Electrodeposited Cu-Pd bimetallic catalysts for the selective electroreduction of CO2to ethylene

Article abstract of DOI:10.1039/d0gc03051a

Cu-Pd bimetallic catalysts were fabricated on carbon paper (CP) by the electrodeposition method via a dynamic hydrogen bubble template approach. At a potential of -1.2 V vs. RHE, the Faradaic efficiency (FE) of C2H4 could reach 45.2% with a current density of 17.4 mA cm-2 in an H-type electrolytic cell. Detailed studies suggest that the enhanced performance of Cu-Pd/CP was attributed mainly to the synergistic effect, low interfacial charge transfer resistance, and the 3D architecture of the catalysts.

Full text of DOI:10.1039/d0gc03051a

View Article Online
View Journal
Green
Chemistry
Cutting-edge research for a greener sustainable future
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: R. Feng, Q. Zhu,
M. Chu, S. Jia, J. Zhai, H. Wu, P. Wu and B. Han, Green Chem., 2020, DOI: 10.1039/D0GC03051A.
Volume 20
Number
May 2018
Pages 1919-2160
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
9
7
Green
Chemistry
Cutting-edge research for a greener sustainable future
rsc.li/greenchem
Accepted Manuscripts are published online shortly after acceptance,
before technical editing, formatting and proof reading. Using this free
service, authors can make their results available to the community, in
citable form, before we publish the edited article. We will replace this
Accepted Manuscript with the edited and formatted Advance Article as
soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes to the
text and/or graphics, which may alter content. The journal’s standard
Terms & Conditions and the Ethical guidelines still apply. In no event
shall the Royal Society of Chemistry be held responsible for any errors
or omissions in this Accepted Manuscript or any consequences arising
from the use of any information it contains.
ISSN 1463-9262
PAPER
Paul T. Anastas et al.
The Green ChemisTREE: 20 years after taking root with the 12
principles
rsc.li/greenchem

Page 1 of 5
Please Gd roe en no tC ha ed mj u iss tt r my argins
View Article Online
DOI: 10.1039/D0GC03051A
Journal Name
PAPER
Electrodeposited Cu-Pd Bimetallic Catalysts for the Selective
Electroreduction of CO to Ethylene
2
a
b
a
a
a
a
Received 00th January 20xx,
Accepted 00th January 20xx
Ruting Feng, Qinggong Zhu, Mengen Chu, Shuaiqiang Jia, Jianxin Zhai, Haihong Wu* , Peng
a
a,b
Wu* , Buxing Han*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Cu-Pd bimetallic catalysts was fabricated on carbon paper (CP) by carbon catalysts have been reported to enhance the
[
24]
electrodeposition method via
a
dynamic hydrogen bubble electroreduction of CO
2
2 4
to C H .
Plasma-activated oxide
+
template approach. At a potential of -1.2 V vs RHE, the Faradaic derived-Cu (OD-Cu) catalysts with high stability of Cu species
[
25]
efficiency (FE) of C
1
2
H
4
could reach 45.2% with a current density of have been reported to promote C
2
product formation.
RR to
Exploration of electrochemical systems for
-2
7.4 mA cm in an H-type electrolysis cell. Detailed studies While significant progress has been achieved on CO
2
[
26, 27]
suggest that the enhanced performance of Cu-Pd/CP was
2 4
C H .
attributed mainly to the synergistic effect, low interfacial charge electrocatalytic C-C coupling in aqueous electrolytes is still an
transfer resistance, as well as 3D architecture of the catalysts.
open challenge due to low selectivity, activity, and large
overpotential.[
28-30]
Design of catalyst holds the key to address
Carbon dioxide (CO
2
) reduction has garnered intense interest
[31, 32]
those challenges.
with the global energy and environmental crises.[
1, 2]
An ideal
Recently, Cu-based bimetallic catalysts have shown great
2
route for the chemical utilization of CO is to develop catalytic
potential in enhancing catalytic ability toward C
increasing strains and synergistic effects of atoms in the catalyst.
