REVIEW
Electrocatalysis
Electrode Materials Engineering in Electrocatalytic CO2
Reduction: Energy Input and Conversion Efficiency
Rong-Bin Song, Wenlei Zhu, Jiaju Fu, Ying Chen, Lixia Liu, Jian-Rong Zhang, Yuehe Lin,*
and Jun-Jie Zhu*
Electrocatalytic CO2 reduction (ECR) is a promising technology to simulta-
neously alleviate CO2-caused climate hazards and ever-increasing energy
demands, as it can utilize CO2 in the atmosphere to provide the required
feedstocks for industrial production and daily life. In recent years, substantial
progress in ECR systems has been achieved by the exploitation of various
novel electrode materials. The anodic materials and cathodic catalysts that
have, respectively, led to high-efficiency energy input and effective heterog-
enous catalytic conversion in ECR systems are comprehensively reviewed.
Based on the differences in the nature of energy sources and the role of
materials used at the anode, the fundamentals of ECR systems, including
photo-anode-assisted ECR systems and bio-anode-assisted ECR systems, are
explained in detail. Additionally, the cathodic reaction mechanisms and path-
ways of ECR are described along with a discussion of different design strate-
gies for cathode catalysts to enhance conversion efficiency and selectivity.
The emerging challenges and some perspective on both anode materials and
cathodic catalysts are also outlined for better development of ECR systems.
1. Introduction
The ever-increasing global energy demand for economic
growth has spurred scientific researches and policy settings to
drive the development of clean and renewable energy sources,
but the traditional fossil fuels still occupy an unshakable posi-
tion in today’s energy structure. According to relevant statis-
tics, the current annual global fossil fuel combustion generates
roughly 35.5 Gt of carbon dioxide (CO2) emissions, while the
total global CO2 fixation amount (≈200 Mt) by green plants
and autotrophic organisms per year is less than 6% of the
Dr. R.-B. Song, J. Fu, Y. Chen, L. Liu, Prof. J.-R. Zhang, Prof. J.-J. Zhu
State Key Laboratory of Analytical Chemistry for Life and Collaborative
Innovation Center of Chemistry for Life Sciences
School of Chemistry and Chemical Engineering
Nanjing University
Nanjing 210023, P. R. China
E-mail: jjzhu@nju.edu.cn
Dr. W. Zhu, Prof. Y. Lin
School of Mechanical and Materials Engineering
Washington State University
Pullman, WA 99164, USA
E-mail: yuehe.lin@wsu.edu
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adma.201903796.
DOI: 10.1002/adma.201903796
Adv. Mater. 2019, 1903796 1903796  (1 of 25)
www.advmat.de
a­forementioned emission amount. This
stark imbalance between anthropogenic
emission and natural consumption gives
rise to a net increase in atmospheric CO2
concentration, and eventually leading to
global warming and some other related
environmental hazards like melting of
polar ice caps and sea level rise. Therefore,
creating sustainable solutions to offset the
atmospheric CO2 increase is becoming
one of the most urgent tasks facing the
entire human race.[1]
Following the concept of storage, the
geological and deep-sea sequestrations
have been proposed to lower the atmos-
pheric CO2 concentration; however, their
high cost, laborious process as well
as high requirement of space may seem
inconsistent with the spirit of sustain-
able development.[2] On this context,
the CO2 reutilization is brought into
schedule naturally. Unlike CO2 storage,
CO2 reutilization involves the conversion of CO2 into various
carbon-containing chemicals, endowing it with promising
potential in relieving the CO2-caused environmental hazards
and maintaining the global carbon cycle.[3] The origin of CO2
reutilization could date back to 1869, when CO2 was used as
feedstock for the production of salicylic acid.[4] After over a
century of evolution, the portfolio of technologies for CO2 con-
version has become diversified, and now includes electrocatalytic
reduction, photocatalytic reduction, chemical transformation,
biological transformation by microorganism or enzyme, and
so on.[5] Among them, electrocatalytic CO2 reduction (ECR) is
given more attention on account of the following points.[6] The
first is its mild operation conditions (ambient temperature and
pressure). Second, ECR has a wide product distribution, and it
can be easily adjusted by altering the various applied param-
eters. Third, ECR is driven by electrical energy, which can be
converted from some renewable energy sources like light energy,
tidal energy, wind energy, and even chemical energy in wastes.
The fourth crucial point is that the abundant theories and experi-
ences from the investigations of electrocatalytic oxygen reduction
reaction (ORR) and hydrogen evolution reaction (HER) will afford
some importuned reframes for the development of ECR.
CO2 molecule possesses a linear centrosymmetric struc-
ture with the presence of two identical C=O bonds. These
C=O bonds have triple bond-liked features, and the dissocia-
tion energy is about 750 kJ mol−1, making the CO2 molecule
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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stable.[7] Therefore, many efforts have been dedicated to devel-
oping novel cathode materials as heterogenous catalysts with
the intention of lowering the active energy in ECR. On the one
hand, the optimized compositions and crystal facets of these
cathode catalysts are supposed to give preferred electronic
structures,[8] which guarantee the activity of the catalytic sites
and balance the CO2/catalysts interactions for realizing excel-
lent catalytic properties. On the other hand, the tailored sizes
and morphologies of these cathode catalysts are possible to
expose more active sites that are accessible to CO2 molecules,
eventually offering an improved catalytic performance. In addi-
tion to cathode catalysts, a substantial energy input is necessary
for ECR. To satisfy this demand, the usual practice is to directly
use electrical energy supplied by power device. Considering the
good combination of ECR with other renewable energy sources,
researchers expand their horizon and point to the conversion
of renewable energy sources into electrical energy in ECR for
obviating external power sources.[9] In this case, novel nano-
materials with special properties, including some physical and
chemical features required for high-efficient hosting of biocata-
lyst or excellent photoelectric conversion property, have been,
respectively, developed as electrode materials with the purpose
to transform chemical energy in wastes or light energy to power
the CO2 reduction reaction in ECR.[10] As the consequence of
these investigations and developments on cathode catalysts and
anode materials, the bottle-neck problems in energy input and
conversion efficiency aspects of ECR are expected to be over-
come for ultimately pushing the practical application of ECR.
With the rapid development of ECR in recent years, its dif-
ferent subfields have been comprehensively reviewed, including
electrode material, electrolyte, commercial application, and so
on.[11] As to electrode material, the reviews mainly focus on the
progresses on cathodic catalysts and reaction mechanisms. In
this review, by taking both the energy input and conversion
efficiency into consideration, we summarize important strides
toward the building of anode materials and cathode catalysts,
and highlight the design strategies of electrode materials in
terms of the enhancement on the anodic energy conversion effi-
ciency and the cathodic CO2 conversion efficiency. Hopefully,
this review will further intensify the research on the exploration
of novel electrode materials to advance the development on the
energy input and catalytic efficiency aspects of ECR, as well as
offer assistance to the guidance on the future researches and
real-world applications.
2. Fundamentals
2.1. Basic Principles of ECR Systems
Since the last three decades, significant strides have been made
in ECR, which are now considered as an effective and prom-
ising CO2 conversion technology capable of keeping pace with
a sustainable society. Similarly to traditional fuel cells, the ECR
is conducted in a double chamber reactor (Figure  1A). The
anode (counter electrode) is positioned in one chamber, which
is the site of the oxygen evolution reaction (OER), while the
cathode electrode (working electrode) and reference electrode
are placed into the other chamber for CO2 reduction reaction.
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Yuehe Lin is a professor at
Washington State University
and a laboratory fellow at
Pacific Northwest National
Laboratory. He is active in
the field of nanotechnology,
particularly in the synthesis
of functional nanomaterials
for energy and environmental
applications. His other
research activities include the
development of new biosen-
sors and bioelectronic devices and nanomaterials for
biomedical diagnosis and drug delivery.
Jun-Jie Zhu is a professor
of chemistry at Nanjing
University, China. He received
his B.S. (1984), and Ph.D.
(1993) degrees in chemistry
from Nanjing University. He
then started his academic
career at Nanjing University.
During 1998 and 1999 he
was a postdoctoral fellow at
Bar-Ilan University, Israel. His
current research interests are
analytical chemistry and materials chemistry, with a focus
on the study of nanobioanalytical chemistry including
bioelectrochemistry, photoelectrochemistry, nanoelectro-
chemistry, and the fabrication of biosensors.
The proton exchange membrane is used to separate these two
chambers for preventing the transport of the oxygen and liquid
products into the chambers opposite to where they are pro-
duced, respectively. Generally, a potentiostat serves as external
energy to power the ECR system, and a Pt electrode is employed
as the anode.[12] Motivated by a desire to reduce or even elimi-
nate the reliance on the external electrical energy, the anode has
been upgraded to converse other renewable energy resources
into electricity within the ECR system. These upgraded anodes
mainly include two categories: photo-anode and bio-anode.[13]
The former is to transform the light energy into electrical
energy, while the latter is capable of capturing chemical energy
of waste to produce electrical energy.
The CO2 reduction reaction is the heart of the ECR system,
which inevitably requires a high overpotential in the process
of actual operation for smashing the energy barrier. Such high
overpotential gives rise to the waste of electrical energy as well as
brings about some by-products like H2, which consequently leads
to poor selectivity.[11e,14] To alleviate these issues, heterogenous or
homogenous catalysts with high activity are needed. The cathode
materials often act as the heterogenous catalysts to directly cata-
lyze the reduction of CO2 at the electrode/solution interface by
receiving the electrons from the electrode and the protons from
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Figure 1.  Schematic diagrams for various ECR system using A) general anode, B) photo-anode, and C) bio-anode.
the electrolyte. On the contrary, most of the homogenous cata-
lysts (molecularly defined compounds) exist in solution, which
can work as shutters to mediate the electron transfer between
CO2 and the cathode. In this case, the reduction on the cathode/
electrolyte interface occurs at the potential of the homogenous
catalyst instead of that of CO2, while the homogenous catalyst
in reduction state subsequently catalyzes the reduction of CO2,
which is defined as indirect electrolysis.[15] As electrode materials
of the ECR are the main focus of this review, we will not discuss
the homogenous catalysts here. The detailed description of them
can be found in some excellent reviews.[16]
2.2. Photo-Anode-Assisted ECR (PA-ECR) System
PA-ECR system is a new type device for electrochemical
reduction of CO2, which consists of a photo-anode containing
photo­electric conversion materials and a conventional cathode
containing electro-catalysts. The principle of PA-ECR system is
shown in Figure 1B. Under light illumination, the photo-anode
absorbs the incident photons, yielding valence band (VB) holes
and conduction band (CB) electrons. These holes can oxidize
H2O to generate O2, while the photo-induced electrons transfer
via the external circuit and reach the cathode for the electro-
chemical reduction of CO2 with the aid of electro-catalysts.
Owing to this ability to capture light energy for electricity gen-
eration, the PA-ECR system can theoretically work with less
or even no additional external bias voltage, which is its major
appeal.[17] Furthermore, the PA-ECR system also displays sev-
eral distinct merits when compared with the most commonly
studied photo-electrochemical CO2 reduction system with
photocathode.[10b,18] First, the n-type semiconductors are usually
chosen for the fabrication of photo-anode in PA-ECR system,
which are better than the p-type semiconductors used in photo­
cathode-involved CO2 reduction system for light-harvesting,
mainly relying on their earth-abundant and intrinsically stable
features. Second, unlike the photo-electrochemical CO2 reduc-
tion system where the functions of harvesting light energy and
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providing catalytic sites are integrated into the photocathode,
these two functions are separated at anode and cathode in
PA-ECR. A natural outcome of this separation is the improved
flexibility in the selection of cathode catalysts, with which the
photo-electrocatalysts can be replaced by abundant electrocat-
alysts to improve the conversion efficiency or even reach the
unattainable CO2 reduction products.
For the design of an ideal PA-ECR system, the energetics
suitability of both the photoelectric conversion material and
the reaction species is a high priority item. In other words,
the VB of the material carried by photo-anode should have the
adequate positive potential for H2O oxidation (0.82 V, vs
standard hydrogen electrode, SHE, pH = 7), while the CB level
need to be adequate negative for CO2 reduction (e.g., −0.38 V to
methanol, vs SHE, pH = 7).[19] Furthermore, the overpotentials
are, respectively, about 0.4 V and over 1 V for water oxidation
and CO2 reduction,[20] which must be included in the actual
potentials for operating these two reactions. In this case, photo-­
sensitive materials that have large band gaps are possible to sat-
isfy the operating redox potentials. However, the trouble is that
less of the solar spectrum in nature can be absorbed by them.
Another challenge is that only a few photo-sensitive materials
have a more negative CBs compared to the CO2 reduction level.
For examples, CdS, SrTiO3, and LaTi2O7,[21] but they suffer
either poor stability or low charge carrier mobility. Stacking
multiple photo-converters in series seems to be a solution for
this challenge,[19a,20] but the current density will be decreased in
proportion to the number of the involved photo-converters. In
fact, an external bias voltage is usually given to PA-ECR system
for assisting the migration of electrons from photo-anode to
cathode. Undoubtedly, this bias voltage is much smaller than
that applied for the ECR system with a dark anode.
2.3. Bio-Anode-Assisted ECR (BA-ECR) System
As another promising new form for electrochemical reduction
of CO2, BA-ECR system is distinct from the PA-ECR system in
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which the electricity originates from the photoelectric material- Table 1. Possible ECR half-reactions in aqueous solution and the
involved conversion of light energy rather than the anodic bio- ­corresponding electrode potentials.
catalyst-involved conversion of chemical energy.[22] Indeed, the
Possible half-reactions for electrochemical CO2 Electrode potentials
traditional anodic catalysts in fuel cells can also be integrated reduction (V vs SHE) at pH 7
into ECR system to undertake the same functions as biocata-
CO2 (g) + 2H+ + 2e−→CO (g) + H2O (l) −0.53
lysts in BA-ECR systems. However, the intrinsic features of
biocatalysts, including low cost, renewability, mild catalytic CO2 (g) + 2H+ + 2e−→HCOOH (l) −0.61

