fundamental interest that the C–C
coupling by electrocatalysis may proceed via a different mecha-
nism from those by thermocatalytic hydrogenation,7,8 offering
Wenchao Ma received his BSc
degree from Xiamen University
in June 2016. He is currently a
PhD candidate in Professor Ye
Wang’s group in the Colla-
borative Innovation Center of
Chemistry for Energy Materials
(iChEM) at Xiamen University.
His research interests focus on
photo- and/or electro-catalytic
upgrading of C1 molecules.
Wenchao Ma
Wei Wang received his BSc degree
from Dalian University of
Technology in June 2019, and
studied the conversion of CO2.
He is currently a MSc candidate
in Professor Ye Wang’s group. His
research interest is heterogeneous
catalysis.
Wei Wang
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
a new opportunity to control the C–C coupling and the product
selectivity.
Besides the electrocatalytic CO2RR, the electrocatalytic CO
reduction reaction (CORR) to C2+ compounds has also attracted
much attention in recent years.9 This is not only because CO is an
abundant and cheap carbon feedstock, which can be produced
from a variety of resources such as natural/shale gas, coal and
biomass,3,10 but also because an indirect route for the conversion
of CO2 to C2+ compounds via CO can be constructed (Fig. 1b).
Xiaoyang He received his BSc
degree from Dalian University of
Technology in June 2019. He is
currently a MSc candidate in
Professor Ye Wang’s group. His
research interest focuses on the
electrocatalytic reduction of CO2.
Xiaoyang He
Shunji Xie received his BSc and
MSc degrees from Hunan Univer-
sity of China in 2008 and 2011,
and obtained his PhD degree
from Xiamen University in 2014.
He then carried out a post-
doctoral research at the Colla-
borative Innovation Center of
Chemistry for Energy Materials
(iChEM). He is currently a full
professor in the College of
Chemistry and Chemical Engi-
Shunji Xie neering of Xiamen University.
His research interest focuses on
photocatalysis and electrocatalysis for C1 and sustainable
chemistry, including CO2 reduction, CH4 oxidation, biomass
conversion and ethylene glycol synthesis.
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
The indirect route involves two steps, i.e., the electrocatalytic
CO2RR to CO, which is technically mature, followed by the
electrocatalytic CORR to C2+ compounds. The indirect route
would be promising if efficient catalysts with high selectivity,
activity and stability for the electrocatalytic CORR could be
developed.
A number of excellent review articles have already been
published on the direct electrocatalytic CO2RR.4,6–8,11,12 However,
so far, few review articles have been devoted to the electrocatalytic
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
CORR.9 Since CO is generally considered as the key reaction
intermediate in the electrocatalytic CO2RR to C2+ compounds,4
there must exist similarities between the electrocatalytic CO2RR
and CORR. The most common feature is that, copper is the only
electrocatalyst that shows high selectivities of C2+ compounds in
both the CO2RR and CORR. However, differences are also known
between the CO2RR and CORR. For example, the selectivity of
C2H4 is often higher than that of C2+ oxygenates (mainly C2H5OH)
in the electrocatalytic CO2RR over Cu catalysts, whereas C2+
oxygenates are obtained as the major C2+ products in the electro-
catalytic CORR in many publications. To the best of our knowl-
edge, so far, no review article has been devoted to the comparison
between the electrocatalytic CO2RR and CORR.
This tutorial review focuses on the similarities and differ-
ences in the electrocatalytic CO2RR and CORR into C2+ com-
pounds (including C2H4, C2H5OH, CH3COO and n-C3H7OH)
over Cu-based catalysts. First, we will introduce the funda-
mental aspects of the electrocatalytic reduction of CO2 and
CO, including the cathode and anode reactions, electrocatalytic
reactors, and crucial performance parameters. Next, the reac-
tion mechanism, in particular the C–C coupling mechanism,
will be discussed. Furthermore, the advances in the develop-
ment of efficient catalysts and systems for these two routes will
be highlighted. We will analyse the key factors (mainly includ-
ing catalysts, reactor configurations and reaction conditions)
that determine the selectivity, activity and stability for the
Qinghong Zhang received her BSc
and MSc degrees from Nanjing
University in 1989 and 1992,
and obtained her PhD degree
from Hiroshima University of
Japan in 2002. She joined
Xiamen University in October
2002 and was promoted to a full
professor in 2010. Her research
interests include the synthesis
and characterization of novel
materials with advanced cata-
Qinghong Zhang lytic properties.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
electrocatalytic CO2RR and CORR. Finally, we will highlight
the opportunities, challenges and possible future developing
trends for this booming research field.
2. Fundamental aspects of the
electrocatalytic CO2RR and CORR
2.1. Cathode and anode reactions
The cathode is the site of reduction, where CO2 or CO mole-
cules are reduced on the catalyst surface by reacting with
protons (H+) and electrons (e ). Different products can be
obtained depending on the number of protons and electrons
transferred. For CO2RR products, HCOO , CO, CH4, C2H4,
C2H5OH, CH3COO and n-C3H7OH have all been observed,
while CH4, C2H4, C2H5OH, CH3COO and n-C3H7OH are
usually reported products in CORR (Table 1). H2 is also a
product in both the CO2RR and CORR, which comes from the
competitive reduction of protons in the same reduction
potential range. Regarding the significance of C2+ products
formed during the CO2RR and CORR, C2H4 is one of the most
important feedstocks for the production of various chemicals
and synthetic materials, in particular plastics,1–3 while
C2H5OH, which can be used as a fuel additive, solvent and
disinfectant, is a key chemical in both the energy and chemical
industries.2 Although the versatility is not as high as ethylene
and ethanol, acetic acid is also an important chemical in the
current chemical industry.9 n-Propanol can be used as an
engine fuel because of the high octane number (18) and
impressive volumetric energy density (27 MJ L 1), thus having
a high economic value and deserving particular research
attention.2
As displayed in Table 1, the electrocatalytic CORR to each
target C2+ product, including C2H4, C2H5OH, CH3COOH or
n-C3H7OH, has a more positive equilibrium potential than that
Ye Wang received his BSc degree
from Nanjing University and PhD
degree from Tokyo Institute of
Technology. He then worked at
Tokyo Institute of Technology,
Tohoku University and Hiroshima
University, and was promoted to
associate professor at Hiroshima
University in 2001. He became
full professor of Xiamen
University in August of 2001. He
serves as associate editor of ACS
Ye Wang Catalysis and council member of
International Association of
Catalysis Societies. The research interest of Prof. Ye Wang’s group is
catalysis for C1 and sustainable chemistry, including C–H activation
and C–C coupling of C1 molecules and C–O/C–C cleavage chemistry
for cellulose/lignin valorization.
Chem. Soc. Rev.

Tutorial Review
Table 1 Electrocatalytic CO2RR and CORR to different products and the corresponding equilibrium potentials (E0) versus reversible hydrogen electrode
(RHE)
CO2RR E0 (V vs. RHE)
2H+ + 2e - H2 0 2H+ + 2e - H2
CO2 + 2H+ + 2e - HCOOH 0.19
CO2 + 2H+ + 2e - CO + H2O 0.11
CO2 + 8H+ + 8e - CH4 + 2H2O 0.17
2CO2 + 12H+ + 12e - C2H4 + 4H2O 0.06
2CO2 + 12H+ + 12e - C2H5OH + 3H2O 0.08
2CO2 + 8H+ + 8e - CH3COOH + 2H2O 0.12
3CO2 + 18H+ + 18e - n-C3H7OH + 5H2O
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
0.10
of the CO2RR. In addition, the electrocatalytic CORR to a
specific C2+ product involves fewer proton/electron transfer
steps. These facts indicate that the electrocatalytic CORR may
have a higher activity than the CO2RR under the same reaction
conditions. In an aqueous medium, the solubilities of CO2 and
CO are very low, and their values are 34 and 1 mM, respectively.
Therefore, although the equilibrium potentials for the CO2RR
and CORR to C2+ products are all more positive than that for
the hydrogen evolution reaction (HER), the formation of C2+
products still needs significant energy inputs because of intrin-
sically sluggish kinetics and mass-transport limitations in an
aqueous medium.
The anode is the site of oxidation. The oxygen evolution
reaction (OER) is typically used as the anode reaction for the
electrocatalytic CO2RR and CORR, but the design of an anode
reaction to produce value-added products would be of great
interest. The OER is a four-electron transfer process (2H2O -
O2 + 4H+ + 4e ), and has a high equilibrium potential (1.23 V vs.
RHE). The OER usually does not affect the selectivity of the
cathodic CO2RR or CORR, but its sluggish reaction kinetics
increases the full-cell voltage, resulting in a low full-cell energy
conversion efficiency (ECE). Anode catalysts with high activity
and stability under an industrial-relevant current density
should be further designed and developed.
2.2. Electrocatalytic reactors
There are mainly three types of electrocatalytic reactors for the
CO2RR and CORR, i.e., H-cell, flow cell and membrane elec-
trode assembly (MEA) cell (Fig. 2). In this section, we briefly
describe the setup of each reactor and the experimental proce-
dure for electrocatalysis. The advantages and disadvantages of
each reactor will be discussed in Section 4 with examples.
Fig. 2 Schematic illustration of three types of electrocatalytic reactors. (a) H-cell. (b) Flow cell. (c) MEA.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
CORR E0 (V vs. RHE)
0
— —
— —
CO + 6H+ + 6e - CH4 + H2O 0.28
2CO + 8H+ + 8e - C2H4 + 2H2O 0.28
2CO + 8H+ + 8e - C2H5OH + H2O 0.30
2CO + 4H+ + 4e - CH3COOH 0.34
3CO + 12H+ + 12e - n-C3H7OH + 2H2O
0.43
The H-cell is typically composed of a cathode compartment
for the CO2RR or CORR and an anode compartment for the
OER, and the two compartments are separated by an ion
exchange membrane (Fig. 2a). During the reaction, CO2 or CO
gas is purged into the aqueous catholyte, and the dissolved CO2
or CO molecules are adsorbed on the electrocatalyst surfaces
and undergo reduction. The flow cell is typically composed of
three compartments, i.e., a gaseous cathode compartment for
CO2 or CO gas flow, a liquid cathode compartment for the flow
of the catholyte, and an anode compartment for the OER
(Fig. 2b). The gaseous and liquid cathode compartments are
separated using a hydrophobic gas diffusion electrode (GDE),
and the CO2RR or CORR takes place in the triple-phase bound-
ary of the GDE. The MEA cell (Fig. 2c), in which the cathodic
GDE and anodic catalyst are directly pressed on both sides of
an ion exchange membrane, is another type of promising
reactors for the CO2RR or CORR. In the MEA, no catholyte is
needed for the cathode side and H2O is provided by the vapour
phase or diffusion from the anolyte. Depending on the type of
electrolyte, different types of membranes can be employed.
Typically, anion- and cation-exchange membranes are used in
alkaline and neutral electrolytes, respectively. Although a few
studies reported that non-carbon-based GDEs such as porous
polytetrafluoroethylene (PTFE) showed enhanced stability,13,14
carbon-based GDEs are still the most widely used GDEs for
the electrocatalytic CO2RR or CORR because of the high con-
ductivity. The gaseous products from the cathode compartment
are directly sampled to a gas chromatograph for analysis. The
liquid products are usually collected after the reaction and
analysed by 1H NMR spectroscopy.
The H-cell is adopted for the electrocatalytic CO2RR and
CORR in many fundamental studies because of the low cost
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
and the easy operation. However, the H-cell cannot be employed
for future practical applications or industrial-relevant studies
because of the low activity resulting from the limited solubility
of either CO or CO2 in aqueous electrolytes. Although the flow cell
has achieved high half-cell performances for the electrocatalytic
CO2RR and CORR, the full-cell performance is still far from
commercial requirement because of high cell voltages and low
energy conversion efficiencies. In the MEA, no catholyte is needed
in the cathode side, leading to lower cell resistance and cell
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
voltages to achieve a high activity. In addition, the MEA reactor
has been widely applied in the fuel cell, whose technology is
relatively mature for scale-up.15 Thus, the MEA reactor holds great
potential for scalability and practical applications for the electro-
catalytic CO2RR and CORR.
2.3. Crucial performance parameters
Selectivity, activity and stability are the core parameters of a
catalytic reaction. High selectivity, activity and stability indicate
the low capital and operating costs, and thus are crucial to
industrial applications.
Selectivity is of paramount importance for the electrocataly-
tic CO2RR and CORR, since many types of products can be
obtained as shown in Table 1. The faradaic efficiency (FE) of a
specific product is usually used to express the selectivity of an
electrocatalytic reaction (Fig. 3), which is defined as the selec-
tivity on a molar electron basis and can be calculated by eqn (1),
FE = z  n  F/Q (1)
where z, n, F and Q are the number of electrons for a specific
reaction as shown in Table 1 (e.g., z = 12 for CO2RR to C2H4), the
molar number of a specific product, the Faraday constant
(96 485 C mol 1) and the total charge consumed to implement
the reaction, respectively. A high FE value reduces the total
charge required for the target reaction rate and minimizes the
downstream separation cost. The minimum requirement for
C2+ FE is 80% for the practical applications of either the
electrocatalytic CO2RR or CORR.6
For an electrocatalytic reaction, the parameters usually
measured to evaluate the activity include the current density,
the formation rate of a target product and the overpotential
(Fig. 3). The current density is usually defined as the electrical
current flow per geometric area of the electrode. The formation
Fig. 3 Crucial performance parameters for an electrocatalytic reaction.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
rate of the target product is usually expressed as the molar
numbers of the target product per hour per geometric area of
the electrode. The high current density and the high formation
rate of the target product are desirable for lowering capital
costs. A current density of 200 mA cm 2 is generally considered
as the threshold for commercialization.2 The overpotential, an
important parameter in electrochemistry, is the absolute dif-
ference between the applied potential and the equilibrium
potential. A low overpotential reduces the total electrical energy
input and minimizes the electricity cost. The overpotential at
industrial-relevant current density should be lower than B0.4 V
for the practical applications of the electrocatalytic CO2RR and
CORR.6
Stability is also a key parameter for the electrocatalytic
CO2RR or CORR, in particular for industrial-relevant high-rate
systems. Stability refers to the time taken to maintain constant
selectivity and activity (Fig. 3). Evaluating the stability of an
electrocatalytic system is a complex and systematic engineering.
Not only the catalyst lifetime needs to be considered, but also the
stability of membrane integrity and cell operation should be taken
into consideration. Disentangling these different aspects that
degrade the performance will be beneficial to the design of a
stable system. The high stability reduces the maintenance and
replacement costs as well as the associated downtime. A stable
operation of 5000 h is believed to be necessary for a large-scale
electrocatalytic process.6
In addition, ECE is also a key parameter for evaluating the
electrocatalytic performance, which is calculated by using
the ratio of chemical energy stored in the target products and
the electrical energy needed to implement the reaction. For
economic viability, the full-cell ECE of C2+ products needs to
reach at least 60%.5,6
3. The reaction mechanism
It is generally believed that the binding strength of CO, a
potential intermediate, with the metal surface plays a key role
in determining the selectivity of a metal catalyst.2,16 When the
interaction between CO and metal catalysts is too strong
(e.g., Fe, Co, Ni and Pt), the active site for the electrocatalytic
CO2RR will be poisoned, and thus the competing HER becomes
dominant. Metals with relatively weak CO binding energies,
e.g., Zn, Au and Ag, tend to desorb CO as the final product
rather than its further C–C coupling to C2+ compounds. Metals
with further weaker CO binding energies, e.g., In, Sn, Bi, Pb and
Hg, offer formate as the major product. So far, only Cu has been
reported to be the efficient single-metal catalyst for the for-
mation of C2+ compounds probably because of its optimal CO
affinity. Several bimetallic catalysts without Cu, e.g., Pd–Au,
Ni–Ga and Ni–Al, have been reported to catalyze the formation
of C2+ compounds.17 However, the FEs or selectivities of C2+
compounds for these bimetallic catalysts are very low (B5%).
Nitrogen-doped carbon materials as metal-free catalysts show
high C2+ FE (B80%) for the electrocatalytic CO2RR, but they
suffer from low current density (B1 mA cm 2).17
Chem. Soc. Rev.