2
product by
processes for the selective conversion of CO
2
into value-added
[20,
chemicals and fuels.[ Among all the developing techniques, 33, 34]
3-5]
Enhancement in the selectivity for C
H
2 4
has been observed on
the electrocatalytic reduction is a promising route for
various bimetallic catalysts. For example, Au-Cu bimetallic catalysts
utilization of CO
2
as a carbon feedstock to value added-
[35]
have been investigated to arise C
2
H
4
selectivity with 46.7%. Ag-
RR toward C with FE
chemicals.[
6-11]
Up to date, extensive efforts have been
Cu nanoparticles showed a selectivity of CO
2
2 4
H
devoted to the development of electrocatalysts for CO
2
[36]
of 41.3%.
Besides, Cu-Ru bimetallic alloy could catalyze CO
2
H with FE of 19%. Nano porous Cu−Ag bimetallic
2 4
reduction reaction (CO
Ethylene (C
2
RR) to higher value products.[
12-14]
[37]
conversion to C
H
4
) is a popular chemical commodity used in
Compared with C products, C possesses
impressive energy densities and higher economic value.
Currently, copper (Cu) is the promising candidate as a catalyst
[38]
2
16]
catalyst was also reported to reduce CO
However, even after such extensive research efforts, achieving high
selectivity for C on facile prepared bimetallic catalysts is still
highly desired in this field.
2 4
to C H with FE of 60%.
2
industry.[15,
1
2 4
H
[
13, 17, 18]
2 4
H
[39, 40]
2
that could produce C products, but often a wild range of
products are formed with low product selectivity.[
19,
20]
Self-supporting bimetallic catalysts by electrodeposition is a very
useful technique that can form three-dimensional (3D) porous
To
2
product,
overcome the poor selectivity of pure Cu toward C
various strategies have been proposed, including alloying,
[
21] structure and increased surface area by a one-step strategy of
potentiostatic co-electrodeposition utilizing hydrogen bubble
[
22]
[4a]
doping, changing the composition and morphology, and
creating special electrolytic devices.[23] For instance, Cu-doped
[
41, 42]
dynamic templates.
Compared with other synthesized method,
the corresponding technology is often known as electroplating,
which can simplify the experimental process, further reduce the
cost and increase the electrode efficiency due to their extraordinary
a. Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of
Chemistry and Molecular Engineering, East China Normal University, Shanghai
chemical
electrodeposition.
properties
in
The electrocatalysts also provide some
RR, such as fast electron transfer rate,
the
electrolyte
during
the
2
00062, P. R. China
[43]
b.
Beijing National Laboratory for Molecular Sciences, CAS Key Laboratory of Colloid
and Interface and Thermodynamics, CAS Research/Education Center for
Excellence in Molecular Sciences, Institute of Chemistry, Chinese Academy of
Sciences, Zhongguancun North First Street 2, Beijing, 100190, P. R. China
E-mail: hhwu@chem.ecnu.edu.cn; pwu@chem.ecnu.edu.cn; hanbx@iccas.ac.cn
obvious advantages in CO
large specific area and high electrochemical performance.
In this work, we focus on enhancing the selectivity of CO
on Cu-Pd bimetallic catalysts, which were prepared by
2
[
12]
2
RR to
2 4
C H
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See galvanostatically electrodeposition using self-supporting technique.
DOI:10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please Gd roe en no tC ha ed mj u iss tt r my argins
Page 2 of 5
PAPER
Journal Name
The resulting Cu-Pd bimetallic catalysts had a high selectivity bimetallic catalysts. The Cu-Pd bimetallic samples aVileswoAertixchleibOintleinde
toward C
(45.2%) at applied potential of -1.2 V vs RHE and Cu O diffraction peaks of (110), (111), andD(2O2I:01)0, .w10h3i9c/hD0aGssCo0c3ia0t5e1Ad
2 4
H
2
-2
current density of 17.4 mA cm in aqueous electrolyte. The high
catalytic activity of bimetallic Cu-Pd catalysts was attributed to the
synergistic effect between Cu and Pd, fast electron transfer rate, as
well as 3D architecture of the catalyst.