conditions, and the use of waste organic matters as substrates,
conform more to the concept of sustainable development
of CO2 reduction.[23] Based on the different natures of used
biocatalysts, the bio-anode can be divided into two categories: 1)
enzyme-involved anode and 2) microbe-involved anode.[24] Yet,
as far as we know, there is still no reported case of the combi-
nation of enzyme-involved anode into ECR system, maybe due
to the high cost and poor stability of enzyme relative to those
of microbe. Therefore, the bio-anode specifically refers to the
microbe-involved anode for the moment.
In a typical BA-ECR system, the microbes, termed “electroac-
tive bacteria” or “electricigens,” oxidize the organic matters to
produce electrons and transfer these electrons into the anode
by the extracellular electron transfer (EET) paths. The electrons
then flow to the external circuit and reach the cathode where
they participate in the CO2 reduction (Figure 1C). Thus, the
BA-ECR system can be considered as a special microbial fuel
cell (MFC) with CO2 as cathodic electron acceptors, but not as
a microbial electrolysis cell, where the microbes are placed at
the cathode for bioelectrocatalytic CO2 reduction.[25] In theory,
the BA-ECR system can operate without external energy, which
is highly influenced by the theoretical cathode potential for
different CO2 reduction reactions. For example, when using
acetate as the substrate for electroactive bacteria, the theoretical
anodic potentials (Ean) is about −0.296 V (vs SHE, pH = 7),[26]
and the anodic reaction can be written as follow
CO2 (g) + 4H+ + 4e−→HCHO (l) + H2O (l) −0.48
CO2 (g) + 6H+ (l) + 6e−→CH3OH (l) + H2O (l) −0.38
CO2 (g) + 8H+ + 8e−→CH (g) + 2H2O (l) −0.24
4
2CO2 (g) + 8H2O (l) + 12e−→C2H4 (g) + 12OH− −0.34
2CO2 (g) + 9H2O (l) + 12e−→C2H5OH (l) + 12OH (l) −0.33
and CH4, the C2 products including C2H4 and C2H5OH can be
also generated due to the C–C coupling reaction.[27] According
to standard redox potential (E  0), it is evident that the CO2 reduc-
tion to hydrocarbon products are more thermodynamically
favorable processes than the CO2 reduction toward oxygen-
contained products. From the perspective of energy storage, C1
products are less attractive compared to C2 products.
The electrochemical CO2 reduction on the cathodic cata-
lyst is a multi-step process, which involves the adsorption of
CO2 molecule on the catalyst surface, the surface interactions
between the electrons, protons, and absorbed CO2 molecule
as well the desorption of the products formed by the previous
step (Figure  2A). Specifically, the neutral hydrated CO2 mole­
cule that is regarded as the reactive species will convert into
CO2•− through the interaction with one electron (adsorption
step). During this conversion process, the C=O bond undergoes

CH3 COO− + 4H2 O → 2HCO3− + 9H+ + 8e −

If the theoretical cathode potential for CO2 reduction (Ecat) is

positive than the value of Ean, the value of standard cell electro-
motive force (Eemf) is positive based on the equation of Eemf  =
Ecat – Ean. This thus yields a negative Gibbs free energy based on
the equation of ΔG = − nFEemf, reflecting that the involved ace-
tate oxidation and CO2 reduction reactions are thermodynami-
cally spontaneous. On the contrary, if the theoretical cathode
potential is more negative than the value of Ean, external energy
input is necessary for driving the BA-ECR system. But in
practice, the anodic overpotential resulted from ohmic loss, acti-
vation loss, bacterial metabolic loss, and concentration should
be taken into account. A higher overpotential implies a less neg-
ative anodic potential, and thus a smaller scope of CO2 reduc-
tion reaction will be self-driven in BA-ECR or a higher energy
demand for the actuation of a certain CO2 reduction reaction.

2.4. Cathodic Reaction Products and Pathways

The cathodic CO2 reduction reaction may undergo two-, four-,

Figure 2.  The proposed reaction pathways of electrocatalytic reduction of
six-, eight-, or twelve-electron transfer process, thus allowing CO2 to main products. A) C1 products. Reproduced with permission.[27a]
a variety of products to be generated. As shown in Table  1, Copyright 2017, Wiley-VCH. B) C2 products. Reproduced with permis-
besides the C1 products like CO, HCOOH, HCHO, CH3OH, sion.[34] Copyright 2013, Wiley-VCH.

Adv. Mater. 2019, 1903796 1903796  (4 of 25) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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strong perturbation, and the electrons are shared by both the
CO2 molecule and catalyst. The generated CO2•− intermediate
then reacts with H2O molecule to form HCO2•− (interaction
step), which will further convent into HCO2− due to the pres-
ence of unstable unpaired electron. The desorption of HCO2−
species from active sites occurs finally (desorption step).[28]
Thus, the reaction pathways are highly associated with the types
of cathodic catalysts, which possess different adsorption ener-
gies toward different intermediates. For Sn and Pb metals,[29]
the HCO2* intermediates can be easily desorbed from their
surfaces, thus they generate formate preferentially. The noble
metals like Au and Ag have enough ability to bind with COOH*
intermediate but possess weak CO* intermediate binding capa-
bility,[30] thus leading to the generation of CO as the predomi-
nant product. The boron-doped diamond has the sp3-bonded
carbons that can serve as the active sites for the reduction of
CO2 to formaldehyde in various electrolytes, such as methanol,
seawater, and aqueous NaCl.[31] As a typical type of catalyst for
ECR, Cu-based materials are conducive to binding with CO*
intermediate and transforming it to H3CO* intermediate by
further proton–electron transfer. On the surface of Cu2O, the
formed H3CO* intermediate is stable and the proton will add to
the oxygen atom instead of carbon atom, thus resulting in the
formation of CH3OH.[32] In contrast, Cu is in favor of the for-
mation of CH4 due to the addition of proton to carbon atom.[33]
The prerequisites for the formation of C2 products are that the
coverage of C1 intermediates should be high enough and the C2
intermediate products should be stabilized by favorable energy
for dimerization. Based on density functional theory (DFT)
calculations, Koper and co-workers investigated the formation
pathways of C2H4 and C2H5OH from CO on Cu(100) surface.[34]
The results revealed that the coupling of two CO molecules to
form C2O2* was the rate-determining step (Figure 2B).
In addition to the cathodic catalyst, the pathway of ECR
shows a strong dependence on the experimental conditions.
The pH has been demonstrated to possess an obvious influ-
ence on the CO2 reduction on Cu(211) surface toward C2 prod-
ucts. It is found that C2 products were generated preferentially
under alkaline conditions.[35] Besides, the investigations in the
effect of reaction temperature and pressure on the product
selectivity have also been performed. By using Cu electrode for
ECR, Yoshio et al. discovered that the selectivity of C2H4 sig-
nificantly increased when the reaction temperature increased
in the range from 0 to 40 °C.[36] In a different research, the
potential of ECR at meso-tetraphenylporphyrin-modified metal
gas-diffusion electrode was positively shifted with the increase
in the reaction pressure.[37] The electrolyte plays the role to
transfer electrons and protons, which is another important
factor that can influence the pathway of ECR. Mizuno and
­co-worker probed the relationship between the types of anionic
species and the products selectivity for the ECR in methanol by
using Cu electrodes. They proposed that the selectivity of C2H4
formation over CH4 improved in the sequence B− > I− > Cl− >
SCN− > CH3COO−.[38] The product selectivity for ECR has also
been proven to be highly correlated with the applied potentials.
Jaramillo et al. investigated the ECR on a metallic copper sur-
face across a range of potentials.[27b] They found that the H2,
CO, and formate were the main products at the potentials more
positive than −0.75 V (vs reversible hydrogen electrode, RHE).
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When the applied potential went more negative, the main prod-
ucts were changed to C2H4 and CH4 due to the increased per-
centage of current for ECR. Once the potential reached −0.96 V,
some new C2 products (e.g., ethanol and acetate) emerged and
their yields increased with increasing potential. But after the
potential exceeds −1.05 V, the predominated product was grad-
ually turned to CH4. These results have been further confirmed
by a recent research, where the predominated products of ECR
on four Cu-based films were revealed to be CO and formate
at low potential region (>  −0.7 V, vs RHE), C2H4 and ethanol
at medium potential region (−0.8 to −1.1 V), and CH4 at high
potential region (< −1.1 V), respectively.[39]
3. Electrode Materials for ECR System
3.1. Anodic Materials for PA-ECR System
The anodic materials in PA-ECR systems are specialized; they
should have the photo-generated potential that can sufficiently
bracket the potentials of water oxidation and CO2 reduction as
well as their corresponding overpotentials.[5c] As the CB level of
photo-sensitive materials is insufficient to match the operating
potential for CO2 reduction, the as-mentioned requirement is
still a major challenge.[17d] Even so, various n-type semiconduc-
tors with sufficiently positive VBs, including CdS, TiO2, BiVO4,
ZnO, and Si, have been widely used as anode materials for
PA-ECR system, which at least can diminish the external energy
input. In general, the smaller band gap indicates higher theoret-
ical photoelectric conversion efficiency, as an increased fraction
of solar radiation can be utilized.[40] Among these mentioned
materials, Si has the smallest band gap and thus the superior
photoelectric conversion efficiency. However, the high fabrication
cost and poor stability should be noted when using Si as photo-
anode material. In contrast, the semiconductor materials with
board band gap like TiO2 and ZnO possess relatively low theoret-
ical photoelectric conversion efficiency. But, they are stable, cost-
effective, along with good charge transport properties. Although
CdS and BiVO4 are medium band gap semiconductors, they can
absorb visible light, making them attractive for the fabrication
of photo-anodes. However, their poor charge mobility lowers
their actual photoelectric conversion efficiency.[41] On another
level, the electrons–holes recombination rate can severely influ-
ence the photoelectric conversion efficiency. Unfortunately, all of
these pure semiconductors suffer from extensive electron–hole
recombination.[42] In this regard, several typical strategies have
been developed, including the improvement of specific surface
area (SSA), the modification of photo-sensitive materials with
co-catalysts and the combination of different photo-sensitive
materials, to further increase the photo-currents and the yields
of products from CO2 reduction. Thus, the following section will
focus on the photo-sensitive materials and the anodic enhance-
ment strategies in the developed PA-ECR systems.
3.1.1. TiO2 and Its Composites
During the course of research on the PA-ECR systems, n-CdS
is the first photo-sensitive materials that have been used as
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Figure 3.  A) Schematic representation of an electrochemical flow cell using TiO2 nanorod photo-anode and Sn-coated GDE cathode. Reproduced with
permission.[45] Copyright 2017, Elsevier. B) Scanning electron microscope (SEM) image of 5% Pt-modified TiO2 nanotube. C) Current–time curve of
a PA-ECR system using 5% Pt-modified TiO2 nanotube as photo-anode and GO/Ni foam as cathode with and without light illumination. Reproduced
with permission.[48] Copyright 2016, American Chemical Society.