Tutorial Review
Extensive experimental and theoretical studies have been
conducted to gain insights into the reaction mechanism for the
electrocatalytic CO2RR to C2+ compounds over Cu-based cata-
lysts. It is commonly accepted that CO2 is first reduced to form
adsorbed *CO via the *COOH intermediate and the *CO species
is a key intermediate for the formation of C2+ compounds. C–C
coupling is one of the most important steps in the formation of
C2+ compounds. To understand how C–C coupling occurs and
how it can be controlled would be vital for the rational design of
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
highly active and selective catalysts for C2+ formation. This
section discusses the C–C coupling mechanisms in the electro-
catalytic CO2RR and CORR. The mechanisms for post-C–C
coupling steps for the formation of C2H4 and C2H5OH, as well
as the differences in the CO2RR and CORR, are also discussed.
According to the reaction mechanisms for the electrocatalytic
CO2RR and CORR to C2+ compounds, the major difference
between the two processes lies in the step of electrocatalytic
CO2RR to CO, and the following C–C coupling mechanisms are
similar (Fig. 4). The energy consumption difference between the
CO2RR and CORR mainly comes from the step of electrocatalytic
CO2RR to CO. The standard Gibbs free energy change (DG) for the
electrocatalytic CO2RR to CO is +21 kJ mol 1, indicating the
higher energy consumption of the CO2RR than that of the CORR.
Regarding the C–C coupling in the direct CO2RR to C2+
compounds, three major mechanisms have been proposed.
First, the dimerization of *CO species to form a OC**CO
intermediate has been proposed in most of the studies reported
so far (Fig. 4a).8 Through time-resolved attenuated total
reflection-surface enhanced infrared absorption spectroscopy
(ATR-SEIRAS), Hwang and co-workers observed a broad band at
1550–1562 cm 1 during the electrocatalytic CO2RR over a
Cu(OH)2-derived Cu catalyst, and this band was assigned to
the surface-bound CO of OC**CO or OC**COH species.18 This
provides evidence for the mechanism of direct coupling of *CO.
Second, a hydrogen-assisted C–C coupling mechanism has
Fig. 4 (a) Possible C–C coupling mechanisms in the electrocatalytic
CO2RR. (b) Possible C–C coupling mechanisms in the electrocatalytic
CORR.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
been proposed over a fluorine-modified Cu catalyst. In this
mechanism, the hydrogenation of *CO into *CHO is believed to
occur and then the *CHO species undergoes coupling to form
*OCHCHO* (Fig. 4a).19 In situ ATR-FTIRS measurements con-
firmed the generation of *CHO species during the CO2RR on
the F–Cu catalyst, which showed both a high FE and a high
formation rate of C2+ compounds, whereas the *CHO species
was not observed on the sole Cu catalyst.19 This is probably
because of the lower coverage of the *CHO species on Cu alone,
which showed both a lower FE and a lower formation rate of C2+
compounds. Thus, the *CHO species is assumed to play a vital
role in C–C coupling over the highly active and selective F–Cu
catalyst. These results also suggest that the C–C coupling
mechanism may be different over different catalysts. Third,
Head-Gorden and co-workers proposed a mechanism of C–C
coupling between *CO and *CHO to O*CCHO for the formation
of C2H4 and C2H5OH on Cu(100) and Cu(111) surfaces through
DFT calculations (Fig. 4a).20
The C–C coupling mechanism for the electrocatalytic CORR
to C2+ compounds has also been investigated. Like in the
CO2RR, the direct coupling between two *CO species is believed
to be the major C–C coupling mechanism in most studies
reported to date (Fig. 4b). From in situ FT-IR measurements,
Koper and co-workers found two vibrational bands at 1191 and
1584 cm 1 on Cu(100) during the electrocatalytic CORR in the
LiOH electrolyte, and these bands were ascribed to the C–O–H
and CQO stretching modes of the OC**COH intermediate
based on DFT calculations.21 The OC**COH intermediate may
arise from the hydrogenation of OC**CO, providing evidence
for the direct coupling between two *CO. However, the
OC**COH species was not detected on Cu(111), indicating that
the direct dimerization of *CO may be structure-sensitive and
be favoured by Cu sites with square symmetry.21 Because of the
significantly increased concentration of CO, the C–C coupling
mechanism in the electrocatalytic CORR also shows some
distinct features from that in the CO2RR. For example, besides
the C–C coupling via the Langmuir–Hinshelwood mechanism
between two *CO species, the coupling via the Eley–Rideal
mechanism between *CO and gaseous CO, denoted as CO(g),
may also be possible (Fig. 4b).22 Furthermore, the high CO cover-
age on the catalyst surfaces in the CORR makes the possibility of
coupling between two *CHO species quite low. Instead, the
coupling between *CO and *CHO becomes possible (Fig. 4b).
Two major mechanisms have been proposed for the for-
mation of C2H4 and C2H5OH after the C–C coupling step. Koper
and Bell’s group suggest that the CH2CHO* species serves as
the selectivity-determining intermediate, which originates from
the proton and electron transfer of the OC**COH or *OCH-
CHO* intermediate.20,23 The hydrogenolysis of CH2CHO*
results in C2H4, whereas the hydrogenation of CH2CHO* leads
to CH3CHO* and consequently to C2H5OH (Fig. 5). Koper and
co-workers showed that the barrier for C2H4 formation was
0.2 eV lower than that for C2H5OH formation via CH3CHO*.23
This may explain why the Cu-based catalyst usually has higher
C2H4 selectivity over C2H5OH. On the other hand, Goddard III
and co-workers propose that the *CH*COH species, which
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
Fig. 5 Mechanisms for the formation of C2H4 and C2H5OH after C–C
coupling.
comes from the hydrogenation of OC**COH, is the selectivity-
determining intermediate.24 The dehydroxylation of *CH*COH
to *C*CH directs the reaction to C2H4, whereas the hydrogena-
tion of *CH*COH provides *CHCHOH, eventually resulting in
C2H5OH (Fig. 5). The CO coverage on the catalyst surfaces can
significantly affect the dehydroxylation and hydrogenation
processes, leading to the difference in selectivity between the
electrocatalytic CO2RR and CORR. A higher CO coverage may
suppress the dehydroxylation of *CH*COH, leading to lower
selectivity of C2H4 in the electrocatalytic CORR than that in the
CO2RR.25 Knowledge on the mechanisms for the formation of
CH3COO and n-C3H7OH is less accumulated, and future
studies are needed to gain more insights into the formation
mechanism for these C2+ oxygenates.
4. Efficient catalysts and systems for
the electrocatalytic CO2RR and CORR
to C2+ compounds
Both the direct and indirect routes for electrocatalytic CO2
transformations have advantages and disadvantages. There is
no doubt that the process for the direct CO2RR is simpler and
potentially more energy-saving, because no separation or puri-
fication of CO are needed. High FEs of C2+ compounds, in
particular C2H4 and C2H5OH, with high current densities are
also achieved in the electrocatalytic CO2RR with a flow cell with
a GDE and an alkaline electrolyte, but the long-term stability
remains challenging because the GDE suffers from losing
hydrophobicity and being flooded as well as the salt accumula-
tion during the long-term reaction. Furthermore, the formation
of carbonates between CO2 and hydroxide under alkaline con-
ditions would cause energy and carbon losses. Great advance
has been achieved in the electrocatalytic CO2RR to CO, and
the FE of CO reaches about 100% with a current density of
4100 mA cm 2 and a full-cell energy conversion efficiency of
45–64%.5 Actually, a full-scale electrocatalytic CO2RR to CO
device with a 45.4% total energy conversion efficiency using the
solid-oxide electrolyser technology has been commercialised by
Haldor Topsoe.26 In addition, the electrocatalytic CO reduction
to C2+ compounds under alkaline conditions may overcome the
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
problem of carbonate formation, making the indirect route
via CO a promising alternative. Significant progress has been
achieved in the field of electrocatalytic CO2RR and CORR to C2+
compounds over Cu-based catalysts. In this section, the devel-
opment of efficient catalysts and systems for the two reactions
will be critically reviewed. We focus on their similarities and
differences in terms of selectivity, activity and stability to
provide insights into the design of catalysts and electrochemi-
cal systems for future practical applications.
4.1 Selectivity
Since HCOO and CO are usually produced in the electro-
catalytic CO2RR but not in the CORR, a higher FE of total
C2+ products can be expected in the electrocatalytic CORR.
Furthermore, as already mentioned, although CO is considered
as the key intermediate in the CO2RR involving C–C coupling,
the distributions of C2+ products are usually different in the
CO2RR and CORR. A higher ratio of oxygenates/olefins in C2+
products is observed in the CORR than that in the CO2RR.27
It is proposed that the selectivity toward olefins and oxygenates
depends on the surface coverage of CO and H; the higher
surface coverage of H favours the formation of olefins, while
the formation of C2+ oxygenates is facilitated on the surface
with a lower H coverage.27 Therefore, the higher ratio of C2+
oxygenates/olefins in the electrocatalytic CORR is attributable
to the higher CO coverage under CO atmosphere. Nevertheless,
the tuning of the selectivity of a specific C2+ compound is
crucial for the future industrial applications of the electro-
catalytic CO2RR and CORR.
Here, we discuss the strategies to improve the selectivity of a
specific C2+ product in both the electrocatalytic CO2RR and
CORR. The systems that can achieve high selectivity of four
major C2+ products, i.e., C2H4, C2H5OH, CH3COO and
n-C3H7OH, are highlighted. Some typical systems for the electro-
catalytic CO2RR and CORR to C2+ compounds are summarized in
Tables 2 and 3.14,19,25,28–39
4.1.1. Formation of C2H4. As discussed above, the electro-
catalytic CO2RR offers high selectivity of C2H4 over Cu-based
catalysts. A lot of efforts have been devoted to the modification
of Cu catalysts to improve the FE of C2H4 in the electrocatalytic
CO2RR. The strategies include facet tuning and polymer modi-
fication, and several recent studies have demonstrated 470%
FEs of C2H4.28,29
Early studies on Cu single-crystal electrocatalysts by Hori
et al. showed that the product distribution in the electro-
catalytic CO2RR strongly depended on the facet of the
catalyst.40 In a 0.1M KHCO3 electrolyte, different types of
products, including H2, HCOO , CO, CH4, C2H4, CH3COO ,
C2H5OH and n-C3H7OH, were all formed on single-crystal Cu
catalysts with three different crystalline planes (Fig. 6a). At a
fixed current density of 5 mA cm 2, CH4 and C2H4 were the
major products on Cu(111) and Cu(100), respectively, whereas
Cu(110) exhibited suppressed FEs of CH4 and C2H4 but
favoured the formation of C2+ oxygenates, mainly including
CH3COO and C2H5OH.40
Chem. Soc. Rev.
 View Article Online