2
with the presence of Cu O phase in the bimetallic catalysts.
X-ray photoelectron spectroscopy (XPS) further identified
the element contents and valence states of Cu and Pd in the
catalysts (Fig. 2B-2C,). The results of XPS investigations on
Cu/CP and Pd/CP are consistent with the results of XRD. For
Cu-Pd/CP It can be seen the Cu/Pd ratio is 6.83, which
indicates the formation of bimetallic catalysts (Table S1). The
binding energies Cu 2p spectra were fitted with two
I
0
components, which are Cu + Cu (2p3/2, 932.4 eV; 2p1/2, 952.0
eV) and Cu (2p3/2, 934.2 eV; 2p1/2, 954.0 eV) respectively. The
II
intensities of Pd 3d5/2 peaks of Cu-Pd catalysts at 337.2 eV and
0
II
3
3
37.8 eV correspond to the metallic Pd and Pd , and the Pd
0
d
3/2 peaks at 342.5 eV and 342.8 eV corresponding to Pd and
Pd . This indicates that O species exist on the catalysts surface.
II
The presence of O species may yield enhancement in C
2 4
H
production efficiency.[
38]
Fig. 1 A) Schematic illustration of the procedure for preparing Cu-Pd
bimetallic catalysts; SEM images: B) CP; C) Cu/CP catalysts; D) Pd/CP
catalysts; E) Cu-Pd/CP catalysts; F) TEM image of Cu-Pd/CP catalysts;
G) The elemental mappings of Cu-Pd/CP catalysts. The images in green
and red represent H) Cu and I) Pd, respectively.
The Cu-Pd bimetallic catalysts were synthesized by a facile
electrodeposition method, which is schematically described in
Fig. 1A. In the deposition process, Cu and Cu-Pd samples were
2
+
2+
electrodeposited in an acid solution containing Cu and Pd
at pH=1. During the deposition, the dynamic hydrogen bubble
was used as template to prepare functional porous materials.
Cu-Pd was electrodeposited galvanostatically at a constant
current density. The catalysts were characterized by scanning
electron microscopy (SEM) and transmission electron
microscopy (TEM). Fig. 1B-D provide the SEM images of CP,
Cu/CP and Pd/CP. It is shown that a rough surface of Cu
deposit and a half-baked dendritic 3D structure for Pd were
formed on CP. Unlike these catalysts, Cu-Pd bimetallic catalysts
Fig. 2 A) XRD patterns of Cu-Pd/CP, Cu/CP, Pd/CP, CP; XPS spectra of B)
Cu 2p and C) Pd 3d levels of catalysts.
The electrocatalytic performances of Cu-Pd/CP were investigated
in CO -saturated KCl aqueous solution in a typical three-electrode
2
electrochemical system. The linear sweep voltammetry (LSV) was
conducted to investigate the performance of Cu-Pd in 0.1 M KCl
aqueous solution, and the LSV curves were swept in the potential
-1
range from 0 to -1.4 V (vs. RHE) at a sweep rate of 50 mV s . As
shown in Fig. 3A, the Cu-Pd/CP exhibited a higher current density
than other electrodes (CP, Pd/CP, Cu/CP), suggesting that Cu-Pd
shows observable structural changes (Fig. 1E) and
a
tetrahedron structure was formed with nanostructured
features on the scale of 90-200 nm (Fig. 1F, TEM). We also
examined Cu-Pd/CP catalysts using elemental distribution
mappings (EDS, Fig. 1G-I), which show that Cu (green), and Pd
bimetalliccatalysts was favorable to the binding of CO
the much higher current density of CO -saturated catholyte than
-saturated catholyte implied the reduction of CO (Fig. S1).
Controlled potential electrolysis was performed using a typical
2
. In addition,
2
N
2
2
(red) atoms are homogeneously distributed, forming a
bimetallic structure.