­ hoto-anode to power the CO2 reduction reaction.[43] However,

p due to its large band gap of 3.2 eV. A promising way to depress
n-CdS is vulnerable to photo-corrosion, which limits its practical
application. In this case, the use of TiO2 as photo-anode began to
flourish, mainly due to its excellent stability against photo-corro-
sion and appropriate band edge positions toward water oxidation.
In mid-1980s, the n-TiO2 has been used as photo-anode to couple
with the platinum-coated cathode for the fabrication of PA-ECR
system.[44] The 13C NMR confirmed that the system solely pro-
duced the methanol with an external bias. The SSA of photo-
sensitive materials has a positive effect on its light absorption
intensity. As the low dimensionality nanostructures can improve
the SSA, the TiO2 has been engineered to possess a 1D nano-
structure for improving the photo-anode efficiency. Irtem and
co-workers used TiO2 nanorods as the photo-anode materials,
and CO2 reduction reaction was conducted on a gas diffusion
electrode (GDE) coated by the electrodeposited Sn (Figure 3A).[45]
The result showed that the applied bias potential for the reduction
of CO2 into the HCOO− decreased to 1.2 V due to the presence
of TiO2 nanorods photo-anode. At this bias potential, the energy
efficiency reached over 70%. Furthermore, the TiO2 thin film
based on an ordered array of TiO2 nanotubes has also been dem-
onstrated as a high-efficient photo-anode for PA-ECR system as
a result of the improved SSA and the reduced light scattering.[46]
In addition to the aforementioned merits, however, the TiO2
suffers two obvious disadvantages. The first one is the easy
recombination of photo-generated electron–hole pairs, and the
other is the exclusive light absorption (UV fraction of solar light)
the recombination of electron–hole pairs is to associate TiO2
with metal co-catalyst. Compared to other metal co-catalysts, the
noble metal catalysts are more beneficial for trapping e­ lectrons
as a result of their relative low Fermi level.[47] Inspired by this,
the Pt-modified TiO2 nanotube (Figure 3B) has been used as
photo-anode in PA-ECR system.[48] By the optimization of the
Pt loading amount (5%) on the photo-anode, the best photocat-
alytic activity was achieved. As a result, the current density of
PA-ECR system was as high as 4 mA cm−2, and the carbon atom
conversion rate on the Pt/reduced graphene oxide cathode was
about 1250 nmol h−1 cm2 (Figure 3C). Subsequently, the same
group integrated this photo-anode with an octahedral catalyst-
modified cathode for the production of alcohol by CO2 reduc-
tion.[49] Similarly, this photo-anode has been demonstrated to
have more energy input compared with dark anode under the
same applied voltage. In contrast to the extensive investigation
on the suppression of electrons–holes recombination, equiva-
lent researches to extend the light-absorption range of TiO2 are
scarce in the field of PA-ECR. For this reason, the development
of photoelectric materials with a lower band gap as photo-anode
has become another active topic.
3.1.2. BiVO4 and Its Composites
BiVO4 with a monoclinic scheelite-like crystalline structure is
another popular semiconductor material for photo-anode. It

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possesses a medium band gap (2.4 eV) and thus can absorb
visible light, offering an enhanced utilization of solar radiation
on earth surface when compared with TiO2.[41,50] However, the
pure BiVO4 suffers low charge mobility and extensive recom-
bination of electron–hole pairs. So when using it for photo-
anode of PA-ECR system, the BiVO4 is frequently associated
with OER catalysts for improving the photoelectric efficiency.
Lee et al. reported a nanoporous CoPi/BiVO4 photo-anode for
PA-ECR system,[51] while the cathode was fabricated by the
encapsulation of FDH enzyme and its cofactor (NADH) into
the polydopamine matrix (EC-PDA, Figure  4A). In this hybrid
photo-anode, the presence of CoPi could substantially reduce
the kinetic overpotential for water oxidation, thus the photo-
generated holes could transfer to electrolyte solution more
easily for the suppression of electron–hole recombination. In
this case, the current density of CoPi/BiVO4 was much supe-
rior to that of BiVO4 (Figure 4B). The BiVO4 component in the
photo-anode showed a CB edge of −0.6 V (vs Ag/AgCl), which
was more negative than the formal potential of redox cofactor
in the cathode (−0.53 V, vs Ag/AgCl, Figure 4C). Thus, the con-
structed PA-ECR system converted CO2 into formate at a Fara-
daic efficiency (FE) of ≈99.2% without any external bias. As the
deposition of OER catalysts may obscure the surface of photo-
sensitive materials, Aoi et al. have used a transparent OER cata-
lyst (FeO(OH)) to combine with BiVO4 for improving the light
absorption.[52] The oxidation potential difference of FeO(OH)/
BiVO4/FTO photo-anode with or without light illumination was
about 1.5 V, which was much lower than the normal band gap

Figure 4.  A) Schematic illustration of a PA-ECR system using Co-Pi/BiVO4 photo-anode and EC-PDA bio-cathode. B) Linear sweep voltammograms
of bare BiVO4 and CoPi/BiVO4 electrodes under illumination. C) Proposed light-driven CO2 reduction processes. Reproduced with permission.[51]
Copyright 2016, Wiley-VCH. D) Scheme illustration of a PA-ECR system using Co-Ci/BiVO4/WO3 photo-anode and Cu cathode. E) Photocurrent and
F) current conversion efficiencies of different photo-anodes. Reproduced with permission.[54] Copyright 2015, Elsevier. G) SEM images of CNTs-
ZnO-Co3O4 NW. H) Current–voltage curves of PA-ECR systems with CNTs-ZnO-Co3O4 NW (T-ZnO) and pristine ZnO (P-ZnO) photo-anodes. Repro-
duced with permission.[55] Copyright 2016, Royal Society of Chemistry.