Tutorial Review Chem Soc Rev

Table 2 Typical electrocatalytic systems for CO2RR to C2+ compounds

FE (%)
Electrocatalyst Cell Ea (V) j (mA cm 2) C2H4 CH3COO C2H5OH n-C3H7OH C2+ Ref.
(100)-Rich Cu Flow cell 0.63 320 68 8 10 2 88 28
Cu–Polyamine Flow cell 0.47 32 87 0 7 0 94 29
Ag0.14–Cu0.86 alloy Flow cell 0.67 250 35 5 41 0 82 30
CunAgm bimetallic nanoparticles H-Cell 1.33 — 21.2 — — — 21.2 31
N-Doped graphene quantum Flow cell 0.9 282 25 5 45.4 7 82.4 14
dots/Cu nanorods
Cu single atom/carbon H-Cell 0.7 1.23 — — 91 — 95 32
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.

Dendritic Cu H-Cell 0.9 24 13 0 10 13.1 36.1 33

Fluorine-modified Cu Flow cell 0.89 1600 65 2 12 1 80 19
a
The potential refers to RHE.

Table 3 Typical electrocatalytic systems for CORR to C2+ compounds

FE (%)
a 2
Electrocatalyst Cell E (V) j (mA cm ) C2H4 CH3COO C2H5OH n-C3H7OH C2+ Ref.
Cu particles/GDE H-Cell 0.7 28 52.7 3.7 7.4 8.7 72.5 34
Oxide-derived Cu Flow cell 0.72 1250 65 7 18 4 94 25
N-Doped graphene quantum Flow cell 0.7 302.4 7 11 48.1 27.2 93.3 14
dots/Cu nanorods
Cu Nanoflowers H-cell 0.23 0.21 0.39 23.76 15.38 59.32 (CH3CHO) 98.85 35
Cu Nanosheets Flow cell 0.736 200 16.3 48 2.4 2.0 68.7 36
Ag-Doped Cu Flow cell 0.46 13.6 29.7 4.7 5.9 33.3 73.6 37
Oxide-derived Cu Flow cell 0.72 1050 44.1 10.1 19.9 4.9 79 38
Cu nanoparticles MEA 2.4b 144 35.2 30.4 3.6 1.8 71 39
a b
The potential refers to RHE. The potential represents the full-cell potential (V).

Although Cu(100) is selective for C2H4 formation, it is less

stable than Cu(111) and easily undergoes surface reconstruc-
tion into Cu(111) during electrocatalysis.28 The design and
preparation of the Cu(100) catalyst with outstanding stability,
especially in the catalytic process, is attractive. Recently,
Sargent and co-workers demonstrated that the adsorbed spe-
cies on the catalyst surfaces formed in the electrocatalytic
CO2RR, including *CO2, *COOH and *CO, reshaped the facet
of Cu catalysts, stabilizing the Cu(100) facet.28 The density
functional theory (DFT) calculations indicate that in the
absence of the adsorbed species, the surface energy of the
Cu(111) facet is 1.25 J cm 2, lower than that of Cu(100)
(1.43 J cm 2) (Fig. 6b). The surface energy of Cu(100) decreased
significantly with an increase in the coverage of the adsorbed
species formed during the CO2RR, while the surface energy of Fig. 6 (a) Product distributions in the electrocatalytic CO2RR over Cu
Cu(100) changed only slightly with an increase in the coverage single-crystal catalysts at a current density of 5 mA cm 2 in the H-cell with
a 0.1M KHCO3 electrolyte.40 (b) Surface energy as functions of surface
of *H species derived from the HER (Fig. 6b). On the contrary, coverage in the CO2RR and HER intermediates.28 (c) Molecular structures
the surface energy of Cu(111) remained unchanged in the of different polyamines.29 (d) FE of C2H4 over Cu–polyamine catalysts in
presence of surface species formed either in the CO2RR or the flow cell with a 1M KOH electrolyte.29
HER (Fig. 6b). These results suggest that the adsorbed species
formed in the CO2RR favour the reconstruction of Cu surfaces
into Cu(100) under CO2RR conditions in the presence of CO2, Cu-HER). Because of the higher fraction of Cu(100), the Cu-CO2RR
whereas Cu(111) is favoured under HER conditions in the absence catalyst offered FEs of C2H4 and C2+ compounds of 70% and 90%,
of CO2. By the in situ electrodeposition of Cu using Cu(II) bitartrate respectively, with a current density of about 310 mA cm 2 at
under CO2RR conditions with a current density of 400 mA cm 2 0.67 V vs. RHE in an alkaline flow cell (7M KOH). In contrast,
(denoted as Cu-CO2RR), a 70% increase in the ratio of the Cu(100) when the Cu-HER catalyst was used for the electrocatalytic CO2RR,
facet area to the total facet area was observed as compared to the FEs of C2H4 and C2+ became significantly lower, being 57%
that under HER conditions in the absence of CO2 (denoted as and 77%, respectively.28

Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
The modification of Cu by organic polymers with desired
functionality can influence the adsorption and activation of
reactants and intermediates, offering an opportunity to tune
the selectivity of CO2RR products. Gewirth and co-workers
recently demonstrated that the incorporation of polyamine
onto the Cu catalyst significantly improved the C2H4 selectivity
in the electrocatalytic CO2RR.29 Poly-N-(6-aminohexy) acryla-
mide (R-NH2) was selected as the precursor polymer, and the
methylation of R-NH2 resulted in the mixture of R-NHMe,
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
R-NMe2, and R-NMe3+ groups in the polymer (Fig. 6c). The
polyamine without methylation was denoted as P1. The methy-
lated product that contained only R-NMe3+ was defined as the
100% methylated polymer, and P2, P3 and P4 were 35%, 65%
and 100% methylated, respectively. The co-electroplating of Pi
(i = 1–4) and CuSO4 on the gas diffusion layer led to a Cu-
polyamine hybrid catalyst (denoted as Cu-Pi). As compared to
Cu without polyamine modification, the Cu-P1 catalyst exhib-
ited significantly enhanced C2H4 selectivity in the whole
potential range in the CO2RR using the flow cell with a 1.0M
KOH electrolyte. The FE of C2H4 over the Cu-P1 catalyst reached
72% with a current density of 433 mA cm 2 at 0.97 V vs. RHE,
whereas the FE of C2H4 over Cu alone was only 27% with a
current density of 207 mA cm 2 (Fig. 6d). The methylation of
polyamine decreased the FE of C2H4 but significantly increased
that of H2 and a higher degree of methylation resulted in a
lower FE of C2H4 (Fig. 6d). This indicates that the amino group
in P1 is the key to enhancing C2H4 formation, whereas the
presence of methyl groups favours H2 evolution. The amino
group might promote CO2 adsorption via an acid–base inter-
action, resulting in a higher local CO2 concentration on the
surface. In addition, it was emphasized that the presence of
amino groups shifted the equation of HCO3 + R–NH2 -
CO32 + R–NH3+ to the right, resulting in an increased amount
of CO32 and a high pH value at the surface region, which
might enhance the C–C coupling.29 An increase in KOH
concentration from 1.0 to 10M increased the FE of C2H4 to 87
 3% with a current density of 32 mA cm 2 at 0.47 V vs. RHE
over the Cu-P1 catalyst, further demonstrating that the higher
pH is beneficial to C2H4 formation. To the best of authors’
knowledge, this represents the highest FE value reported to
date in the electrocatalytic CO2RR to C2H4.29
Similar to the CO2RR, the electrocatalytic CORR also shows
the facet dependence of product selectivity. Through studies
with Cu single crystals, Koper and co-workers found that in the
electrocatalytic CORR, CH4 formation was favoured on Cu(111),
whereas C2H4 was favoured on Cu(100) at low overpotentials.41
The Cu(110) facet showed a similar potential dependence to
Cu(111), but the formation of some alcohols was observed.41
It is known that the increase in the alkalinity of the electro-
lyte is beneficial to enhance the C2H4 selectivity in the electro-
catalytic CO2RR.13 However, in the electrocatalytic CORR over
an oxide-derived Cu catalyst, although the FE of C2+ com-
pounds increased with the concentration of the KOH electro-
lyte, the molar ratio of acetate (CH3COO ) to other C2+
compounds increased with the alkalinity.25 The highest FE of
C2H4 in the electrocatalytic CORR with pure CO as the reactant
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
over the Cu-based catalyst was about 50%, which was signifi-
cantly lower than that (87%) in the CO2RR.
A few recent studies have been devoted to developing
strategies to facilitate C2H4 formation in the electrocatalytic
CORR. Usually, in the case of using an H-cell, the low solubility
of CO in aqueous electrolytes results in a low concentration of
local CO on the catalyst surfaces, thus limiting the product
selectivity because of the competitive H2 evolution. Deng and
co-workers reported that the increase in the hydrophobicity of
catalyst supports (carbon papers) by PTFE treatment reduced
the H2O availability and improved the CO availability on Cu
surfaces, thus improving the FE of C2H4 at the expense of that
of H2.34 When the PTFE content increased from 5 to 13 wt%
and further to 25 wt%, the contact angle of water droplets
increased from 132.81 to 143.91 and further to 147.21 (Fig. 7a),
indicating an increase in the hydrophobicity. The FE of C2H4
increased significantly with an increase in the PTFE content
during the CORR at 0.7 V vs. RHE over a Cu nanoparticle
catalyst in a 1M KOH in the H-cell (Fig. 7a). The loading of the
Cu catalyst onto the GDE, which had a contact angle of 155.61,
offered 52.7% FE of C2H4 with a current density of 28 mA cm 2
(Fig. 7a).34
Sinton, Sargent and co-workers demonstrated that the
control of CO concentration on the catalyst surfaces by manip-
ulating the partial pressure of CO played a crucial role in tuning
the selectivity of C2H4 during the electrocatalytic CORR.25 The
flow cell and alkaline electrolyte (KOH) were employed in their
work. When pure gaseous CO without dilution was used as
a reactant in the CORR over an oxide-derived Cu catalyst, a wide
distribution of C2+ products, including C2H4, CH3COO ,
C2H5OH and n-C3H7OH, was observed, and the FE of C2H4
was about 30% at 0.44 V vs. RHE in 1M KOH, lower than that
of C2+ oxygenates (42%). Upon decreasing the CO concentration
from 100% to 10% (diluted with N2), the FE of C2H4 increased
significantly from 30% to 50% at the expense of CH3COO and
n-C3H7OH (Fig. 7b). A further decrease in CO concentration to
Fig. 7 (a) FEs of CORR products over Cu catalysts with different hydro-
phobicity at 0.7 V vs. RHE in an H-cell with a 1M KOH electrolyte.34
(b) FEs of CORR products with different CO concentrations over an oxide-
derived Cu catalyst at 0.44 V vs. RHE in a flow cell with a 1M KOH
electrolyte.25 (c) The proposed scheme to explain the effect of CO
coverage on the formation of C2H4 and C2+ oxygenates.25
Chem. Soc. Rev.

Tutorial Review
2.5% rather decreased the FE of C2H4 and increased that of H2.
This suggests that a suitable CO concentration is beneficial to
the selectivity of C2H4; a too higher CO concentration leads to
the formation of more C2+ oxygenates, whereas H2 is formed
seriously at a too lower CO concentration due to the mass-
transport limitation of CO. By further tuning the conditions to
constrain local CO concentrations, the FE of C2H4 reached
65–72% at a current density of 120–1250 mA cm 2. Such an
FE of C2H4 represents the highest value reported to date in the
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
electrocatalytic CORR. DFT calculations unravelled that a low
CO coverage on Cu surfaces promoted the dehydroxylation of
*CH*COH into *C*CH, and thus enhanced the formation of
C2H4 (Fig. 7c). On the other hand, a high CO coverage favoured
the hydrogenation of *CH*COH to *CHCHOH, leading to C2+
oxygenates (Fig. 5c).25 It is noteworthy that, experimentally,
the formation of C2H5OH was not significantly affected by
changing the local CO concentration and the FE of C2H5OH
even slightly increased with a decrease in CO concentration
(Fig. 7b). Future studies are needed to elucidate the difference
in mechanisms for the formation of C2H5OH and other C2+
oxygenates (i.e., CH3COO and n-C3H7OH).
4.1.2. Formation of C2+ oxygenates. As already mentioned,
C2H4 is usually the major product during the Cu-based electro-
catalytic CO2RR, although C2+ oxygenates, including C2H5OH,
CH3COO and n-C3H7OH, can also be formed. The ratio of FEs
of C2+ oxygenates to olefins is typically lower than 0.5 on a
single Cu catalyst. DFT calculations also indicate that the
formation of C2H4 is energetically more favourable than that
of C2H5OH, which is the major product in C2+ oxygenates, via a
CH2CHO* intermediate on the Cu(100) surface.23 Thus, if C2+
oxygenates are the target products in the electrocatalytic
CO2RR, new strategies are needed to improve the FE of C2+
oxygenates.
On the other hand, as compared to the CO2RR, the
Cu-catalysed electrocatalytic CORR often shows higher selectiv-
ity of C2+ oxygenates because of higher local CO concentration
on Cu surfaces.25 Considering these facts, it is generally
believed that the design of bimetallic catalysts composed of
Cu and a metal that is capable of catalyzing CO2 to CO, such as
Ag, Au and Zn, would enhance the selectivity of C2+ oxygenates
in the electrocatalytic CO2RR (Fig. 8).11,30,31 The combination of
Cu with carbon materials and the engineering of catalyst
Fig. 8 Functioning mechanism of bimetallic Cu catalysts composed of
Cu and a metal with CO-producing ability, such as Ag, Au or Zn, for the
electrocatalytic CO2RR to C2H5OH.
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
morphology have also been demonstrated to be useful strate-
gies to enhance the selectivity of C2+ oxygenates in the electro-
catalytic CO2RR.14,32
Among the bimetallic catalysts investigated, the Cu–Ag
catalyst shows great promise for obtaining high selectivity of
C2+ oxygenates, in particular C2H5OH, in the electrocatalytic
CO2RR. Through DFT calculations, Sargent and co-workers
demonstrated that the introduction of Ag onto Cu(111) surfaces
enabled the formation of C2H5OH more favourably than that
of C2H4.30 They fabricated bimetallic Cu–Ag catalysts with
different Ag/Cu ratios by a co-sputtering method. The XRD
and XAS characterization studies revealed that Ag and Cu were
in an alloy phase. The best CO2RR-to-C2H5OH performance was
obtained on the catalyst with an Ag/Cu ratio of 0.14/0.86, and
the FE of C2H5OH reached 41% with a current density of 250
mA cm 2 at 0.67 V vs. RHE in a flow cell with a 1.0M KOH
electrolyte. On the other hand, the FE of C2H5OH on pure Cu
was only 29% at the same time. The key intermediate for the
formation of C2H4 (*C*CH) is more unsaturated than that of
C2H5OH (*CH*CHOH) (Fig. 5). It is likely that a highly coordi-
nated surface can stabilize a more unsaturated intermediate.30
Thus, Sargent and co-workers emphasized that the formation of
C2H4 was more favoured on the highly coordinated surface. The
introduction of Ag on the Cu surface disrupted the coordina-
tion environment of Cu, thus destabilizing the *C*CH inter-
mediate and promoting C2H5OH formation.30
Meyer and co-workers reported that smaller Cu–Ag bimetal-
lic nanoparticles promoted the formation of CH3COO during
the electrocatalytic CO2RR in an H-cell with the KHCO3
electrolyte.31 A series of CunAgm bimetallic nanoparticles were
fabricated by the electroreduction of poly-Fe(vbpy)3(PF6)2 film
electrodes on glassy carbon followed by the surface binding of
salts of cations (Cu2+, Ag+) and electroreduction. It was found
that the FE of CH3COO increased significantly with an
increase in the Ag content in the bimetallic catalyst during
the electrocatalytic CO2RR in a 0.5M KHCO3 at 0 1C and
reached a maximum over the Cu2Ag3 catalyst (Fig. 9a). The
further optimization of reaction conditions resulted in a
CH3COO FE of 21.2% over the Cu2Ag3 catalyst at 1.33 V vs.
RHE in a 0.5M KHCO3 with 8 ppm benzotriazole added
at 0 1C.31
The combination of Cu catalysts with carbon nanomaterials
is another promising strategy to enhance C2+ oxygenate selec-
tivity in the electrocatalytic CO2RR. Han and co-workers
reported that a catalyst composed of an N-doped graphene
quantum dot (NGQ) and oxide-derived Cu nanorod (Cu-nr) was
both highly selective in the formation of C2+ alcohols (including
C2H5OH and n-C3H7OH) and highly stable during the CO2RR.14
The NGQ/Cu-nr catalyst was fabricated by blending an NGQ
and a CuO nanorod through sonication, followed by electro-
reduction on a PTFE-based GDE. Characterization studies of
the catalyst morphology by SEM and TEM and the local
structure of Cu by X-ray absorption spectroscopy (XAS) indi-
cated that the NGQ was uniformly dispersed on the Cu-nr and
the NGQ did not change the coordination structure of Cu. In
the electrocatalytic CO2RR over the NGQ/Cu-nr catalyst, the FE
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
Fig. 9 (a) FE of CH3COO over CunAgm catalysts in an H-cell with a 0.5M
KHCO3 electrolyte.31 (b) FEs of C2+ products in the electrocatalytic CO2RR
(left panel) and CORR (right panel) over different catalysts at 0.9 V vs. RHE
in a flow cell with a 1.0M KOH electrolyte.14 (c) FE of C2H5OH in the
electrocatalytic CO2RR over a carbon-supported Cu catalyst with different
Cu loadings in an H-cell with a 0.1M KHCO3 electrolyte.32 (d) Product
distributions in the electrocatalytic CORR over a Cu nanoflower catalyst in
an H-cell with a 0.1M KOH electrolyte.35
of C2+ alcohols reached 52.4% with a current density of
282 mA cm 2 at 0.9 V vs. RHE in a flow cell with a 1M KOH
electrolyte, whereas the FEs of C2+ alcohols over bare NGQ and
Cu-nr were only 15% and 28.1%, respectively (Fig. 9b). The
NGQ/Cu-nr catalyst was stable during the electrocatalytic
CO2RR and the performance was maintained for 100 h of
operation at 0.9 V vs. RHE. Furthermore, the NGQ/Cu-nr
catalyst was highly selective toward the formation of C2+
alcohols in the electrocatalytic CORR and the FE of C2+ alcohols
reached 75.3%, whereas the FE of C2+ alcohols over the Cu-nr
alone was only 35.1% during the CORR (Fig. 8b). This result
suggests that the increased FE of C2+ alcohols over the NGQ/
Cu-nr catalyst may not arise from the high local CO via spillover
or the tandem effect like over the Cu–Ag bimetallic catalyst but
stem from the improved stability of intermediates towards the
formation of C2+ alcohols. DFT calculations revealed that the
incorporation of a layer of N-doped graphene onto Cu(111)
stabilized the O atom of the CH2CHO* intermediate, enabling
the formation of C2H5OH more favourably than C2H4 via the
CH2CHO* intermediate.14
Recently, Xu, Liu and co-workers demonstrated that not only
the nature of carbon materials but also the dispersion of
Cu atoms modulated the performance in the electrocatalytic
CO2RR.32 They developed a carbon-supported Cu catalyst with
different loadings (denoted as Cu/C-x, where x is the Cu loading
in wt%) and dispersions using amalgamated Cu–Li as the
precursor. The high-angle annular dark-field and aberration-
corrected scanning transmission electron microscopy (HAADF-
STEM) and the extended X-ray absorption fine structure
(EXAFS) characterization study indicated that the Cu species
in the as-prepared catalyst was mainly in the form of a single
atom with low Cu loadings of 0.1–0.4 wt%, and then evolved
into a mixture of Cu single atom, CuO and Cu clusters as the
Cu loading increased to 0.8 wt% or higher. For the Cu/C-0.1,
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
Cu/C-0.4 and Cu/C-0.8 catalysts, the FE of C2H5OH displayed
almost the same profile with a change in potential; the onset
potential was 0.4 V vs. RHE and the FE of C2H5OH reached a
maximum of about 90% at 0.7 V vs. RHE in an H-cell with a
0.1M KHCO3 electrolyte (Fig. 9c). As the Cu loading increased to
1.6 wt% or higher, the maximum FE of C2H5OH dropped to less
than 40% (Fig. 9c) and the FE of H2 increased. This result
suggests the important role of atomically dispersed Cu sites in
the as-prepared catalyst in promoting C2H5OH formation.
Further operando XAS studies showed the reversible trans-
formation of atomically dispersed Cu species to Cun clusters
(n = 3, 4) under CO2RR conditions.32 During the procedure of
catalyst synthesis, a highly basic solution from the dissolved
LiOH was formed, activating the carbon surface to form hydro-
xyl groups, and the hydroxyl groups were found to play a key
role in tuning the interaction between the catalytic centre and
the carbon substrate.32 It is worth mentioning that the 91% FE
of C2H5OH achieved in this work represents the highest value
reported to date for the electrocatalytic CO2RR despite the low
current density (1.23 mA cm 2).
As already mentioned, the electrocatalytic CORR achieves
high selectivity of C2+ oxygenates than the CO2RR. Many recent
studies have contributed to further enhancing the selectivity
of C2+ oxygenates in the electrocatalytic CORR. Jaramillo and
co-workers demonstrated that the increase in the roughness
factor of Cu catalysts is an effective strategy to direct the
electrocatalytic CORR towards C2+ oxygenates.35 Through
studies using Cu catalysts with different morphologies, such
as nanodendrites, nanoflowers, nanorods and nanowires, they
found that the geometric current density and the FE of C2+
oxygenates increased significantly with an increase in the
roughness factor.35 Over a Cu nanoflower catalyst with the
highest roughness factor, the FE of C2+ oxygenates, including
C2H5OH, CH3CHO and CH3COO , attained nearly 100% at only
0.23 V vs. RHE in an H-cell with a 0.1M KOH electrolyte in
spite of the low current density (0.2 mA cm 2) (Fig. 9d).
CH3CHO was the major product with an FE of about 60% at
0.23 V vs. RHE, and the change of potential to 0.33 V vs. RHE
offered C2H5OH as the major product with an FE of about 60%.
The roughness factor-normalized current densities were not
significantly different over different catalysts, further indicating
that the roughness factor determined the product selectivity in
the electrocatalytic CORR. It is proposed that the porous
mesostructure with a high roughness factor may contribute
to suppressing the HER and enabling the highly selective
formation of C2+ oxygenates.35
As discussed earlier, the product selectivity during the
electrocatalytic CORR depends on the facet of Cu catalysts,
and the studies using Cu single crystals have shown that the
Cu(100) and (110) facets are favourable for C2H4 and C2H5OH
formation, respectively, whereas the formation of C2+ com-
pounds is not favoured on Cu(111).40 Recently, Kang, Jiao and
co-workers reported that a two-dimensional Cu nanosheet
catalyst with the (111) facet selectively exposed surprisingly
worked for the electrocatalytic CORR to CH3COO .36 The
catalyst was fabricated through the chemical reduction of
Chem. Soc. Rev.
 View Article Online