H-type electrolysis cell in the same system. After electrolysis, the
gas and liquid products were analyzed by gas chromatography (GC)
According to X-ray diffraction (XRD, Fig. 3A), the diffraction peak
located at 24.8° was assigned to (002) plane of the CP. Cu
diffraction peaks of (111), (200), and (220) facets are present for
the bimetallic samples. The diffraction peaks of these samples had
an appreciable shift in comparison with that of Pd. No Pd-related
peaks were found, indicative of the low amount of Pd in the
1
and nuclear magnetic resonance ( H-NMR), respectively. The main
2 4 2
gaseous products were C H , H and a trace amount of CO, no liquid
product was detected by NMR. Fig 3B shows the FE of main
products over various electrodes, it indicates that CP and Pd/CP has
2 2 4
little catalytic effect in electrocatalytic reduction of CO to C H . The
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Please Gd roe en no tC ha ed mj u iss tt r my argins
Journal Name
PAPER
main product on Pd/CP was syngas, which contains H
Cu/CP, FE of C was 29.97% with a CO FE of 24.3%. Among these
samples, Cu-Pd/CP was the best catalyst with a C FE of 45.23% at
1.2 V (vs. RHE). Comparing with the reported results using different
2
, CO. On the
View Article Online
DOI: 10.1039/D0GC03051A
H
2 4
2 4
H
-
bimetallic electrocatalysts (Table S2), the FE and current density
were high in aqueous electrolyte by using H-type cell.
To gain kinetic insights for the CO
2 2 4
RR to C H on Cu-Pd
catalysts, the current density for C at various overpotentials
2 4
H
were measured. As shown in Fig. 3C, the onset potential over
Cu-Pd/CP was -0.65 V, which was more positive than those of
Cu/CP (-0.72 V) and Pd/CP (-0.88 V), indicating that the initial
-
electron transfer to CO
2
to form an adsorbed CO
2
intermediate was much easier over Cu-Pd/CP.[ We also
44]
studied the change of C
potentials. As the electrolytic potential increased, the FE of Fig. 3 A) LSV curves of various electrodes with a scan rate of 50 mV ;
B) the FE of C at -1.2 V (vs. RHE) over various electrodes; C) Partial
current density of C H over various electrodes at different applied
2 4
H over Cu-Pd/CP at different applied
-1
2 4
H
2 4 2 4
C H increased first and then decreased. The FE of C H
-2
reached 45.2% with a current density of 17.4 mA cm at -1.2 V
vs. RHE (Fig. 3D). The decrease in the FE of C at a high
applied potential resulted from the enhancement in the
production rate of H
2 4
potentials; D) the FE and current density of C
different applied potentials in CO -saturated 0.1 M KCl solution.
2 4
H over Cu-Pd/CP at
2 4
H
2
2
.
The electrochemical activity of Cu-Pd/CP was also
characterized according to the Randle-Sevcik equation. The
reduction current density plotted against the root of the scan
rate is illustrated in Fig. S2. According to the result, the Cu-
Pd/CP has the largest slope among the electrodes, indicating
We also studied the electrolyte effect over Cu-Pd/CP electrode.
In addition to 0.1 M KCl electrolyte, other electrolytes that contain
different cations and anions were used in this work (Fig. S5). For
example, in the NaCl electrolyte, H
exhibited better performance for C
KHCO electrolyte. In 0.1 M KH PO and K
of C was very low with H as the main product. In KCl electrolyte,
even if the electrolyte concentration is increased, the FE of C did
not increase significantly, which indicates that 0.1 M KCl was the
best electrolyte. We think that the electrolyte affects CO reduction
2
was the main product. CO
with FE of 35% in 0.1 M
HPO electrolyte, the FE
2
RR
2 4
H
3
2
4
2
4
the highest reduction rate for CO
with the electrochemical impedance spectroscopy (EIS) result
Fig. S3-4), which provides the charge transfer rate at the
2
RR. This result is consistent
H
2 4
2
2 4
H
(
electrode/electrolyte interface. The results indicated that the
charge transfer resistance (Rct) of the Cu-Pd/CP was lower than
that of the Cu/CP. The above result shows that Pd or Cu could
2
+
+
mainly in two ways. First, the alkali metal cation (such as Na , K ) in
the electrolyte is known to influence the electrocatalytic ability of
2 4
not promote the generation of C H product efficiently, and
2
CO reduction. Density functional theory (DFT) calculations have
the excellent performance of Cu-Pd/CP can be attributed to shown that the alkali metal cations influence the distribution of
the synergistic effect between Cu and Pd in the catalysts. On products formed as a consequence of electrostatic interactions
one hand, Cu-based bimetallic catalysts have shown great between solvated cations present at the outer Helmholtz plane and
potential in enhancing catalytic ability toward C
2
product by adsorbed species having large dipole moments. Therefore,
increasing alkali metal size leads to higher selectivity to C
2
increasing strains and synergistic effects of atoms in the
catalyst. Oxygen-bearing Cu catalysts could enable the C-C
[
46, 47]
products.