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of BiVO4, reflecting that this phot-anode diminished the total
bias for water oxidation and CO2 reduction. When this photo-
anode was coupled with a cobalt(II) chlorine (CoII(Ch)) cathode,
the CO2 has been reformed into CO with an FE of ≈99.2% and
a bias voltage of −1.3 V.
The integration of another photo-sensitive material with
BiVO4 is also an effective way to improve the charge mobility
and depress the electron–hole recombination. Under the
­guidance of this idea, the WO3/BiVO4 film has been tried to
use as photo-anode for the PA-ECR system equipped with Ag
plate cathode.[53] In this system, the value of photo-to-chemical
efficiency was positive when the applied voltage was lower than
1.5 V. Correspondingly, the value of electro-to-chemical effi-
ciency was over 100%, suggesting that the related energy losses
during the water oxidation and CO2 reduction have been all
compensated by the solar energy captured by WO3/BiVO4 photo-
anode. To further a better photoelectric efficiency of BiVO4
photo-anode, the strategies of using photo-sensitive materials
and OER catalysts as modifiers can be integrated. For example,
the FTO/WO3/BiVO4/cobalt carbonate (Co-Ci) has been devel-
oped as photo-anode in the PA-ECR system (Figure 4D).[54] In
this ternary complex, the presence of WO3 first guaranteed
the better charge separation of BiVO4 and thus its photo-
electric performance. After the deposition of Co-Ci on WO3/
BiVO4, the photocurrent increased from 2.6 to 3.5 mA cm−2
(Figure 4E), and the photocurrent onset potential shifted from
0.5 to 0.2 V (vs RHE, Figure 4F) due to the excellent catalytic
performance of Co-Ci toward water oxidation. Notably, the
WO3/BiVO4/Co-Ci showed an incident photon to current con-
version efficiency of 60% under the given conditions (up to
450 nm), which was almost the highest value reached by the
BiVO4-based photo-anode. Thanks to the high photoelectric
efficiency, the CO2 reduction on the Cu cathode of this PA-ECR
system can be carried out with a lower bias potential.
3.1.3. Other Photo-Sensitive Materials or Devices
Some other semiconductor materials have been used as photo-
anode in PA-ECR system as well, such as ZnO and Si. In a
reported PA-ECR system,[55] the ZnO nanowire (NW) array
decorated with carbon nanotubes (CNTs) and Co3O4 NPs
(CNTs-ZnO-Co3O4 NW) was fabricated as photo-anode mate-
rial (Figure 4G), while mesoporous Pd-Cu alloy was prepared
as cathodes for the reduction of aqueous CO2 into CO. With
regard to the photo-anode, the CNTs and Co3O4 accelerated the
charge separation of ZnO and reaction rate of water oxidation
as in the case of TiO2 and BiVO4, thus the photo-responses
of CNTs-ZnO-Co3O4 NW surpassed that of ZnO NW and the
photocurrent showed a 2.3-fold increase at −1.4 V (Figure 4H).
In another example, a PA-ECR system fabricated with a Ni-
coated Si photo-anode and a nanoporous Ag cathode has been
developed for the conversion of CO2 into CO.[56] The thin Ni
layer in the photo-anode could take the functions of protecting
the Si wafer from photo-corrosion and catalyzing the water oxi-
dation. Consequently, the photo-voltage of this photo-anode is
about 0.4 V, equaling to an energy saving of about 17% for the
cathodic CO2 reduction. To eliminate the applied bias potential,
the solar cells have been coupled to PA-ECR system. Urbain
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et al. integrated an adapted silicon heterojunction solar cell
structure with nickel foam for the anode of PA-ECR system,[57]
while Nath et al. developed the WO3/dye-sensitized solar cell
as dual-absorber photo-anode for the fabrication of PA-ECR
system.[58] Undoubtedly, the PA-ECR systems have widely been
developed by using various photo-sensitive materials as the
anode. However, it is hard to make a direct comparison in the
performances of these photo-anodes, because of the use of dif-
ferent cathode materials and bias voltages as well as illumina-
tion conditions. Thus, some relevant standard measures should
be established, which are beneficial for searching the most
promising direction for the future researches on this field.
3.2. Anodic Materials for BA-ECR System
Although the electrical energy is originated from the micro-
bial metabolism, the energy conversion efficiency in the bio-
anode of BA-ECR system shows a strong dependence on the
anodic material. In the anodic chamber, the anode undertakes
the function of providing an area for bacterial attachment. Its
surface area and properties determine the amount of bacterial
loading, thus affecting the magnitude of the generated cur-
rent.[59] With regard to overpotential, the inherent features in
the aspects of conductivity, biocompatibility, and structure are
highly associated with the flow of electrons through anode, the
growth situation of bacteria on the anode as well as the mass
transport rate of the substrate for bacteria, eventually control-
ling the ohmic losses, bacterial metabolic losses, and concen-
tration losses.[60] Furthermore, the microbial EET that links
with the ohmic losses and the generation of current is closely
correlated with the anode tailoring. At present, the proposed
mechanisms for the EET between the electrode and microbes
can be summarized as three types: mediated electron transfer
(MET) through extraneous or microbial-secreted mediators
to shuttle the electrons between electrode and the cells, direct
electron transfer (DET) through contact between the electrode
and the outer member (OM) proteins of cells, and DET through
microbial-generated pili as conductive NW to connect the elec-
trode and the cells.[61] The anodes armed with some special sur-
face properties are believed to improve their interactions with
bacteria cells, thus achieving close proximities between the
anodes and the OM proteins to guarantee the fast DET. On the
level of MET, endowing the anodes with the 3D porous struc-
tures will extend the area for accepting the electrons from medi-
ators and accelerate the diffusion of mediator in the anodes.
However, researchers still give little attention to the anode in
spite of its above-mentioned significance to BA-ECR system. To
stimulate the research interest, we not only describe the state of
the art of anodic materials in BA-ECR in this part, but also dis-
cuss the potential strategies to improve the anode performance
by drawing on research results related to MFC anode.
3.2.1. State of the Arts
The first example of BA-ECR system was developed in 2012 by
Zhao and co-workers.[22] The BA-ECR system was designed with
a carbon fiber (CF) anode to harvest the microbial generated
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
Figure 5.  A) Schematic illustration of an MFC-driven BA-ECR system using microbe-inoculated carbon fiber anode and MWCNT/CoTAPc cathode.
Reproduced with permission.[22] Copyright 2012, American Chemical Society. B) Potential–time curves of different anodes. Reproduced with permis-
sion.[66] Copyright 2019, Elsevier.
electricity. Driven by the power from the anode and an extra
MFC, the cathode modified with multi-walled CNT (MWCNT)/
cobalt tetra-amino phthalocyanine (CoTAPc) composite suc-
cessfully reduced CO2 to formic acid with a production rate
of up to 21.0 ± 0.2 mg L−1 h−1 (Figure  5A). After that, several
BA-ECR systems have been established by using commercial
materials as the anode, such as non-wet-proofed CF, carbon
cloth, and tin plate.[62] As these anode materials inherently
suffer from poor bacterial attachment and low EET efficiency,
the formed bio-anodes cannot solely satisfy the energy demand
for ECR. On this context, two strategies were used in these
BA-ECR systems to solve the aforementioned issue. As used
in Zhao’s work, the first strategy is to connect MFC in series
with BA-ECR system.[63] Owing to extra energy supply from a
series-connected MFC stack, the reduction of CO2 to formic
acid has been realized at the Pd cathode of BA-ECR system
with an FE of 64.8%. The other is to optimize the condition of
cathodic reaction for reducing the overpotential and thus the
energy demand. When selecting an ionic liquid (1-ethyl-3-meth-
ylimidazolium tetrafluoroborate, EMIM-BF4) as catholyte for a
S. oneidensis MR-1 inoculated BA-ECR system, the external
voltage applied for initiating the conversion of CO2 into CO at
AgNPs/graphite block cathode was as low as −0.1 V.[64] Further-
more, with the option of replacing the Sn-loaded brass mesh
electrode (SE) by the Sn-loaded GDE (SGDE) in the BA-ECR
system, the energy consumption for the electrolytic production
of formic acid at the SGDE was deceased by about 67.2–73.6%,
because the improved CO2 mass transfer guaranteed the high-
concentration CO2 around the catalytic active sites.[65]
Unfortunately, the potential that the tailor of electrode mate-
rials can boost the energy conversion efficiency of bio-anodes
has not been explored yet in the presented BA-ECR system,
but it has already been identified in some other bio-anode-
assisted electrochemical synthetic systems. For examples, in a
bio-anode-assisted electrocatalytic system for hydrogen evolu-
tion,[66] the bacterial incubation and EET were both improved
by using self-supported carbon aerogel (CA) to replace the tra-
ditional CF, because the CA anode possessed enhanced inter-
action with bacterial cells, 3D porous structure, large surface
area as well as excellent conductivity. As a result, the anodic
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potential decreased from −0.227 to −0.266 V (vs SHE), which
was near to the theoretical value (−0.296 V), and the Pt cathode
coupled with this bio-CA anode showed a fivefold increase in
the H2 production compared to that with bio-CF (Figure 5B).
Besides, the functionalization of the anode with p-phenylene-
diamine (PDA2+) has been found to optimize the orientation
of [NiFe]-hydrogenase at the anode for improving the direct
communication between them.[67] Thus, the anodic potential
for the oxidation of H2 (−0.51 V) was extremely close to the
formal potential (−0.58 V, pH = 6.5, vs Ag/AgCl), and the bio-
electrochemical formate generating system equipped with this
bio-anode and formate dehydrogenase-modified bio-cathode
could operate without external energy input. We expect that
these related results would cause researchers’ attention to the
design of advanced anode materials for the development of self-
sustained BA-ECR systems.
3.2.2. Potential Enhancement Strategies
As noted previously, the function of bio-anode in BA-ECR
system is the same as the component of MFC, in spite of the
different ways to use the electricity. Thus, the strategies for
reducing the anode overpotential and improving the anode oxi-
dation current in BA-ECR system can borrow from those for
MFC. In the past decades, a number of novel nanomaterials
have been systematically developed and applied as anode mate-
rials for improving the electricity-generating ability of MFC.
Thus, we briefly discuss these presented anode materials of
MFCs in terms of enhancement strategies with the intention
of providing guidance to the rational and effective tailor of the
anode of BA-ECR system for minimizing the external energy
input.
At the early stage, the anode designs in MFCs have revolved
around efforts to improve the surface properties. In this case,
some electrode treatments or modification strategies, such as
surface oxidation, bio-affinity materials modification, and posi-
tive charged materials modification,[68] have been developed to
endow the anode with good hydrophilicity, high bio-affinity,
or the ability to connect bacterial cells in the ­ electrostatic
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
a­ ttraction way. These strategies are promising for the enhance-
ment of the anode/bacteria interactions and thus the EET
efficiencies. Accompanied by the development of nanotech-
nologies, various 3D nanomaterials with elaborated porous
structures have emerged continuously.[69] The use of these 3D
nanomaterials has thus become another mainstream strategy
for improving anode performance, as it could extend the anodic
exterior surface and even expose the anodic interior surface for
bacterial adhesion. Certainly, these two types of strategies have
also been used in combinations. In a typical example, the 3D
macroporous G/MWCTs/Fe3O4 foam has been demonstrated as
a ­high-performance anode for MFC, where the 3D G/MWCTs
provided the expanded anode area for bacterial adhesion and
the Fe3O4 component with a high bio-affinity toward bacterial
cell improved the anode/bacteria interactions.[70]
Afterward, the MFC anode has advance onto the age of elec-
troactive nanomaterials-hybridized biofilm. Compared to the
traditional mode where the bacterial cells attach to the anodic
materials by means of natural growth, the mode of artificial
nanomaterials-hybridized biofilm possesses higher bacterial
cell density and enhanced EET efficiency. Inspired by this, an
rGO-hybridized biofilm with 3D macroporous network has
been achieved by the self-assembly of GO nanosheets and bac-
terial cells.[71] In this hybrid biofilm, more cells could directly
contact with conductive graphene and even be encapsulated
within the graphene layers, offering an improved bacteria–­
graphene interaction and multiplexed conductive pathways for
enhancing the DET (Figure 6A). As a result, the hybrid biofilm
Figure 6.  The proposed EET processes of different hybrid biofilms. A) rGO/Shewanella hybrid biofilm. Reproduced with permission.[71] Copyright 2014,
Wiley-VCH. B) the PPy-coated Shewanella hybrid biofilm. Reproduced with permission.[72] Copyright 2017, Wiley-VCH.
Adv. Mater. 2019, 1903796 1903796  (10 of 25)
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showed a 25-fold increase in the anodic oxidation current than
that of natural biofilm. To ensure that each cell in artificial bio-
film is highly associated with the nanomaterials, the individual
cell-surface modification strategy has also been applied into the
design of MFC anode. Song et al. reported the use of polypyr-
role (PPy)-modified bacterial cell as an anode for MFC.[72] After
coating with PPy, the bacterial cells located in any positions of
anode could efficiently inject the produced electrons into the
substrate electrode through the conductive coatings, leading to
a high-efficiency DET. In contrast, the propagation of electrons
produced by the bacterial cells far away from the substrate elec-
trode had to go along the adjacent nonconductive bacteria cell
(Figure 6B). Thus, a 23 times decrease in the charge transfer
resistance and a 14.1-fold increase in the electricity-generating
ability have been observed for the PPy-modified bacterial cell.
3.2.3. Cathodic Materials for ECR System
The low product selectivity, high overpotential, and poor con-
version efficiency are key issues that baffle the development of
ECR system. To solve the mentioned issues, the use of high-­
performance heterogenous catalysts as cathodic materials has
flourished. The performance of catalysts for CO2 reduction is
highly related to their compositions and structures. For examples,
the size of catalyst can affect the performance in CO2 reduction,
as it has a direct influence on the number of atoms at corner and
edge positions where the atoms have lower ­coordination number
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and higher surface energy.[73] Furthermore, porous structures are
beneficial for the adsorption and diffusion of CO2, which will
offer a positive effect on catalyst performance.[74] Last, the dis-
parity of the compositions will lead to the alternation in the types
of active sites and the interactions between CO2 and catalysts,
which thus can tune the performance of catalysts toward CO2
reduction.[75] Thus, various nanocatalysts with different compo-
sitions, sizes, shapes, surface structures, and porous structures
have been developed and used for CO2 reduction. In this section,
we focus on the monometallic nanocatalysts, hybrid metallic
nanocatalysts, inorganic metal compounds, metal-organic
frameworks (MOFs), and metal-free carbon materials, because
they are by far the most frequently used catalysts for CO2 reduc-
tion. During the discussion, we will highlight the strategies to
improve the CO2 reduction performance of catalysts, such as
size control, surface structure optimization, porous structure for-
mation, heteroatom doping, and so on.
3.2.4. Monometallic Nanocatalysts
As an important part of monometallic nanocatalysts, metal
NPs have been widely used for ECR due to their high surface
to volume ratio. In recent years, with the development of nano-
technology, synthetic strategies that can precisely tailor the size
and shape of metal NPs at a molecular level have been evolved
to bring new opportunity for ECR. On this context, the inves-
tigations in the size effects of various metal NPs has been
carried out to optimize their performance for ECR. Bao and
co-workers investigated the CO2 reduction performance of Pd NPs
with different sizes from 2.4 to 10.3 nm.[76] For all tested Pd
NPs, the FEs of CO production first increased with increased
applied potential and then decreased at high applied poten-
tial due to the limited mass transport of CO2 in 0.1 m KHCO3
solution. The maximum FE was 91.2%, which was achieved
by using 2.4 and 3.7 nm Pd at −0.89 V (vs RHE, Figure  7A).
With the further increase in the size, the FEs sharply decreased
at any applied potentials. Furthermore, the turnover frequen-
cies (TOFs) for CO formation on Pd NPs within this size range
presented a volcano-like curve (Figure 7B), suggesting that the
adjustment of Pd NPs sizes could tune the CO2 adsorption,
COOH* formation, and CO* removal during the reduction
process due to the varying ratio of corner, edge, and terrace
sites. The Gibbs free energy diagrams from DFT calculations
confirmed that the adsorption of CO2 and the formation of key

Figure 7.  A) FEs and B) TOFs of CO production on Pd NPs with different sizes at various potentials. C) Free-energy profiles for electrochemical
reduction of CO2 to CO on Pd(111), Pd(211), Pd55, and Pd38. Reproduced with permission.[76] Copyright 2015, American Chemical Society. D) FEs of
formate, H2, and CO formation on 3.7 nm Pd NPs at various potentials. The bottom is the corresponding Tafel plots. Reproduced with permission.[78]
Copyright 2017, Springer. E) SEM image of 8 nm Au NPs. F) FEs of CO formation on Au NPs with different sizes at various potentials. G) Density of
Au(111), Au(100), edge, and corner on-top sites on closed-shell cuboctahedral Au clusters with different diameters. The gray dots are the weight frac-
tion of Au bulk atoms. Reproduced with permission.[79] Copyright 2013, American Chemical Society.