Tutorial Review Chem Soc Rev

cupric nitrate by L-ascorbic acid in the presence of hexadecyl-

trimethylammonium bromide (CTAB) and hexamethylenetetra-
mine (HMTA).36 During the electrocatalytic CORR in a flow cell
with a 2M KOH electrolyte, the Cu-nanosheet catalyst offered
CH3COO with an FE of 48% and a current density of
200 mA cm 2 at 0.736 V vs. RHE. This is the highest FE of
CH3COO in the CORR reported to date. Since the Cu
nanosheets selectively exposed the (111) facet, it was proposed
that the high FE of CH3COO over the Cu nanosheet catalyst
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.

might be attributable to the suppressed formation of C2H4 and

C2H5OH, probably because of the decreased exposure of the
(100) and (110) facets. DFT calculations suggested that the
formation of CH3COO proceeded via a *CHCO intermediate
containing an oxygen from CO, and the further incorporation of
another oxygen from OH in the electrolyte led to CH3COO
formation.36
It is noteworthy that the selectivity towards C3 compounds
still remains low in both the electrocatalytic CO2RR and CORR,
although significant advances have been achieved in the selec- Fig. 10 (a) Schematic illustration of the morphology and product selec-
tive formation of C2 compounds, including C2H4, C2H5OH and tivity of a dendritic Cu catalyst before and after thermal annealing for the
electrocatalytic CO2RR.33 Reproduced from ref. 33 with permission from
CH3COO . This is because the formation of a C3 product
American Chemical Society, copyright 2017. (b) DFT calculated reaction
requires active sites not only for C1–C1 coupling but also for barriers (Ea) for C1–C1 and C1–C2 coupling on screened M-doped Cu
C1–C2 coupling. Several strategies have been developed to catalysts (M = Ag, Au, Ru, Rh, and Pd).37 Reproduced from ref. 37 with
enhance the selectivity of C3 oxygenates, in particular n-C3H7OH, permission from Spring-Nature, copyright 2019.
in the electrocatalytic CO2RR and CORR.
Broekmann and co-workers showed that the fabrication of a
have different electronic structures, which might be favourable for
dendritic Cu catalyst by a stepwise method, which included the
the intermolecular coupling between C1 and C2 species, i.e., the
electrodeposition of dendritic Cu under mass-transfer control
asymmetric C1–C2 coupling.37 Among the different metals (Ag, Au,
of Cu(II) ions followed by thermal annealing at 300 1C for
Ru, Rh and Pd), the doping of Ag into Cu displayed the lowest
3 h, enhanced the formation of n-C3H7OH during the electro-
barrier for the C1–C2 coupling as well as a low barrier for the C1–C1
catalytic CO2RR.33 The initial electrodeposited dendritic Cu
coupling (Fig. 10b), and thus, the Ag-doped Cu catalyst might be
catalyst offered HCOO with an FE of 49.2% at 0.7 V vs.
selective for the formation of C3 compounds. A galvanic replace-
RHE and C2H4 with an FE of 34.3% at 1.1 V vs. RHE. It was of
ment reaction driven by the difference in the reduction potential
interest that the thermal annealing treatment of the dendritic
of Ag vs. Cu was exploited to fabricate the Ag-doped Cu catalyst.
Cu catalyst directed the major CO2RR product from C2H4 to C2+
This catalyst offered n-C3H7OH with an FE of 33% at a current
alcohols, including C2H5OH and n-C3H7OH (Fig. 10a). The FE
density of 13.6 mA cm 2 at 0.46 V vs. RHE during the electro-
of n-C3H7OH reached 13.1% with a current density of about
catalytic CORR in a flow cell with a 1M KOH electrolyte.37 This FE
11 mA cm 2 over the thermally treated-Cu catalyst during the
of n-C3H7OH represents the highest value reported to date in the
CO2RR at 0.9 V vs. RHE in an H-cell with a 0.5M KHCO3
electrocatalytic CORR.
electrolyte. It was proposed that the presence of nanometre-
sized Cu particles/Cu crystallites and nanocavities at the
surface of the dendritic Cu after the reduction of oxide pre- 4.2. Effects of reactor design on activity
cursor was responsible for the multiple C–C coupling and the Activity is another key parameter in the electrocatalytic CO2RR
formation of C2+ alcohols.33 and CORR. Both CO2 and CO are stable molecules with high
As compared to the CO2RR, the electrocatalytic CORR carbon–oxygen bonding energy, and thus are not easy to be
achieves higher selectivity towards C3 products. Sargent, Sinton activated and transformed under ambient conditions. There-
and co-workers have developed several strategies to improve the fore, one of the key challenges for the CO2RR and CORR is how
selectivity of n-C3H7OH for the electrocatalytic CORR. These to design catalysts that enable the efficient activation of CO2
strategies include the confinement effect to enhance the con- and CO molecules. Moreover, the formation of C2+ compounds
centrations of C1 and C2 intermediates,42 and the creation of by the electrocatalytic CO2RR or CORR involves multi-step
interfaces between the (100) and (111) facets that are efficient transfers of protons and electrons, and the C–C coupling. The
for the formation of C2 and C1 intermediates,43 respectively. C–C coupling step is generally believed to have a high energy
These two strategies increase the probability of coupling between barrier.
the C1 and C2 intermediates, thus enhancing the selectivity of In addition to catalysts, the electrocatalytic reactor also
n-C3H7OH. DFT calculations by Sargent and co-workers suggested significantly affects the activity of the electrocatalytic CO2RR
that the metal-doping enabled two neighbouring Cu atoms to and CORR. In this section, we highlight the recent advances in