Second, the local buffering capability of cations
could be able to increase the rate of proton-transfer reaction, which
affects the activity and selectively for CO RR, When the cation
2
coupling in the electrocatalytic CO RR systems. The mixed
0
I
2
valence form of copper (Cu and Cu ) may be dominant species
during the CO RR, which could be the most active species for
product formation. The Cu /Cu interfaces formed through
concentration was too low or too high, it will inhibit the proton-
transfer reaction. Therefore, a moderate concentration facilitates
2
+
0
C
2
[
48, 49]
proton transfer and improves catalytic activity and selectivity.
These arguments are consistent with our experimental results.
+
stabilized Cu facilitate *CO–CO dimerization, promoting
formation of C2+ products and suppressing conversion to C
products. On the other hand, Pd is known to be the excellent
1
We assume that the excellent activity of Cu-Pd bimetallic
catalysts toward C resulted from the synergistic effect of Cu
2 4
H
RR to CO.[
21,
40]
Trace amount of Pd could
catalyst for CO
2
and Pd in Cu-Pd catalysts. Therefore, we prepared the Cu-Pd
catalysts using different electrodeposition methods (CV and
Amperometric mode), which may contain different atomic
ratio of the elements (Table S1). The corresponding electrodes
were then named as Cu-Pd/CP-CV, Cu-Pd/CP-IT (see
experimental section in SI). The SEM image of Cu-Pd/CP-CV
and Cu-Pd/CP-IT electrodes showed a symmetrical and a
homogeneous morphology, respectively (Fig. S6). After
promote the adsorption of *CO intermediate and facilities
their dimerization to form C2 products.[
38, 45]
2 4
electrolysis, we found FE of C H was approximately 25% over
both electrodes with high hydrogen evolution reaction (HER)
than Cu-Pd/CP electrode (Fig. 4A). Therefore, we characterized
the Cu-Pd catalysts prepared using different methods by XRD
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please Gd roe en no tC ha ed mj u iss tt r my argins
Page 4 of 5
PAPER
Journal Name
(
Figure S7) and XPS (Figure S8) to get more information about deposition potential and high current density, the deposition
View Article Online
DOI: 10.1039/D0GC03051A
the surface element states and catalytic performance. Among tended to deposit Cu. At low deposition potential and low
the three methods, Cu-Pd/CP showed the lowest (Cu +Cu )/Cu
and Pd /Pd ratio, which suggests that the existence of oxygen According to this tendency, the FE of C was first increased
0
I
II
current density, the content of Pd in the catalysts increased.
0
II
2 4
H
vacancies in the catalysts (Table S1). Therefore, it is benefit to then decreased with increasing deposition current density,
the adsorption of the intermediates and facilitates the which indicates that a proper Cu-Pd ratio was beneficial to the
formation of C H . The EIS results (Figure S9, Table S3) also reaction. This also can be known from the fact the FE of C H
2 4 2 4
showed that Cu-Pd/CP had lower Rct (Nyquist plot) and larger over electrodeposited Cu/CP or Pd/CP was much lower (Fig.
phase angle at low frequency region (Bode plot) than that of 3B).
Cu-Pd/CP-CV and Cu-Pd/CP-IT, resulting in the increase of
electron transfer and diffusion ability of Cu-Pd/CP.