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reaction ­intermediate COOH* on corner and edge sites were
more favorable than on the terrace sites of Pd NPs, while the
H2 formation on all these sites was similar (Figure 7C). In a
relevant study,[77] Rahaman et al. studied the size effect of Pd
NPs toward the reduction of CO2 into formate, and observed
that the 6.5 nm Pd NPs had a highest FE of formate production
at −0.1 V (vs RHE). But for 3.8 nm Pd NPs, the FE of formate
production was also up to 86% at this applied potential. Such
a different CO2 reduction performance of 3.7/3.8 nm Pd NPs
can be attributed to the use of different potentials in these two
works. To confirm this, a post-study probed the CO2 reduction
performance of 3.7 nm Pd NPs at an applied potential ranging
from 0.05 to −0.9 V (vs RHE).[78] The results displayed the
major product was formate when the applied potential was in
the range of 0.05 to −0.25 V, while CO was the predominated
product in the range of −0.45 to −0.9 V (Figure 7D).
The size effects of Au NPs and Ag NPs on CO2 reduction
performance have also been systematically investigated. In a
typical example, Zhu et al. prepared monodisperse 4, 6, 8, and
10 nm Au NPs and investigated their CO2 reduction perfor-
mance (Figure 7E).[79] Among the tested Au NPs, the 8 nm Au
NPs showed the best selectivity of CO formation with an FE
up to 90% at −0.67 V (vs RHE, Figure 7F). DFT calculations
indicated that the edge sites were active for CO formation and
the corner sites favored the H2 formation, thus the 8 nm Au
NPs that had the optimum ratio of edge sites over corner sites
achieved the optimal performance (Figure 7G). Moreover, the
CO2 reduction performance has been further upgrade (FE was
97% and mass activity reached to about 3 A g−1 at −0.52 V (vs
RHE)) by integrating the 8 nm Au NPs into a matrix of butyl-
3-methylimidazolium hexafluorophosphate, as the ionic liquid
is a more efficient stabilizer for COOH* intermediate. In a rele-
vant study,[80] by using micelle-synthesized Au in the size range
from 1 to 8 nm for CO2 reduction, Strasser and co-workers con-
firmed that 8 nm was the optimal size for Au NPs. As in the
cases of Pd NPs and Au NPs, the CO2 reduction activity of Ag
NPs presented a size-dependent feature, and the optimal size
was 5 nm.[81] In addition to the mentioned noble metal, the Cu
NPs has been demonstrated to have a size-dependent activity
toward CO2 reduction as well. In the mean size range from 2
to 15 nm, the catalytic activity and selectivity for H2 and CO
had a tendency to dramatically increase with a decreased par-
ticle size of Cu NPs.[82] As the low-coordinate atoms can give
strong chemisorption of CO2, CO, and H atom, the obtained
results can be attributed to the increased ratio of low-coordinate
surface atoms in the smaller Cu NPs. In a recent study,[83] the
DFT calculations have been used to investigate the adsorp-
tion of intermediates on Cu NPs with 13, 55, 147, 309, and
561 atoms and the corresponding free energies for CO2 reduc-
tion. The calculation results showed that CO absorbate-induced
charge perturbation on 309 atom Cu was approximated to that
on the Cu(111) surface. Below this size, the charge perturbation
on Cu NPs became more and more local with the increase in
Cu NPs size. Moreover, Cu NPs with 147 atoms was the best
choice for the formation of two-electron products, because they
had optimal binding energy of the key intermediates.
Besides the size effect, the CO2 reduction performance
of monometallic nanocatalysts can also be affected by their
shapes, which have a strong influence on surface structures
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and morphologies. Inspired by this, the Cu rhombi dodecahe-
drons (RDs) with enriched high-energy {110} facets (Figure 8A)
which were prepared by controllable etching the Cu nanocubes
(NCs) have been used for CO2 reduction.[84] The as-prepared Cu
RDs had the most positive onset potential of −1.1 V (vs RHE).
And its current density at −1.4 V was threefold higher than that
of Cu NCs. Such an enhancement in the catalytic activity toward
CO2 reduction can be attributed to the increased ratio of {110}
facets on Cu RDs surface, as the {110} facets are more active
than {100} facets for CO2 reduction. Moreover, the production
of CH4, C2H4, C2H6, and C3H8 on Cu(110) facets was more
favorable than that on original Cu(100) facets, while the produc-
tion of CO on these two facets displayed the opposite tendency.
As a result, the selectivity for the production of C1 and C2 on
Cu RDs was also better than that on Cu NCs (Figure 8B). Later,
the star decahedron Cu NPs (SD-Cu NPs) with twin bounda-
ries and multiple stacking faults have been fabricated for the
reduction of CO2 into hydrocarbon (Figure 8C,D).[85] The onset
potential of SD-Cu NPs for the formation of CH4 was 0.149 V
lower than that of commercial Cu NPs. Based on quantum
mechanics calculations (Figure 8E), the presence of twin
boundaries that could decrease the formation energy of CHO*
was the key reason for such decrease in onset potential. At high
overpotential, CHO* has become a common intermediate for
the formation of CH4 and C2H4, thus the competition between
CH4 and C2H4 occurred. However, the synergistic effect from
additional surface tension strain and stacking faults on SD-Cu
NPs favored the C2H4 production while suppressing CH4 pro-
duction. Thus, the C2H4 production on SD-Cu NPs increased
in the potential range from −0.92 to −0.98 V (vs RHE), which
was accompanied by a decrease in CH4 production. Addition-
ally, the Pd octahedral particles have been demonstrated to have
better activity and higher selectivity for CO production than
Pd cubes and commercial particles.[86] The DFT calculations
revealed that these improvements were originated from the
weaker CO binding energy on the Pd hydride(111) surfaces
of Pd octahedral particles (Figure 8F). The porous structure
is conducive to improve the electrochemical surface area and
the mass transport for CO2 reduction, thus nanoporous metal
catalysts were also developed to further increase the perfor-
mance. Jiao and co-workers investigated the CO2 reduction per-
formance of nanoporous Ag, which was fabricated by two-step
dealloying of Ag-Al precursor using an aqueous HCl solution.
The nanoporous Ag exhibited dramatic increase in both the
electrochemical surface area (≈150 times larger) and the cata-
lytic activity (≈20 times higher) than polycrystalline silver. The
enhanced catalytic activity could be attributed to the better sta-
bilization of CO2− intermediates on the highly curved surface
of nanoporous Ag, which reduced the thermodynamic barrier.
By employing the similar fabrication method, the 3D nano-
porous Au was also developed as catalyst for CO2 reduction. It
also displayed improved catalytic activity than polycrystalline
Au, mainly because of the presence of 3D nanoporous struc-
ture and the creation of new active sites during the formation
of nanoporous structure.
As previously reported, the edge sites of Au NPs possessed
better CO selectivity, while the corner sites was preferable
for H2 formation.[87] Thus, the Au-based nanomaterials with
high edge-to corner ratio should be high-selectivity catalysts
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www.advancedsciencenews.com www.advmat.de

Figure 8.  A) Transmission electron microscopy (TEM) image of Cu RDs. B) FEs of various products for CO2 reduction on Cu NCs and Cu RDs.
Reproduced with permission.[84] Copyright 2016, American Chemical Society. C) Low-magnification and D) high-resolution TEM images of SD-Cu NPs.
E) DFT relative energies for key intermediates with different coverages. Reproduced with permission.[85] Copyright 2018, Wiley-VCH. F) Free energy
diagram of CO2 reduction on Pd(111), Pd(100), Pd hydride (111), and Pd hydride (100). Reproduced with permission.[86] Copyright 2019, Wiley-VCH.

for the reduction of CO2 to CO. To confirm this hypothesis,
Zhu et al. prepared 2 nm wide Au NWs by a seed mediated
growth method, because their calculation result suggested that
ultrathin 2 nm wide Au NW had a higher percentage of edge
sites than polyhedral NP (Figure  9A,B).[88] The aspect ratio of
the 2 nm wide Au NW can be tuned by reducing their lengths
with electron or infrared beam. Among all the tested 2 nm wide
Au NWs, 500 nm long Au NWs showed the best CO2 reduction
performance. The onset potential for CO2 reduction was −0.2 V
(vs RHE), and the maximum FE reached to 94% at −0.35 V
(Figure 9C). Obviously, this work powerfully demonstrated the
potential of 1D morphologies for CO2 reduction. Afterward,
the investigations of metal NWs for CO2 reduction became
more popular. Recently, Zhang and co-workers reported a
twisted Bi NWs with crystal lattice dislocations by the in situ
electrochemical reduction of the Bi2O3 layer on copper foam
(Figure 9D,E).[89] This nanocatalyst displayed a maximum FE
for formate of 95% at −0.69 V (vs RHE), and the FE maintained
a high value (93%) in the potential range of −0.69 to −0.99 V.
Such high performance can be attributed to the crystal lattice
dislocation on twisted Bi NWs as well as the large active area
of porous structure. The Fourier transformed ac voltammetric

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Figure 9.  A) Edge-site weight percentage as a function of Au atoms for 2 nm wide Au NW and Au NP versus B) TEM image of 2 nm wide Au NW with
the length of 500 nm. C) FEs for CO2 reduction on 2 nm wide Au NW with different lengths at various potentials. Reproduced with permission.[88]
Copyright 2014, American Chemical Society. D) Low-magnification and E) high-resolution TEM images of Bi NW. F) Fourth harmonic components of
Fourier-transformed ac voltammograms from different electrodes in a NaHCO3 solution saturated with CO2 (solid traces) and N2 (dashed traces).
Reproduced with permission.[89] Copyright 2019, Royal Society of Chemistry. G) TEM image of Pd nanosheets. Reproduced with permission.[92] Copy-
right 2018, Wiley-VCH. H) SEM and I) TEM image of Bi nanosheets. Reproduced with permission. Copyright 2018, Springer Nature.[93]

investigation (Figure 9F) indicated that the rate-determining
step is the reduction of protonated CO2•−, which was distinct
from that of traditional Bi-based materials. Thus, a new type
of catalytic active sites was formed in the twisted Bi NWs. Fur-
thermore, the modification of metal NWs with polymers can
further optimize their CO2 reduction performance. Zhang et al.
used polytetrafluoroethylene as surface modifier for Cu NWs,
and the obtained catalyst displayed a CO FE of 71% at −0.4 V
(vs RHE) and a formate FE of 68% at −0.6 V as a result of the
increased supply amount of CO2 reactants and the prevention
of excessive proton supply.[90] By replacing the polytetrafluoro-
ethylene with polydopamine, the prepared Cu NWs catalyst
showed 2.3-fold increase in the CH4 selectivity compared to the
original Cu NWs, as the amino groups in the polydopamine
could capture and transfer protons for the hydronation of CO*
intermediates while the phenolic hydroxyl groups could stabi-
lize the CO* intermediates.[91]
In order to further improve the atom utilization efficiency, the
catalysts with 2D morphologies have also emerged in the field
of ECR. Gong and co-worker investigated the CO2 electrore-
duction performance of the hexagonal Pd nanosheets.[92] The
obtained hexagonal Pd nanosheet presented a 5 atomic thick-
ness and 5.1 nm edge length (Figure 9G). The CO2 reduction
results illustrated that the hexagonal Pd nanosheets have a