Chem. Soc. Rev. This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
boosting the activity in the electrocatalytic CO2RR and CORR
in both the H-cell and flow cell. Different trends have been
observed for the CO2RR or CORR in different reactors due to
the difference in the mass-transport limitation. Very recently,
some exciting results that exceed the threshold of commercia-
lization (200 mA cm 2) have emerged for the electrocatalytic
CO2RR and CORR. The product formation rate, the single-pass
conversion of CO2 or CO and the product yield if available are
discussed to offer data for potential industrial consideration.
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
4.2.1. H-Cell. Jaramillo and co-workers systematically
studied the electrocatalytic CO2RR and CORR in an H-cell over
a polycrystalline Cu catalyst.27 The CO2RR and CORR were
conducted in CO2-saturated 0.1M KHCO3 and CO-saturated
0.1M KOH electrolytes, the two most widely employed electro-
lytes, respectively. Over a wide range of potentials, the partial
current densities of C2+ products exhibited similar trends in
these two measurements (Fig. 11a), indicating the shared
mechanisms in the two cases. This observation also confirms
that CO is a key intermediate for the formation of C2+ products
in the CO2RR. Despite this similar trend, the onset potentials
for the formation of C2+ products in the CO2RR and CORR were
quite different. The onset potentials of C2+ products in the
CORR were typically about 0.4 V more positive than those in the
CO2RR (Fig. 11a).27 This agrees well with the trend of thermo-
dynamic equilibrium potentials as displayed in Table 1.
Although a lot of efforts have been devoted to enhancing
the activity of the electrocatalytic CO2RR/CORR in an H-cell, the
highest current densities achieved in an H-cell without the
help of a GDE were only B100 mA cm 2 in the CO2RR and
B10 mA cm 2 in the CORR. The highest current density in an
Fig. 11 (a) Partial current densities of individual products in the electro-
catalytic CO2RR and CORR over a polycrystalline Cu in H-cell.27 Repro-
duced from ref. 27 with permission from American Chemical Society,
copyright 2018. (b) C2H4 formation rate with various ratios of CO2/CO in
an H-cell with a 0.1M KHCO3 electrolyte.22 (c) C2+ formation rates over the
F–Cu catalyst in a flow cell with different concentrations of KOH
electrolyte.19
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
H-cell is determined by the mass-transport limitation. According
to the simple semi-infinite diffusion model, the limiting current
density can be calculated by eqn (2),44
jlimit = z  F  D  C/d (2)
where z, F, D, C and d represent the number of electrons, the
Faraday constant, the diffusion coefficient, the solubility and
the diffusion layer thickness, respectively. Under similar reac-
tion conditions, the limiting current density is proportional
to the solubility. In aqueous electrolytes, the solubility of CO2
(34 mM) is significantly larger than that of CO (1 mM), leading
to a significantly higher limiting current density in an H-cell for
the electrocatalytic CO2RR than that for the CORR.
Strasser and co-workers demonstrated that the co-feeding of
CO2 and CO significantly enhanced the formation of C2H4 as
compared to the feeding of CO2 or CO alone onto an oxide-
derived Cu nanoparticle catalyst in an H-cell.22 The rate of C2H4
formation was markedly enhanced by co-feeding CO2 and CO
over the entire range of feed ratios (Fig. 11b). At a CO2/CO ratio
of 1 : 1, the rate of C2H4 formation was about 1.5 times higher
than that with pure CO2 and about 2.3 times higher than that
with pure CO (Fig. 11b). Through studies with an operando
differential electrochemical mass spectrometry (DEMS) capil-
lary flow cell with millisecond time resolution, it was elucidated
that the enhanced C2H4 formation originated mainly from the
cross-coupling between *CO (from CO) and *CO (from CO2).
It was proposed that the co-fed CO did not compete with CO2
for adsorption sites, indicating separate and non-scrambling
reactant-specific adsorption sites for CO2 and CO. Based on
these results, a tandem-catalysis system, which was composed
of a Ni–nitrogen-doped carbon catalyst for the CO2RR to CO
and a Cu catalyst for the CO–CO coupling, was designed to
facilitate the electrocatalytic CO2RR to C2H4.22
4.2.2. Flow cell. The low reaction rate in the H-cell (current
density r100 mA cm 2 for the CO2RR and r10 mA cm 2 for
the CORR) is because, the limited CO2/CO solubility in aqueous
electrolytes has driven studies using reactors of other config-
urations to meet the commercial requirement (current density
Z200 mA cm 2).2 As discussed in Section 2.2, the flow cell with
GDE configuration enables the direct feeding of the reactant
gas through the GDE, thus circumventing the mass-transport
limitation in the H-cell. This makes high reaction rates (current
density Z200 mA cm 2) possible. In particular, over a fluorine-
modified Cu catalyst and an oxide-derived Cu catalyst, the
employment of GDEs and alkaline electrolytes can enhance
the current density to a level of 1 A cm 2 and significantly reduce
the overpotential while maintaining high C2+ selectivity.19,25
The GDE enhances the current density or reduces the over-
potential by increasing the local CO2/CO concentration. The
decreased overpotential at a higher pH value may arise from the
following effects. First, since the C–C coupling is the key step
for the formation of C2+ compounds and usually does not
involve proton transfer, it is suggested that the activity should
be compared at potentials referenced to the standard hydrogen
electrode (SHE).46 Under the same SHE potential, a higher
pH value indicates the lower overpotential according to the
Chem. Soc. Rev.

Tutorial Review
equation of overpotential = E0(vs. RHE) E(vs. SHE) pH  59 mV.
Second, a higher pH can increase the electrolyte conductivity, thus
lowering the charge-transfer resistance.13,38 The enhanced C2+
product selectivity at a higher alkalinity is generally believed to arise
from the following reasons: (i) a higher pH of the electrolyte can
suppress the HER because of the slow kinetics of the first H2O
reduction step, thus enhancing the reduction of CO2; (ii) computa-
tional studies reveal that a higher pH environment promotes C–C
coupling through enhancing the dimerization of *CO.45 It should be
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
noted that a higher pH may reduce the local CO2 availability
because of the reaction between CO2 and OH , and thus may not
always enhance the performance of the electrocatalytic CO2RR to
C2+ compounds.
Recently, our group reported that a halogen-modified Cu
(denoted as X–Cu) catalyst achieved high activity during the
electrocatalytic CO2RR to C2+ compounds in an alkaline flow
cell.19 The fluorine-modified Cu catalyst was fabricated by the
electroreduction of the Cu(OH)F precursor synthesized by a
solvothermal method. Other halogen-modified Cu catalysts
were obtained by the anion exchange of Cu(OH)F, followed by
electroreduction. Both the FE of C2+ products (mainly C2H4 and
C2H5OH) and the current density increased with the electro-
negativity of halogen in the X–Cu catalysts, and the F–Cu
catalyst offered the best performance. A higher concentration
of KOH electrolyte favoured the formation rate of C2+ com-
pounds at a lower applied potential, but accelerated the carbo-
nate formation, reducing the availability of CO2 for the
operation under a higher current density (Fig. 11c). At a KOH
concentration of 0.75M, an ultrahigh current density of
1.6 A cm 2 was achieved with a C2+ FE of 80% at 0.89 V vs.
RHE, and the C2+ formation rate reached B4 mmol h 1 cm 2
(Fig. 11c), the highest value reported to date.19 The CO2 single-
pass conversion and the C2–4 selectivity on a molar carbon
basis at a CO2 flow rate of 20 mL min 1 reached 19.3% and
85.8%, respectively, which are comparable to the best values
obtained in thermocatalytic processes at high temperatures
and pressures.19
Current densities of 41 A cm 2 have also been achieved in
the electrocatalytic CORR to C2+ compounds in alkaline flow
cells. For example, Jiao and co-workers reported that an oxide-
derived Cu catalyst attained a current density of 1.05 A cm 2
with a C2+ FE of 79% in a 1M KOH electrolyte.38 Sargent, Sinton
and co-workers demonstrated a current density of 1.25 A cm 2
with a 65% FE of C2H4 by constraining local CO concentration
as discussed in Section 4.1.1.25
Kanan and co-workers recently achieved a high CO single-
pass conversion for the electrocatalytic CORR using the MEA
cell.39 At a cell voltage of 2.4 V, the CO single-pass conversion
reached 43% and the concentration of CH3COO , the major
product, attained 1.1M after 24 h of operation. The current
density and the FE of CH3COO were 144 mA cm 2 and 43%,
respectively. It is noteworthy that a very low CO flow rate
(1.0 mL min 1) and a relatively high CO pressure (4 bar) were
adopted in this work.39
Comparative studies for the electrocatalytic CO2RR and
CORR in a flow cell have been performed.19,38 Under a fixed
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
potential of 0.6 V vs. RHE, our group found that the current
density during the electrocatalytic CORR was similar to that
during the CO2RR over Cu alone, and only a slightly larger
current density was observed during the CORR over halogen-
modified Cu catalysts.19 Jiao and co-workers showed that the
cell voltage for the electrocatalytic CORR was about 0.1 V lower
than that for the CO2RR over an oxide-derived Cu catalyst at a
constant current density of 300 mA cm 2.38 These observa-
tions indicate that the electrocatalytic CORR possesses a
similar or only a slightly higher activity as compared to the
CO2RR at high reaction rates without the mass-transport
limitation. This similarity also suggests that the formation
of CO may not be the rate-determining step in the electro-
catalytic CO2RR to C2+ compounds. It is noteworthy that
although the electrocatalytic CO2RR and CORR show similar
current densities or voltages in a flow cell, the electrocatalytic
CORR usually exhibits higher C2+ formation rate than that of
CO2RR because fewer electrons are involved as discussed in
Section 2.1.
4.3. Stability
Stability is also an important parameter for the electrocatalytic
CO2RR and CORR, in particular for industrial-relevant high-
rate systems. However, the stability issue under reaction
conditions has attracted considerably less attention as com-
pared to the selectivity and activity issues. The stability issue
includes the stability of catalysts and electrochemical systems.
In this section, some key parameters determining the stability
are analysed, including the potentials, alkalinity and reactor
configurations. Strategies to improve the stability, including
the doping of heteroatom, the modification of the GDE and
the design of new reactor configurations, are highlighted.
To maintain long-term stability is a challenge for Cu-based
catalysts because of the restructuring of surfaces under reaction
conditions. For example, as discussed in Section 4.1, although
Cu(100) shows high selectivity for C2H4 formation, it undergoes
reconstruction during electrocatalysis.28,47 Buonsanti and co-
workers demonstrated that small clusters were detached from
Cu nanocubes that mainly exposed the (100) facets during the
electrocatalytic CO2RR.47 The gradual disintegration of indivi-
dual cubes occurred during the reaction, eventually leading to
coalescence. This was accompanied by a decrease in FE for the
CO2RR and an increase in that for the HER. It was proposed
that a potential-induced fragmentation into nanoclusters was
the predominant degradation pathway for Cu nanocubes.47
Another example is the stability of oxide-derived Cu catalysts.
As compared to pure metallic Cu, the oxide-derived Cu catalyst
usually show improved selectivity towards C2+ products.
Although the nature of actives sites is still under debate, it is
generally believed that the Cud+ site plays an important role in
enhancing C2+ formation.2,48,49 However, Cud+ is easily reduced
to metallic Cu under CO2RR conditions, leading to decreased
C2+ selectivity. The doping of boron or nitrogen was reported to
stabilize the Cud+ site, enabling the stable operation of B40
h.48,49 We propose that anodic pulses to re-oxidize the Cu
surface at regular intervals can also be helpful to maintain or
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
restore the performance. More effective strategies should be
developed to improve the stability of Cu-based catalysts.
In addition, it is also a big challenge to maintain the
operational stability of the entire electrochemical reactors. As
discussed in Section 4.2.2, the flow cell with GDE configuration
successfully circumvents the mass-transport limitation of CO2
in aqueous solutions, attaining high reaction rates in the
electrocatalytic CO2RR to C2+ compounds. In particular, the
employment of an alkaline GDE improves the current density
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
during the electrocatalytic CO2RR to 41 A cm 2.19,25 However,
to achieve long-term stability remains a challenging task using
the alkaline flow cell due to the flooding of GDE and the salt
accumulation.
The flooding issue arises from the penetration of H2O into
the GDE when the surface of carbon in the GDE turns from
hydrophobic to hydrophilic during the long-term operation.
The flooding becomes more serious at high applied potentials
and high concentrations of OH in the electrolyte. Because of
the flooding, the diffusion of CO2/CO in the gas phase toward
the electrocatalyst would be obstructed after a few hours of
operation (Fig. 12a). The modification of the carbon-based GDE
by superhydrophobic fluoroalkyl silane to enhance the hydro-
phobicity is a useful strategy to suppress the flooding of GDE.
The electrocatalytic CO2RR to C2H4 and C2H5OH was stable for
40 h at a fixed current density of 400 mA cm 2 by such a
modification.19 Another strategy to overcome the problem of flood-
ing is to use a non-carbon-based GDE such as a porous PTFE
membrane, which is chemically stable in a highly alkaline
environment.13,14 For example, Han and co-workers demonstrated
that the PTFE-based GDE could be operated for 100 h with a current
density of 282 mA cm 2 at 0.9 V vs. RHE during the electrocatalytic
CO2RR to C2+ alcohols as discussed in Section 4.1.2.14
The salt accumulation issue on the GDE mainly originates
from the formation of carbonates by the reaction of CO2 with
OH , as well as the accumulation of products such as formate
and acetate. This would block the pores of GDE, hindering the
diffusion of CO2 on the catalyst surface and reducing the
conductivity of the GDE (Fig. 12b). The undesirable reaction
of CO2 with OH also results in carbon loss and a lower pH
value of the electrolyte, which is unbeneficial to sustain the
high activity and C2+ selectivity as discussed above. Refreshing
the electrolyte regularly or purging the electrolyte without
circulation supresses the salt accumulation, but the operating
Fig. 12 (a) Illustration of the GDE flooding issue in the electrocatalytic CO2RR and CORR. (b) Illustration of the GDE salt accumulation issue in the
electrocatalytic CO2RR. (c) The electrocatalytic CORR without salt accumulation.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
cost and the energy consumption would be increased signifi-
cantly. In this regard, the indirect route via CO may avoid the
carbonate formation, because the reaction of CO with OH in
the electrocatalytic CORR in the alkaline flow cell is not serious,
and thus improved stability may be expected (Fig. 12c). Never-
theless, so far, there has been no report disclosing the long-
term stability for the electrocatalytic CORR to C2+ compounds
in the alkaline flow cell.
The design of the MEA cell may be a promising strategy to
improve the stability. As discussed in Section 2.2, the cathodic
GDE is directly pressed up against an ion exchange membrane
without using a catholyte in the MEA system. By eliminating the
catholyte, the problems caused by the flooding of the GDE and
the carbonate formation may be circumvented, resulting in
better stability. Recently, Sargent and co-workers demonstrated
a stable operation for 190 h during the electrocatalytic CO2RR
to C2H4 with an FE of C2H4 of about 60% and a current density
of 120 mA cm 2 at a cell voltage of 3.65 V in MEA with a neutral
medium.50 This is probably the longest lifetime reported to
date for the electrocatalytic CO2RR to C2+ compounds. However,
up to date, the MEA system, which is capable of working for the
selective formation of C2+ compounds, can only be operated at a
low current density as well as a high cell voltage because of the
low local pH and the low ion conductivity. More efforts should be
put into enhancing the ion conductivity of the ion exchange
membrane and the assembly craft.
The acidic flow cell is seldomly investigated for both the
electrocatalytic CO2RR and CORR to C2+ compounds. This is
probably because the competing HER in the acidic medium is
more severe than those in neutral and alkaline media, resulting
in low selectivity of C2+ compounds. However, the acidic
environment can significantly supress the flooding and salt
accumulation issues, and can improve the reaction kinetics.
Thus, better stability and activity can be expected. It is worth
mentioning that the life time of the acidic fuel cell is at least
one order of magnitude longer than that of the alkaline fuel
cell.15 Since the fuel cell has a similar reactor configuration to
the electrocatalytic CO2RR and CORR, making the acidic flow
cell a promising alternative. We propose that the combination
of modifiers containing hydrophobic functional groups with
Cu-based catalysts to suppress the adsorption of H2O and
promote that of CO2 or CO would be helpful to supress the
HER and improve the C2+ selectivity.
Chem. Soc. Rev.