The excellent activity of Cu-Pd catalysts may also result
partially from 3D architecture of the film. Therefore, we
2
The effect of deposition current density on the properties of performed the CO reduction using Cu-Pd catalysts obtained
the catalysts was also studied. Deposition of Cu-Pd bimetallic from various deposition times. Fig. S12 shows that the amount
catalysts under different current density not only affected the of the catalyst increased with increasing deposition time. The
co-deposition process, but also changed the morphology of CO
the catalyst. Therefore, we fixed the total amount of electrons time, but the FE of C
2
RR current density increased continuously with deposition
first increased and then decreased (Fig.
2 4
H
to 12 Coulomb and obtained Cu-Pd catalysts with different 4C). This can be explained by the fact that the 3D structure
morphologies under different current density (Fig. S10). Fig. 4B gradually formed with increasing deposition time. This
shows that the deposition current density of Cu-Pd catalysts structure may provide more opportunity for the C-C coupling
2 4
had great influence on the FE of C H . It may be due to the for the intermediates. When the film of 3D structure was thick
different atomic amount in the catalysts. As shown in Fig. S11, enough (>10 min), excessive catalyst agglomeration is not
the bimetallic solution has an intermediate potential between conducive to the reaction.
the other two monometallic solutions. It indicates that at high
2 4
Fig. 4 the FE of C H over Cu-Pd bimetallic catalysts A) using different electrodeposition methods; B) under different current density; C) obtained from
various deposition time.
Conclusion
Conflicts of interest
There are no conflicts to declare.
In summary, we developed a facile electrodeposition method
to fabricate Cu-Pd catalysts onto conductive substrates
through dynamic hydrogen bubble template approach. The
synthesized Cu-Pd/CP is a highly effective catalyst for CO
reduction to C . The FE and current density of C could
2
Acknowledgements
The work was supported by National Natural Science
Foundation of China (21533011, 21733011), the National Key
H
2 4
2 4
H
-2
reach 45.23% and 17.4 mA cm in 0.1 M KCl aqueous
electrolyte respectively. Detailed study indicates that the
synergistic effect between Cu and Pd in the Cu-Pd catalysts, low
interfacial charge transfer resistance, 3D architecture of the
catalysts, as well as suitable electrolyte are all favourable for the
Research
2017YFA0403102), and Chinese Academy of Sciences (QYZDY-
SSW-SLH013).
and
Development
Program
of
China
(
2 4
formation of C H . We believe that the strategy to prepare
bimetallic catalysts by co-electrodeposition coupling effective
electrolyte can be used to design more efficient catalytic systems
for CO reduction to C products.
2 2
Notes and references
1
.
M. He, Y. Sun and B. Han, Angew. Chem. Int. Ed., 2013, 52,
620-9633.
Z. Sun, T. Ma, H. Tao, Q. Fan and B. Han, Chem, 2017, 3, 560-
87.
9
2
.
5
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
Please Gd roe en no tC ha ed mj u iss tt r my argins
Journal Name
PAPER
3
4
5
6
7
8
.
.
.
.
.
.
W. Lu, B. Jia, B. Cui, Y. Zhang, K. Yao, Y. Zhao and J. Wang, 29. L. Zhang, Z. J. Zhao and J. Gong, Angew. Chem. VInietw. AErdtic.,le2O0n1lin7e,
Angew. Chem. Int. Ed., 2017, 56, 11851-11854. 56, 11326-11353.
S. A. Abbas, S.-H. Kim, H. Saleem, S.-H. Ahn and K.-D. Jung, 30. K. Yao, Y. Xia, J. Li, N. Wang, J. Han, C. Gao, M. Han, G. Shen, Y.
DOI: 10.1039/D0GC03051A
Catalysts, 2019, 9.
L. Fan, C. Xia, F. Yang, J. Wang, H. Wang and Y. Lu, Science
Advances, 2020, 6, eaay3111.
Q. Zhu, J. Ma, X. Kang, X. Sun, J. Hu, G. Yang and B. Han, Sci.
China. Chem., 2016, 59, 551-556.