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www.advancedsciencenews.com
maximum FE for CO of 94% at −0.5 V (vs RHE) without any
decay after 8 h test. At −0.9 V, the mass activity of this catalyst
was over fivefold greater than Pd NPs with similar size. The
DFT calculation suggested that the enhanced performance
was resulted from the edge sites on hexagonal Pd nanosheet.
Moreover, the ultrathin bismuth nanosheets which possessed
single crystallinity and enlarged surface area (Figure 9H,I) was
prepared for electrocatalytic reduction of CO2.[93] Owing to the
advantageous nanostructure, the obtained catalyst showed high
selectivity for formate formation and large current density over
a broad potential range. DFT calculations revealed that the high
formate selectivity was came from the stabilized intermediate
(HCO2*) on Bi (001) surface.
Apart from the aforementioned optimization in the size,
shape, structure, and dimensionality, some other strategies
have been adopted to further improve the performance. The
first one is to dope metal nanocatalysts with foreign atoms.
Doping metal nanocatalysts with heteroatoms could modify the
local electronic structure of metal or facilitate the formation of
the COOH* or favor the activation of water and the formation
of hydrogen species. Thus, these investigated metal nanocata-
lysts showed increased catalytic activities and higher FEs after
doping with heteroatoms.[94] The fabrication of metal nano-
catalyst-based composites is another commonly used strategy,
as this arrangement can take full advantage of the synergistic
effects from different components. Inspired by this, the oxide-
derived Cu/carbon composite was used as catalyst for ECR,
which realized the high-selective production of alcohol com-
pounds with a maximum FE of 71.2% at −0.7 V (vs RHE).[95]
Considering that doping carbon materials with nitrogen
atoms can further improve their catalytic activities, the N-doped
carbon materials has become another good choice to combine
with metal nanocatalysts for obtaining high-­ effective com-
posite catalysts. For instances, the Cu NPs-pyridinic-N rich
graphene and single-crystalline Au NPs-N-doped graphene
quantum dots composites have been proven to be excellent cat-
alysts for ECR.[96]
3.2.5. Hybrid Metallic Nanocatalysts
The electronic properties of atoms on the catalyst surface are
easily affected by their surrounding atoms.[5b] In the case of
monometallic nanocatalysts, this effect is negligible as the
adjacent atoms have a similar electronic structure. In contrast,
this effect appears pronounced for the hybrid metallic nano-
catalysts due to the interplay of different metal elements, thus
leading to the difference in the binding energy of the key reac-
tion intermediates and the CO2 reduction performance. On this
context, various bimetallic NPs have been tested for ECR, such
as AuCu NPs,[97] Au-Sn NPs,[98] Au-Pd alloy,[99] Pb-Pd alloy,[100]
and CuxNiy NPs.[101] In a typical work, the Cu2−xSey nanocata-
lysts which were prepared by solvent coordination molecular
templated method were used for the electrochemical reduction
of CO2 to methanol.[102] The size and morphology of this cata-
lyst could be tuned by changing the ratio of diethylenetriamine
to H2O during the preparation. The Cu1.63Se(1/3) catalyst dis-
played a maximum current density of about 41.5 mA cm−2 at
−2.1 V (vs Ag/AgCl) with very high FE (77%) for methanol
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production (Figure  10A). The reporters attributed this excel-
lent performance to the well-cooperative effect from Cu and
Se. Theoretical optimization of the ratio of different elements
in alloy NPs is beneficial for optimizing the selectivity of CO2
reduction reaction. Cui and co-workers compared the thermo-
dynamic limiting potentials (|UL|) of Sn, CuSn, CuSn3, and Cu
for CO, H2, and HCOOH formation by the aid of DFT calcula-
tions.[103] The results displayed that all the catalysts had similar
theoretical activities toward HCOOH formation. But the CuSn3
had the highest |UL| values toward both CO and H2 production,
which reflected that CuSn3 have the lowest activity toward the
formation of CO and H2 and thus the highest HCOOH selec-
tivity. The experimental results confirmed that the co-deposited
CuSn3 alloys indeed displayed the highest HCOOH selectivity
during the applied potentials. The maximum HCOOH selec-
tivity was up to 95% at −0.5 V (vs RHE) due to the suppression
of hydrogen and CO generation.
As in the case of monometallic nanocatalysts, the shape and
structure of the alloy also play an important role in its CO2
reduction performance. Recently, Luo et al. reported Cu-In cata-
lyst with a thin layer of In supported on the Cu NWs surfaces
for CO2 reduction, which was prepared by a cascade process of
the deposition of In3+ on Cu(OH)2 NWs, mild oxidation, and
in situ electroreduction.[104] The catalyst presented a CO FE of
about 93% in the potential range of −0.6 to −0.8 V (vs RHE)
due to the enhanced adsorption of COOH* and the destabilized
adsorption of H* on the Cu–In interface. To further improve
the CO2 reduction capability of alloy metal NWs, the concept of
single-atom catalysis has been coupled with them. A so-called
atom-pair catalyst (APC) that features a highly active atomic
interface has been developed for ECR.[105] In this APC, the
Cu10–Cu1x+ (four Cu atoms bind with O to form Cu1x+) pairs
were firmly anchored on the Pd10Te3 alloy NWs by the Te sur-
face defects (Figure 10B–D). This APC delivered a total cur-
rent density of 18.74 mA cm−2 at −0.98 V (vs RHE), which was
6.94 times higher than that for pristine Pd10Te3 NWs. More-
over, the maximum CO FE for this catalyst was 92% at −0.78 V,
which was 6.57 times higher than that for pristine alloy NWs
(Figure 10E). DFT calculations attributed these enhancements
to the presence of Cu10–Cu1x+ pairs, which could promote
CO2 activation by using H2O molecule adsorbed on Cu1x+ to
stabilize the CO2 molecule chemisorbed on the adjacent Cu10
(Figure 10F). Additionally, the CuAg catalysts with nanoporous
structure have been investigated for ECR.[106] The catalyst con-
taining 6% Ag possessed high selectivity for both C2H4 (FE,
60%) and C2H5OH (FE, 25%) formation at −0.7 V (vs RHE),
which represented an obvious improvement in the genera-
tion of these two products compared to the Cu-based catalysts
at that moment. The high surface area from porous structure
and the synergistic effects of the enhanced stabilization of
Cu2O overlayer and the abundant CO intermediate provided
by the Ag component were the reasons for the performance
enhancement.
The core–shell configuration is another important form of
hybrid metallic nanocatalysts. Encouraged by the success of
alloy configuration, the potential of multi-metallic catalysts
with core–shell configuration in ECR has thus been tapped.
The Au-Fe core–shell NPs prepared by leaching out the Fe com-
ponent on the Au-Fe alloy surface has been demonstrated to
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Figure 10. A) Catalytic activities of various Cu-based catalysts toward CO2 reduction. Reproduced with permission.[102] Copyright 2019, Springer
Nature. B) SEM and C) high-resolution TEM images of Cu atom pair (0.1 wt%) supported by Pd10Te3 NWs. D) Schematic diagram of Cu atom pair
supported by Pd10Te3 NWs. E) FE for CO and H2 formation on different Cu samples at −0.78 V (vs RHE). F) Free-energy profiles for CO2 activation on
different Cu samples and the proposed models of physisorbed and chemisorbed CO2 on Cu-APC. Reproduced with permission.[105] Copyright 2019,
Springer Nature.

exhibit outstanding CO selectivity, excellent stability, and 0.2 V
lower in overpotential compared to Au NPs,[107] while the onset
potential for the electroreduction of CO2 to ethane on Cu NPs
had a decrease of 200 mV after coating a thin layer of Ru on
Cu NPs to form Ru@Cu NPs.[108] Additionally, the core–shell-
structured NWs and NWs array have also been proved to be
ideal catalysts for ECR.[109] Recently, the concept of applying the
alloy shell to replace the monometallic shell in traditional core–
shell configuration has been proposed to further optimize the
performance. Gong and co-workers reported a new core–shell
nanocatalyst for CO2 reduction, in which the Pd-Au alloy served
as the shell while the Pd NC was the core.[110] The core–shell
catalyst was prepared by a kinetically controlled nucleation and
growth method, and the thickness and alloying degree of Pd-Au
shell could be controlled by adjusting the volumes of precur-
sors (Figure  11A–F). The Pd@Pd3Au7 nanocrystals showed
the best CO2 reduction performance, with a CO FE of about
100% at the potential ranging from −0.6 to −0.9 V (vs RHE,
Figure 11G). Such excellent CO FE and selectivity were come
from the synergistic ensemble and ligand effects, which could
weaken the Pd-C bond in virtue of the adjacent Pd-Au sites and
electron transfer between these sites and thus balance the ΔG
of COOH* and CO* (Figure 11H). Besides the alloy and core–
shell configurations, the dimer configuration has already been
used to fabricate bimetallic nanocatalyst for ECR. In a case of
Ag-Cu nanodimers, the FE of C2H4 formation was enhanced
by 3.4-fold compared with the pure Cu NPs in similar size and
shape, because of the sequential catalysis and electronic effects.

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Figure 11.  A–F) TEM images of A,D) Pd@Pd7Au3, B,E) Pd@Pd3Au7, and C,F) Pd@Pd1Au9 NCs at different magnifications. G) FEs of CO formation on
different samples. H) Free-energy diagram of CO2 reduction. Reproduced with permission.[110] Copyright 2019, American Chemical Society.