Tutorial Review
In this section, we systematically analyse the similarities and
differences in the electrocatalytic CO2RR and CORR in terms of
selectivity, activity and stability. Although CO is believed to be
the key intermediate in the electrocatalytic CO2RR involving
C–C coupling, the distributions of C2+ products are different for
the electrocatalytic CO2RR and CORR. The CO2RR usually
shows better selectivity to C2H4 than that to C2+ oxygenates,
whereas the CORR has demonstrated better selectivity to C2+
oxygenates. Although the electrocatalytic CORR shows more
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
positive onset potentials for C2+ formation in the H-cell, the
highest current density achieved in the electrocatalytic CORR
(o10 mA cm 2) is one-order of magnitude lower than that of
the CO2RR (o100 A cm 2) due to the lower solubility of CO in
aqueous electrolytes. The flow cell with GDE configuration has
successfully circumvented the mass-transport limitation of CO2
or CO and enabled the current density to reach a level of
1 A cm 2. Since both ethylene and ethanol can be formed with
high FEs during the electrocatalytic CO2RR or CORR, and both
are very important chemicals in the current chemical industry,
we envisage that these two products are the most promising
targets in the future practical process for the electrocatalytic
CO2RR or CORR. Despite the significant progress in the selec-
tivity and activity of the electrocatalytic CO2RR and CORR, the
long-term stability is still a challenging issue. The stability
issues include the stability of catalysts and electrocatalytic
reactors. Doping of the heteroatom, modification of the GDE
and the design of new reactor configurations have been demon-
strated to improve the stability.
5. Summary and outlook
There are two major routes for the electrocatalytic CO2RR to C2+
compounds, i.e., the direct route and the indirect route via CO.
Although a lot of efforts have been devoted to elucidating the
mechanism for the electrocatalytic CO2RR and CORR, it is
noteworthy that so far most of the mechanistic insights have
been gained through DFT calculations. More in situ spectro-
scopic studies should be conducted, in particular under con-
ditions with high reaction rates. The comparison of the
differences in reaction intermediates between the electro-
catalytic CO2RR and CORR would also be very helpful to deepen
the understanding of the activation and C–C coupling of CO2
and CO molecules to high-value C2+ compounds.
As compared to the indirect route via CO, the direct CO2RR
possesses advantages of potentially lower capital cost and lower
product separation cost. The CO2RR usually shows better
selectivity to C2H4 than that to C2+ oxygenates. Therefore, if
C2H4 is the target, the direct CO2RR seems very appealing.
However, the problems of CO2 loss because of the carbonate
formation with the alkaline electrolyte and the instability
during long-term operation should be overcome. The CORR
has demonstrated better selectivity to C2+ oxygenates. Therefore,
the electrocatalytic CORR or the indirect electrocatalytic conver-
sion of CO2 via CO would be a better choice if C2+ oxygenates are
the target products. Another advantage of the electrocatalytic
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
CORR lies in the fact that the reaction of the reactant with OH
in the alkaline electrolyte, which is a serious problem in the
CO2RR using an alkaline flow cell, can be avoided. The instability
caused by the salt accumulation in the case of CO2RR may also be
circumvented. It is estimated that if the electricity prices fall below
4 cents per kilowatt hour, the production of CO from the electro-
catalytic CO2RR will be competitive with fossil fuel-derived CO,5
further indicating the techno-economic feasibility of the indirect
route. We expect that the electricity prices will be significantly
lowered because of the recent progress in generating electricity
from renewable energy sources. The toxicity of CO is also an issue
that needs to be considered. Fortunately, CO as a reactant
has been widely used in the field of traditional thermocatalysis,3
and there are mature and safe technologies for the storage and
use of CO.
Cu is the only efficient catalyst for both the electrocatalytic
CO2RR and CORR to C2+ compounds because of the moderate
CO binding energy. Several strategies have been developed to
improve the efficiency of Cu-based catalysts for C2+ formation.
The facet tuning and polymer modification were reported to
enhance C2H4 selectivity, while the bimetallic catalysis, mor-
phology engineering and Cu–carbon composites could promote
the formation of C2+ oxygenates. However, the selectivity of a
specific C2+ product still needs further improvement, and the
active sites of these Cu-based catalysts have not been well
understood because of the complex morphologies and struc-
tures. New strategies and operando characterization studies are
needed in the future. As an example of future directions, we
propose that the functionalization of Cu surfaces with organic
molecules can finely tune the local environment of active sites
and the stabilities of reaction intermediates to direct the
reaction pathway, and thus holds the potential to achieve high
selectivity of a specific C2+ product. In addition, single-atom
and metal-cluster catalysts provide well-defined active sites for
the electrocatalytic CO2RR and CORR, deserving more research
in the future.
The combination of selectivity and activity for the electro-
catalytic CO2RR using a flow cell with an alkaline GDE has met
the requirement for commercialization without considering
other parameters. However, the long-term stability is still a
challenging issue. Thus, to improve the long-term stability, an
industrial-relevant current density should be the first priority
from the viewpoint of practical applications. In addition to the
stability of Cu-based catalysts, the flooding of the GDE and the
salt accumulation during the long-term operation should be
circumvented. The functionalization of the carbon-based GDE
and the exploration of the non-carbon GDE are useful strategies
to extend the lifetime by avoiding the quick flooding of the GDE
under alkaline conditions, particularly at high current densi-
ties. The design of new reactor configurations, such as the MEA
cell, to eliminate the alkaline catholyte holds the potential to
improve the stability. Furthermore, the indirect route via CO
can avoid the carbonate formation, thus contributing to
improving the stability. However, there is still no report demon-
strating the 5000 h of stable operation of the electrocatalytic
CO2RR or CORR, which is believed to be the first cornerstone
This journal is © The Royal Society of Chemistry 2021