3.2.6. Inorganic Metal Compounds
The commonly used inorganic metal compounds in ECR are
metal oxides and metal sulfides. For metal oxides, they can
possess high energy efficiency and selectivity toward CO2
reduction, thus making them attractive.[6a] As a typical metal
oxide, Co3O4 has been widely investigated as a catalyst for
ECR. In 2015, by fast-heating the ultrathin precursor, Xie and
co-workers synthesized the CO3O4 layers with 1.72 and 3.51 nm
thickness for CO2 reduction.[111] The catalyst with 1.72 nm
showed increased FE and better stability compared to the Co3O4
layers with 3.51 nm thickness. The maximum FE of formate
formation was over 64.3% at −0.88 V (vs saturated calomel elec-
trode (SCE)). To explore how the presence of a surface oxide
affects the CO2 reduction performance of Co3O4, this group
subsequently prepared partially oxidized Co layer with 4-atom
thickness (≈0.84 nm, Figure 12A–C),[112] which possessed abun-
dant active sites and improved electronic conductivity provided
by the increased charge density near Fermi level. As a result,
this catalyst maintained a formate FE of about 90.1% at −0.85 V
(vs SCE), which was higher than that of Co 4-atom-thick layer
(Figure 12D), indicating that partial oxidation improved the
intrinsic catalytic activity. The volumetric CO2 adsorption meas-
urement and the electrochemical active surface area corrected
Tafel plots demonstrated that the catalyst had an increased CO2
adsorption capacity and a Tafel slope of approximately 59 mV,
reflecting this catalyst was beneficial for CO2 activation and
CO2•− intermediate stabilization. Apart from the formate pro-
duction, the Co3O4 has been used for CO formation.[113] In
the case of Co3O4 nanofibers, the CO FE reached 65%. Addi-
tionally, some other transition metal oxides have been tested.
For example, the WO3 nanostructure was proved to display
an onset potential of −0.16 V (vs SHE) for CO2 reduction in
acetonitrile media.[114] Aiming at engineering the electronic
properties, the oxygen vacancies have been introduced into the
ZnO nanosheets.[115] The resulted catalyst displayed good cata-
lytic activity toward CO2 reduction, with a CO FE of 83%, as
the oxygen vacancies improve CO2 binding strength and activa-
tion. To further improve the catalytic efficiency in virtue of the
synergistic effect, various metal oxides-based composites have
also been developed toward ECR. Benefiting from the synergy
effect between Au and CeOx, the prepared Au-CeOx composite
catalyst exhibited much better activity and FE than the corre-
sponding single-component catalyst for ECR.[116] Moreover,
the In(OH)3-coupled Cu2O-derived composites have been fab-
ricated as catalysts for ECR. The results showed that the com-
position ratio could influence the synergistic effects of these
composites and thus the catalytic efficiencies. The composite

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Figure 12.  A) Lateral high-angle annular dark-field scanning transmission electron microscopy image of partially oxidized Co 4-atomic-layer. B) The
intensity profile along the pink rectangle. C) The crystal structures. D) FEs of formate production on partially oxidized Co 4-atomic-layer (red), Co
4-atomic-layer (blue), partially oxidized bulk Co (violet) and bulk Co (black) at various potential for 4 h. Reproduced with permission.[112] Copyright
2016, Springer Nature. E) Binding configurations of different intermediates to the Mo atoms (green) and S atoms (yellow) on the edge site of MoS2.
Reproduced with permission.[121] Copyright 2014, Wiley-VCH. Crystal structures of the active sites of F) CO dehydrogenase and G) Fe4.5Ni4.5S8. Repro-
duced with permission.[124] Copyright 2019, Royal Society of Chemistry.

catalyst with an optimal composition ratio reached a CO FE of
90.37% at −0.8 V (vs RHE).[117]
Metal sulfides have a unique advantage that they can break
the linear relationship between the binding energies of dif-
ferent reaction intermediates in certain conditions, endowing
them with great potential to ECR. Luo and co-workers reported
the use of Ag2S NWs for electrochemical CO2 reduction in
ionic liquid with a CO selectivity of 92%,[118] while Zeng and
co-workers utilized cadmium sulfoselenide and achieved a CO
FE of 81%.[119] Considering the high cost of Ag and toxicity of
Cd, the exploration of metal chalcogenide-based catalysts has
been converted to use earth-abundant and low-toxicity transi-
tion metals, such as Cu, Fe, Ni, Mo, Sn. Sargent and co-workers
modified Cu2S core with Cu surface vacancies for steering
post-C–C coupling selectivity in CO2 reduction reaction.[120]
As a result, the FE of C2+ alcohol production reached to about
32%, because the subsurface sulfur atoms and the surface
copper vacancy could together increase the energy barrier for
the ethylene production and shift the balance toward the alco-
hols production. On the basis of DFT, Nørskov and co-workers
probed the active edges of MoS2 and MoSe2.[121] They predicted
that the bridging S or Se atoms were in favor of binding the
COOH* and CHO* intermediates, while the metal at these
edges anchored CO* preferentially (Figure 12E). These fea-
tures signified that the MoS2 and MoSe2 would break the linear
scaling relations and possess a high CO2 reduction activity. The
same group further investigated the scaling relations for var-
ious transition metal-doped MoS2,[122] and they predicted that
doping MoS2 with transition metal could be effective to lower
the overpotential of electrochemical CO2 reduction, as the two
binding sites in the catalyst could provide two distinct linear
scaling relationships for guaranteeing the strong binding ener-
gies of key intermediates over CO*. Recently, this transition
metal-doping strategy has been extended to SnS2, the created
SnS2 nanosheets with Ni doping exhibited an FE of 93% for the
carbonaceous product at −0.9 V (vs RHE).[123] Apart from transi-
tion metal-doping strategy, mimicking the active center struc-
ture of enzymes seems to be another effective strategy because
of the high selectivity and catalytic activity of the enzyme.
Inspired by this, the pentlandite (Fe4.5Ni4.5S8) that possessed a
structure analogous to the active site of carbon monoxide dehy-
drogenase ([Ni-4Fe-5S] cluster (Figure 12F,G) was developed for
CO2 reduction.[124] The peak FE for CO and methane produc-
tion reached 87% and 13%, respectively.
3.2.7. Metal-Organic Frameworks
MOFs are a subclass of coordination polymers, in which metal-
based inorganic building blocks are coordinated to multi-dentate

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organic linkers to form 3D inter-connected networks. Owing to
these 3D networks, MOFs are featured with high porosity and
large surface area, which guarantee the fast mass transport
and high density of active sites. Furthermore, both metal and
organic ligand components of MOFs are abundant elements
and the diversity of organic ligands makes it easy to tune the
properties of MOFs according to the application requirements.
Benefited from as-motioned advantages, MOFs have emerged
as decent catalysts for various processes including OER, HER,
and ORR.[125] In 2012, Kumar et al. have successfully demon-
strated that Cu-based MOF (Cu3(BTC)2-MOF) was an active
catalyst for the electrochemical reduction of CO2 to oxalate in
a nonaqueous medium, initiating the development of MOFs
for ECR.[126] Subsequently, the Cu-based MOFs with different
organic ligands have been widely investigated, such as copper
rubeanate MOF, HKUST-1 ([Cu3(µ6-C9H3O6)2]n), CuAdeAce
([Cu3(µ3-C5H4N5)2]n), and CuDTA mesoporous metal-organic
aerogel ([Cu(µ-C2H2N2S2)]n).[127] Besides, MOFs with other
metal centers including Co, Zn, and Fe have also been reported
as catalyst materials for CO2 reduction.[128] In a typical example,
the cobalt-porphyrin MOF (Al2(OH)2TCPP-Co, TCPP-H2  =
4,4’,4’’,4’’’,-(porphyrin-5,10,15,20-tetrayl)tetrabenzoate) exhib-
ited a CO selectivity of over 76%.[129] The in situ spectroelec-
trochemical analysis revealed that the reduction of CoII sites to
catalytically active CoI state could occur during the test, thus
leading to high CO2 reduction performance.
Although the aforementioned progresses have been made,
the poor stability and conductivity have inevitability limited
the in-depth applications of MOFs in ECR. To address these
issues, a hybrid strategy has been introduced in the design of
new generation MOFs catalysts. With the assist of an in situ
hydrothermal method, Lan and co-workers prepared a series
of polyoxometalate-metalloporphyrin organic frameworks
(M-PMOFs, M = Co, Fe, Ni, and Zn) by the integration of
electron-rich Zn-ε-keggin clusters ({ε-PMo8VMo4VIO40Zn4})
with tetrakis[4-carboxyphenyl]-porphyrin-M (M-TCPP) linkers
(Figure 13A).[130] Owing to the formation of oriented electronic
transportation channel by this direct communication of reduc-
tive polyoxometalate (POM) unit with metalloporphyrin, the
obtained M-PMOFs showed great improvements in the term
of electron collecting and donating as well as migrating, which
eventually facilitated the electron transfer processes in ECR. As
a result, all these M-PMOFs presented excellent performance.
And the Co-PMOFs showed the best performance with a CO FE
of 98.7% and a TOF of 1656 h−1 at −0.8 V (vs RHE). DFT cal-
culation attributed these high performances to the synergistic
effect of reductive POM and Co-porphyrin (Figure 13B). Fur-
thermore, a Cu NPs-embedded Zr-based MOF has been devel-
oped and displayed a formate FE of 28% at −0.82 V.[131]
In addition to hybridization, pyrolysis is also an effective
strategy to improve the conductivity and stability of MOFs.
In most cases, the pyrolysis of MOFs can create atomically
dispersed metal sites (ADMSs), which coordinate to doped N
atoms by strong M-N coordinative bonds. Theses formed
M–Nx structures and the stable carbon networks get together to
improve the chemical and thermal stability as well as ­electronic
conductivity. More importantly, the formed M–Nx struc-
tures can serve as the active sites to adsorb and activate CO2

Figure 13.  A) Schematic diagram of the structures of M-PMOFs (M = Co, Fe, Ni, and Zn), which were constructed by the four-connected TCPP linkers
and zigzag POM chains. B) The proposed CO2 reduction mechanism on Co-PMOF. Reproduced with permission.[130] Copyright 2018, Springer Nature.
C) FEs and D) TOFs of CO formation on different samples at various potentials. E) Free-energy diagrams for electrochemical reduction of CO2 to CO
on Co–N2 and Co–N4. Reproduced with permission.[133] Copyright 2018, Wiley-VCH.