Chem Soc Rev
for an electrocatalytic process.6 More effort should be put in
improving the stability in the future.
In addition to reporting selectivity, activity and stability, we
further emphasize that the energy conversion efficiency, in
particular the full-cell energy conversion efficiency, should be
reported. This would be helpful for further techno-economic
analysis. The highest full-cell energy conversion efficiency
reported to date is only about 30%, still far from the target of
60% with economic viability.5 From the industrial considera-
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
tion, the separation cost usually occupies a large portion and a
high single-pass product yield would reduce the cost required
for product separation. Therefore, we also encourage that the
single-pass product yield should be evaluated and reported.
Furthermore, the cost-efficient and large-scale fabrication of
efficient Cu catalysts should also be investigated in the future.
This would offer guidance for the design of industrial-relevant
catalysts and systems for the synthesis of C2+ compounds.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
Financial support by the National Key Research and Develop-
ment Program of Ministry of Science and Technology (No.
2019YFE0104400), the National Natural Science Foundation of
China (No. 2212100020, 91945301, 22022201 and 21972115)
and Science and Technology Projects of Innovation Laboratory
for Sciences and Technologies of Energy Materials of Fujian
Province (No. RD2020020201) is greatly acknowledged.
Notes and references
1 M. Aresta, A. Dibenedetto and A. Angelini, Chem. Rev., 2014,
114, 1709–1742.
2 S. Xie, W. Ma, X. Wu, H. Zhang, Q. Zhang, Y. Wang and
Y. Wang, Energy Environ. Sci., 2021, 14, 37–89.
3 W. Zhou, K. Cheng, J. Kang, C. Zhou, V. Subramanian,
Q. Zhang and Y. Wang, Chem. Soc. Rev., 2019, 48,
3193–3228.
4 S. Nitopi, E. Bertheussen, S. B. Scott, X. Liu, A. K. Engstfeld,
S. Horch, B. Seger, I. E. L. Stephens, K. Chan, C. Hahn,
J. K. Nørskov, T. F. Jaramillo and I. Chorkendorff, Chem.
Rev., 2019, 119, 7610–7672.
5 P. De Luna, C. Hahn, D. Higgins, S. A. Jaffer, T. F. Jaramillo
and E. H. Sargent, Science, 2019, 364, eaav3506.
6 A. J. Martin, G. O. Larrazabal and J. Perez-Ramirez, Green
Chem., 2015, 17, 5114–5130.
7 D. Gao, R. M. Arán-Ais, H. S. Jeon and B. Roldan Cuenya,
Nat. Catal., 2019, 2, 198–210.
8 Y. Y. Birdja, E. Pérez-Gallent, M. C. Figueiredo, A. J. Göttle,
F. Calle-Vallejo and M. T. M. Koper, Nat. Energy, 2019, 4,
732–745.
This journal is © The Royal Society of Chemistry 2021
View Article Online
Tutorial Review
9 M. Jouny, G. S. Hutchings and F. Jiao, Nat. Catal., 2019, 2,
1062–1070.
10 B. Kamm, Angew. Chem., Int. Ed., 2007, 46, 5056–5058.
11 A. Vasileff, C. Xu, Y. Jiao, Y. Zheng and S.-Z. Qiao, Chem,
2018, 4, 1809–1831.
12 T. N. Nguyen and C.-T. Dinh, Chem. Soc. Rev., 2020, 49,
7488–7504.
13 C.-T. Dinh, T. Burdyny, M. G. Kibria, A. Seifitokaldani,
C. M. Gabardo, F. P. G. de Arquer, A. Kiani, J. P. Edwards,
P. De Luna, O. S. Bushuyev, C. Zou, R. Quintero-Bermudez,
Y. Pang, D. Sinton and E. H. Sargent, Science, 2018, 360,
783–787.
14 C. Chen, X. Yan, S. Liu, Y. Wu, Q. Wan, X. Sun, Q. Zhu,
H. Liu, J. Ma, L. Zheng, H. Wu and B. Han, Angew. Chem.,
Int. Ed., 2020, 59, 16459–16464.
15 W. E. Mustain, M. Chatenet, M. Page and Y. S. Kim, Energy
Environ. Sci., 2020, 13, 2805–2838.
16 J. He, K. E. Dettelbach, D. A. Salvatore, T. Li and C. P.
Berlinguette, Angew. Chem., Int. Ed., 2017, 56, 6068–6072.
17 Y. Zhou and B. S. Yeo, J. Mater. Chem. A, 2020, 8, 23162–23186.
18 Y. Kim, S. Park, S.-J. Shin, W. Choi, B. K. Min, H. Kim,
W. Kim and Y. J. Hwang, Energy Environ. Sci., 2020, 13,
4301–4311.
19 W. Ma, S. Xie, T. Liu, Q. Fan, J. Ye, F. Sun, Z. Jiang, Q. Zhang,
J. Cheng and Y. Wang, Nat. Catal., 2020, 3, 478–487.
20 A. J. Garza, A. T. Bell and M. Head-Gordon, ACS Catal., 2018,
8, 1490–1499.
21 E. Pérez-Gallent, M. C. Figueiredo, F. Calle-Vallejo and
M. T. M. Koper, Angew. Chem., Int. Ed., 2017, 56, 3621–3624.
22 X. Wang, J. F. de Araújo, W. Ju, A. Bagger, H. Schmies,
S. Kühl, J. Rossmeisl and P. Strasser, Nat. Nanotechnol.,
2019, 14, 1063–1070.
23 F. Calle-Vallejo and M. T. M. Koper, Angew. Chem., Int. Ed.,
2013, 52, 7282–7285.
24 T. Cheng, H. Xiao and W. A. Goddard, Proc. Natl. Acad. Sci.
U. S. A., 2017, 114, 1795–1800.
25 J. Li, Z. Wang, C. McCallum, Y. Xu, F. Li, Y. Wang,
C. M. Gabardo, C.-T. Dinh, T.-T. Zhuang, L. Wang,
J. Y. Howe, Y. Ren, E. H. Sargent and D. Sinton, Nat. Catal.,
2019, 2, 1124–1131.
26 Haldor Topsoe, www.topsoe.com/processes/carbon-monoxide.
27 L. Wang, S. A. Nitopi, E. Bertheussen, M. Orazov, C. G.
Morales-Guio, X. Liu, D. C. Higgins, K. Chan, J. K. Nørskov,
C. Hahn and T. F. Jaramillo, ACS Catal., 2018, 8, 7445–7454.
28 Y. Wang, Z. Wang, C.-T. Dinh, J. Li, A. Ozden, M. Golam
Kibria, A. Seifitokaldani, C.-S. Tan, C. M. Gabardo, M. Luo,
H. Zhou, F. Li, Y. Lum, C. McCallum, Y. Xu, M. Liu,
A. Proppe, A. Johnston, P. Todorovic, T.-T. Zhuang,
D. Sinton, S. O. Kelley and E. H. Sargent, Nat. Catal., 2020,
3, 98–106.
29 X. Chen, J. Chen, N. M. Alghoraibi, D. A. Henckel, R. Zhang,
U. O. Nwabara, K. E. Madsen, P. J. A. Kenis, S. C.
Zimmerman and A. A. Gewirth, Nat. Catal., 2021, 4,
20–27.
30 Y. C. Li, Z. Wang, T. Yuan, D.-H. Nam, M. Luo, J. Wicks,
B. Chen, J. Li, F. Li, F. P. G. de Arquer, Y. Wang, C.-T. Dinh,
Chem. Soc. Rev.

Tutorial Review
O. Voznyy, D. Sinton and E. H. Sargent, J. Am. Chem. Soc.,
2019, 141, 8584–8591.
31 Y. Wang, D. Wang, C. J. Dares, S. L. Marquard, M. V.
Sheridan and T. J. Meyer, Proc. Natl. Acad. Sci. U. S. A.,
2018, 115, 278–283.
32 H. Xu, D. Rebollar, H. He, L. Chong, Y. Liu, C. Liu, C.-J. Sun,
T. Li, J. V. Muntean, R. E. Winans, D.-J. Liu and T. Xu, Nat.
Energy, 2020, 5, 623–632.
33 M. Rahaman, A. Dutta, A. Zanetti and P. Broekmann, ACS
Published on 05 October 2021. Downloaded by Kyunghee University on 11/18/2021 6:34:19 AM.
Catal., 2017, 7, 7946–7956.
34 R. Chen, H.-Y. Su, D. Liu, R. Huang, X. Meng, X. Cui,
Z.-Q. Tian, D. H. Zhang and D. Deng, Angew. Chem., Int.
Ed., 2020, 59, 154–160.
35 L. Wang, S. Nitopi, A. B. Wong, J. L. Snider, A. C. Nielander,
C. G. Morales-Guio, M. Orazov, D. C. Higgins, C. Hahn and
T. F. Jaramillo, Nat. Catal., 2019, 2, 702–708.
36 W. Luc, X. Fu, J. Shi, J.-J. Lv, M. Jouny, B. H. Ko, Y. Xu, Q. Tu,
X. Hu, J. Wu, Q. Yue, Y. Liu, F. Jiao and Y. Kang, Nat. Catal.,
2019, 2, 423–430.
37 X. Wang, Z. Wang, T.-T. Zhuang, C.-T. Dinh, J. Li, D.-
H. Nam, F. Li, C.-W. Huang, C.-S. Tan, Z. Chen, M. Chi,
C. M. Gabardo, A. Seifitokaldani, P. Todorović, A. Proppe,
Y. Pang, A. R. Kirmani, Y. Wang, A. H. Ip, L. J. Richter,
B. Scheffel, A. Xu, S.-C. Lo, S. O. Kelley, D. Sinton and
E. H. Sargent, Nat. Commun., 2019, 10, 5186.
38 M. Jouny, W. Luc and F. Jiao, Nat. Catal., 2018, 1, 748–755.
39 D. S. Ripatti, T. R. Veltman and M. W. Kanan, Joule, 2019, 3,
240–256.
40 Y. Hori, I. Takahashi, O. Koga and N. Hoshi, J. Mol. Catal. A:
Chem, 2003, 199, 39–47.
41 K. J. P. Schouten, E. Pérez Gallent and M. T. M. Koper, ACS
Catal., 2013, 3, 1292–1295.
42 T.-T. Zhuang, Y. Pang, Z.-Q. Liang, Z. Wang, Y. Li, C.-S. Tan,
J. Li, C. T. Dinh, P. De Luna, P.-L. Hsieh, T. Burdyny, H.-H.
Li, M. Liu, Y. Wang, F. Li, A. Proppe, A. Johnston, D.-H.
Nam, Z.-Y. Wu, Y.-R. Zheng, A. H. Ip, H. Tan, L.-J. Chen,
Chem. Soc. Rev.
View Article Online
Chem Soc Rev
S.-H. Yu, S. O. Kelley, D. Sinton and E. H. Sargent, Nat.
Catal., 2018, 1, 946–951.
43 Y. Pang, J. Li, Z. Wang, C.-S. Tan, P.-L. Hsieh, T.-T. Zhuang,
Z.-Q. Liang, C. Zou, X. Wang, P. De Luna, J. P. Edwards,
Y. Xu, F. Li, C.-T. Dinh, M. Zhong, Y. Lou, D. Wu, L.-J. Chen,
E. H. Sargent and D. Sinton, Nat. Catal., 2019, 2, 251–258.
44 W. Ma, S. Xie, X.-G. Zhang, F. Sun, J. Kang, Z. Jiang,
Q. Zhang, D.-Y. Wu and Y. Wang, Nat. Commun., 2019,
10, 892.
45 X. Liu, P. Schlexer, J. Xiao, Y. Ji, L. Wang, R. B. Sandberg,
M. Tang, K. S. Brown, H. Peng, S. Ringe, C. Hahn,
T. F. Jaramillo, J. K. Nørskov and K. Chan, Nat. Commun.,
2019, 10, 32.
46 J. Li, D. Wu, A. S. Malkani, X. Chang, M.-J. Cheng, B. Xu and
Q. Lu, Angew. Chem., Int. Ed., 2020, 59, 4464–4469.
47 J. Huang, N. Hörmann, E. Oveisi, A. Loiudice, G. L. De
Gregorio, O. Andreussi, N. Marzari and R. Buonsanti, Nat.
Commun., 2018, 9, 3117.
48 Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna,
H. Yuan, J. Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt,
R. Quintero-Bermudez, T.-K. Sham, S. Bals, J. Hofkens,
D. Sinton, G. Chen and E. H. Sargent, Nat. Chem., 2018,
10, 974–980.
49 Z.-Q. Liang, T.-T. Zhuang, A. Seifitokaldani, J. Li, C.-W.
Huang, C.-S. Tan, Y. Li, P. De Luna, C. T. Dinh, Y. Hu,
Q. Xiao, P.-L. Hsieh, Y. Wang, F. Li, R. Quintero-Bermudez,
Y. Zhou, P. Chen, Y. Pang, S.-C. Lo, L.-J. Chen, H. Tan, Z. Xu,
S. Zhao, D. Sinton and E. H. Sargent, Nat. Commun., 2018,
9, 3828.
50 F. Li, A. Thevenon, A. Rosas-Hernández, Z. Wang, Y. Li,
C. M. Gabardo, A. Ozden, C. T. Dinh, J. Li, Y. Wang,
J. P. Edwards, Y. Xu, C. McCallum, L. Tao, Z.-Q. Liang,
M. Luo, X. Wang, H. Li, C. P. O’Brien, C.-S. Tan, D.-H. Nam,
R. Quintero-Bermudez, T.-T. Zhuang, Y. C. Li, Z. Han,
R. D. Britt, D. Sinton, T. Agapie, J. C. Peters and E. H.
Sargent, Nature, 2020, 577, 509–513.
This journal is © The Royal Society of Chemistry 2021