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www.advancedsciencenews.com
­ olecules and promote the reduction of CO2 molecules.[132] As
m i­ntroduced Lewis base sites by doping N can easily interact with
a representative work, Wu et al. prepared a series of atomically
dispersed Co with different N coordination numbers by the
pyrolysis of Co/Zn zeolitic imidazolate frameworks (ZIFs) and
investigated their CO2 reduction performance.[133] The results
showed that the atomically dispersed Co with two-coordinate N
atoms exhibited the best performance with a CO FE of 94% and
TOF of 23 200 h−1 at −0.68 V (vs RHE, Figure 13C,D). DFT cal-
culations revealed that less energy was required for the forma-
tion of COOH* on Co-N2 and thus lead to high performance.
In contrast, both the adsorption energies of COOH* and H*
were high on Co-N4, but the required energy of H* adsorption
was lower than that of COOH* adsorption, thus lead to poor
performance (Figure 13E). Furthermore, some other ADMSs
materials prepared by the pyrolysis of various MOFs have
been proved to be effective catalysts for ECR, including the
single-atom Ni catalyst derived from Ni-exchanged ZIF-8,[134]
the single-atom Fe catalysts derived from Fe-doped ZIF-8,[135]
the Ni-N sites-doped porous carbon catalyst derived from Zn/
Ni bimetallic ZIF-8,[136] and so on. Besides these MOFs-derived
ADMSs materials, other kinds of ADMS materials like carbon-
based single-metal-atom materials[137] and covalent organic
frameworks[138] have also been investigated as ECR cata-
lysts. For examples, Varela et al. developed metal-containing
N-doped porous carbon black catalysts by processing the mix-
ture of polyaniline, carbon powder, and Fe and/or Mn salts for
ECR,[139] while Lu et al. investigated the performance of atomic
Ni-anchored covalent triazine framework toward ECR.[140] In
analogy to MOFs-derived ADMSs materials, both of these cata-
lysts have displayed decent catalytic efficiencies.
3.2.8. Metal-Free Carbon Materials
Undoubtedly, metal-based materials were the most high-profile
and dominant CO2 reduction catalysts over the past years. In
spite of a bright future, there are still some aspects needed to
be perfected, such as high cost and inferior selectivity. Com-
pared to metal-based materials, carbon materials are more cost-
effective and possess individual inherent features like chemical
and thermal stability, environmental friendliness, large sur-
face area, wide sources, and easy fabrication of various unique
porous structures, thus making them potential alternatives to
ECR.[141] In general, the CO2 reduction performances of pure
carbon materials are negligible since CO2 molecules almost
cannot be activated by the neutral carbon atoms. In this case,
the doping of heteroatoms with electron-donating or electron-
drawing features has been proposed, which can effectively
modulate the electronic properties of carbon atom in pristine
carbon materials for improving their catalytic activity. Further-
more, the heteroatom doping has a positive effect on the wet-
tability of carbon materials, thus facilitating the diffusion of the
hydrated CO2 toward the catalytic sites.[142] Thus, various heter-
oatom-doped carbon materials have been investigated for ECR.
Compared to a carbon atom, the nitrogen atom has a larger
electronegativity, thus more electrons will be attracted into
N-doped carbon materials for improving the electronic or
ionic conductivity. Moreover, N-doped carbon materials also
have superiority in the CO2 adsorption aspect, because the
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the CO2 molecules (weak Lewis acid).[11c] Thus, the nitrogen
atom has become a good dopant for the design of decent heter-
oatom-doped carbon catalysts. In 2015, Ajayan and co-workers
investigated the potential of nitrogen-doped CNTs (NCNTs,
Figure 14A) in ECR.[143] In contrast to CNTs with poor activity
and selectivity toward CO2 reduction, the NCNTs showed a max-
imum CO FE of about 80% at −0.78 V (vs RHE, Figure 14B).
Moreover, the onset potential was −0.70 V, reflecting an overpo-
tential of −0.18 V. Based on the DFT calculations, the potential-
limiting step for CO production was the formation of adsorbed
*COOH. The pyridinic N was proposed to be the most efficient
active site among the different N configurations in NCNTs,
which required an overpotential as low as −0.2 V (Figure 14C).
Furthermore, the pyridinic N had a strong binding energy
of *COOH but weak binding energy of *CO, thus leading to
the high selectivity for CO production. After doping with the
nitrogen atom, some other carbon materials, such as graphene,
nanodiamond, and graphene quantum dots, have also mani-
fested strong catalytic ability toward CO2 reduction.[144] Besides,
the doping of carbon materials with boron atoms or fluorine
atoms can also improve their CO2 reduction performance. For
examples, a boron-doped diamond electrode was proved to pro-
duce formaldehyde with a maximum FE of 74%,[31b] while a flu-
orine-doped carbon was capable of highly selective conversion
of CO2 to CO with a maximum FE of 90%.[145]
To further improve the CO2 reduction ability of heteroatom-
doped carbon materials, two main strategies have been devel-
oped. The first one is the introduction of porous structure,
which can extend the SSA and promote mass transport.[146]
Inspired by this, N-doped 3D graphene was prepared as a cata-
lyst for ECR,[147] which revealed an ultralow onset overpotential
(−0.19 V) for CO formation and a maximum FE of ≈85% at a
lower overpotential of −0.47 V. The DFT calculations revealed
that these excellent catalytic performances were originated
from the pyridinic-N defects, which could lower the free energy
barrier for the formation of adsorbed COOH*. The second
strategy is to dope the heteroatom-doped carbon materials with
another suitable heteroatom for further modulating the elec-
tronic properties. In recent work, the incorporation of electron-
rich fluorine into the pyridinic-N sites has greatly improved the
CO2 reduction performance of N-doped holey carbon layer.[148]
The N,F-co-doped holey carbon layers fabricated at 950 °C
possessed a maximum CO FE of 90% at an overpotential of
−0.19 V (Figure 14D–F). The F doping drastically decreased
the free energy barrier of *COOH formation but increased the
binding energy of H* on the pyridinic-N sites. Additionally, the
S,N-doped polymer-derived carbons also displayed higher FE
of CO and CH4 formation than the S-doped counterpart,[149]
which again proved the superiority of heteroatoms co-doping.
4. Conclusions and Perspectives
In recent years, the exploitation of high-performance electrode
materials has flourished, which helps to push the develop-
ment of ECR system. On one side, a variety of decent photo-
anode materials and substrate materials of bio-anode have
been created to produce as much endogenous electric energy
© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com www.advmat.de

Figure 14.  A) SEM image of NCNTs and the corresponding element mapping images. B) FEs of CO formation on NCNTs and CNTs at different
potentials. C) Free energy profiles for electrochemical reduction of CO2 to CO on NCNTs and CNTs. Reproduced with permission.[143] Copyright 2015,
American Chemical Society. D) High-resolution TEM and E) the corresponding elemental mapping images of N,F-co-doped holey carbon layers fab-
ricated at 950 °C. F) FEs of CO formation as a function of applied potential on N,F-co-doped holey carbon layers fabricated at different temperatures
and N-doped holey carbon layers. Reproduced with permission.[148] Copyright 2019, American Chemical Society.

as possible so that the external power needed for driving the
electrochemical CO2 reduction has been obviously diminished.
On the other side, a number of superior heterogenous catalysts
have been built as cathode materials, which largely upgraded
the CO2 conversion efficiency like selectivity, the yield of prod-
ucts as well as the overpotential. In this review, most of these
electrode materials have been systematically discussed and the
enhancement strategies used in the design of these ­electrode
materials are highlighted from the perspective of electricity
generation efficiency and CO2 conversion efficiency. For photo-
anodes, the integration of photoelectric materials with the
co-catalysts or other suitable photoelectric materials has been
introduced to depress the recombination of electron–hole pair
and improve the photo-to-electric conversion efficiency. As to
bio-anodes, they have high homology with the bio-anodes in
MFCs. The utilization of electrode substrate materials with
special surface properties and appropriate porous structures as
well as the optimized combination modes between substrate
materials and biocatalyst are beneficial for the attachment of
biocatalyst and the EET, eventually leading to a high-efficiency
conversion of chemical energy into electrical energy. For the
cathodic materials, the optimization of size, shape, and mor-
phology of metal nanomaterials as well as alloying treatment
has demonstrated to display positive effects on electronic struc-
tures and inherent catalytic activity. Doping transition metal
and mimicking the active center structure of enzymes have
also been proved to be effective for exploring high-performance
inorganic metal compounds for ECR. The hybrid strategy
and pyrolysis strategy effectively improved the stability and
conductivity of metal-organic frameworks as well as created
new active sites for ECR. Doping heteroatoms successfully
reformed the nature of carbon materials from electrochemically
inert to electrochemically active toward the CO2 reduction reac-
tion. Furthermore, the introduction of porous structures also
improved the CO2 reduction performance of cathodic materials,
as it promoted the diffusion of CO2 molecule and extended the
catalytic active area.
Despite these delicate strategies and sophisticated electrode
materials have brought pronounced strides, there is still great
space to improve ECR system and many issues need to be
addressed for practical application. In the future, the relevant
studies can focus more on the following aspects:
1) Searching new-generation anode that can solely drive the
ECR on the cathode. Except for the cascading of multi-an-
odes in series, the current photo-anode-assisted system and
the bio-anode-assisted system still operated with the need
of a relatively small external bias voltage. For photo-anode-
assisted system and bio-anode-assisted system, the diversity
of photo­ electric materials and substrate materials of bio-
anode as well as the corresponding enhancement strate-
gies are scarce compared to their photovoltaic cell and MFC
counterparts, respectively. Therefore, much more efforts
should be dedicated to developing novel and high-efficiency
photoelectric materials and substrate materials of bio-anode
by drawing on the excellent research results in the anode
of photovoltaic cell and MFC. Moreover, the integration of
photo-anode and bio-anode would be a promising concept, as

Adv. Mater. 2019, 1903796 1903796  (21 of 25) © 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.advancedsciencenews.com
the multiple ­energy conversion will be achieved in this case.
Recently, the photoelectric materials have been introduced as
anode substrate materials for MFCs,[150] where both chemi-
cal energy and solar energy have been converted to electrical
energy for an improved electricity generation ability of the
anode.
2) Developing stable and cost-effective cathode materials to ef-
ficiently generate high value-added products. With the assis-
tance of current cathode materials, the products generated
from the ECR system were often C1 products and C2 prod-
ucts. Thus, studies on the cathode materials with the abil-
ity to generate higher value-added products would further
broaden the appeal of ECR. To realize this goal, the in-depth
understanding of the mechanism for ECR is required. At pre-
sent, the DFT calculations are commonly used to study the
mechanisms for CO2 reduction performance of cathode ma-
terials. These theoretical calculations should be well coupled
with experimental analysis. On this context, more advanced
in situ or in operando characterization methods would be re-
quired. Furthermore, the linear scaling relationship between
the binding energy of key intermediates poses a fundamental
limitation to the catalytic activity of cathode catalysts. Break-
ing these linear scaling relationships would favor the genera-
tion of high value-added products. The current strategies to
overcome this limit are rare. All of them mainly rely on the
concept of providing different binding sites for different in-
termediates, so that different reaction pathways are preferen-
tial. Thus, research on the more effective strategies to break
these linear scaling relationships would make it possible to
obtain multi-carbon products with high efficiencies. Indeed,
the precise synthesis technologies of cathode materials are
also needed to guarantee the realization of high value-added
products. Besides generating high value-added products in
an efficient manner, the stability and cost are also the evalu-
ation criteria of cathodic materials in the practical applica-
tion of ECR. For most of the reported cathodic materials, they
generally display decent catalytic activities within dozens of
hours. Recently, by introducing a polymer-based gas diffusion
layer, the lifetime of cathodic materials has been extended to
150 h,[151] which strongly supports that the long-time stability
of cathodic materials can indeed be improved. Therefore,
more solutions should be searched to further optimize the sta-
bility of catalysts. With respects to the cost, it has been largely
reduced in recent years. As introduced in Section 3.2.3, many
cost-effective materials including transition metal-based ma-
terials, metal-free materials, and natural substance-derived
materials have been created to replace the traditional noble
metal materials. Nevertheless, the fabrication costs of these
materials have been ignored to some extent. In a word, we
should pay more attention to lifetime and cost when develop-
ing high-efficiency cathodic materials toward ECR.
3) Cross-study of the anode materials and cathode materials.
The energy match between anode and cathode is prerequisite
for the achievement of a self-powered ECR system. Over the
past years, most of the investigations on the cathode materi-
als and anode materials of ECR system are isolated. Although
various effective cathode materials have been developed for
traditional ECR system, only a small fraction of them
have been applied in the photo-anode-assisted system and
Adv. Mater. 2019, 1903796 1903796  (22 of 25)
www.advmat.de
bio-anode-assisted system. What will happen if we integrate
the excellent cathode material originated from the traditional
system into the photo-anode-assisted system and bio-anode-
assisted system with high electricity generation efficiency?
Thus, it is better to crosslink the research results of these
two aspects.
In summary, with the continuous efforts devoted to ECR, we
have good reason to believe that the self-powered ECR system
with high value-added products will be realized in the future. At
that time, ECR technology will become an integral part of the
global carbon cycle.
Acknowledgements
R.B.S., W.Z., and J.F. contributed equally to this work. The authors
gratefully acknowledge the financial support from the National Natural
Science Foundation of China (21834004, 21804070, and 21775067),
the International Cooperation Foundation from Ministry of Science and
Technology (2016YFE0130100), and the China Postdoctoral Science
Foundation (2017M621694 and 2018T110475).
Conflict of Interest
The authors declare no conflict of interest.
Keywords
bioanodes, CO2 reduction, electrocatalysis, electrode materials,
photoelectric conversion
Received: June 14, 2019
Revised: August 5, 2019
Published online:
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