H. Yang, L. Wu, H. Wang and J. Lu, Chinese. J. Catal., 2016, 37,
Liu, A. Seifitokaldani, X. Sun and H. Liang, J. Mater. Chem. A.,
2020, 8, 11117-11123.
31. F. Li, L. Chen, G. P. Knowles, D. R. MacFarlane and J. Zhang,
Angew. Chem. Int. Ed., 2017, 56, 505-509.
32. X. Wang, Z. Chen, X. Zhao, T. Yao, W. Chen, R. You, C. Zhao, G.
Wu, J. Wang, W. Huang, J. Yang, X. Hong, S. Wei, Y. Wu and Y.
Li, Angew. Chem. Int. Ed., 2018, 57, 1944-1948.
9
94-998.
A. Loiudice, P. Lobaccaro, E. A. Kamali, T. Thao, B. H. Huang, J. 33. M. J. Mao, M. D. Zhang, D. L. Meng, J. X. Chen, C. He, Y. B.
W. Ager and R. Buonsanti, Angew. Chem. Int. Ed., 2016, 55,
789-5792.
X. Kang, Q. Zhu, X. Sun, J. Hu, J. Zhang, Z. Liu and B. Han, Chem.
Sci., 2016, 7, 266-273.
Huang and R. Cao, ChemCatChem, 2020, 12, 3530-3536.
34. S. Jia, Q. Zhu, H. Wu, M. e. Chu, S. Han, R. Feng, J. Tu, J. Zhai
and B. Han, Chinese. J. Catal., 2020, 41, 1091-1098.
35. Y. Chen, Z. Fan, J. Wang, C. Ling, W. Niu, Z. Huang, G. Liu, B.
Chen, Z. Lai, X. Liu, B. Li, Y. Zong, L. Gu, J. Wang, X. Wang and
H. Zhang, J. Am. Chem. Soc., 2020, DOI: 10.1021/jacs.0c04981.
36. J. Huang, M. Mensi, E. Oveisi, V. Mantella and R. Buonsanti, J.
Am. Chem. Soc., 2019, 141, 2490-2499.
5
9
.
1
1
0. Y. Chen and T. Mu, Green. Chem., 2019, 21, 2544-2574.
1. X. Sun, Q. Zhu, X. Kang, H. Liu, Q. Qian, Z. Zhang and B. Han,
Angew. Chem. Int. Ed., 2016, 55, 6771-6775.
1
2. P. Moreno-Garcia, N. Schlegel, A. Zanetti, A. Cedeno Lopez, M.
J. Galvez-Vazquez, A. Dutta, M. Rahaman and P. Broekmann, 37. J. T. Billy and A. C. Co, Appl. Catal. B-Environ., 2018, 237, 911-
ACS. Appl. Mater. Inter., 2018, 10, 31355-31365. 918.
3. A. Eilert, F. S. Roberts, D. Friebel and A. Nilsson, J Phys Chem 38. T. T. H. Hoang, S. Verma, S. Ma, T. T. Fister, J. Timoshenko, A. I.
1
1
Lett, 2016, 7, 1466-1470.
Frenkel, P. J. A. Kenis and A. A. Gewirth, J. Am. Chem. Soc.,
2018, 140, 5791-5797.
4. Z. Q. Liang, T. T. Zhuang, A. Seifitokaldani, J. Li, C. W. Huang, C.
S. Tan, Y. Li, P. De Luna, C. T. Dinh, Y. Hu, Q. Xiao, P. L. Hsieh, 39. L. Lu, X. Sun, J. Ma, D. Yang, H. Wu, B. Zhang, J. Zhang and B.
Y. Wang, F. Li, R. Quintero-Bermudez, Y. Zhou, P. Chen, Y. Han, Angew. Chem. Int. Ed., 2018, 57, 14149-14153.
Pang, S. C. Lo, L. J. Chen, H. Tan, Z. Xu, S. Zhao, D. Sinton and 40. D. Chen, Q. Yao, P. Cui, H. Liu, J. Xie and J. Yang, ACS Appl.
E. H. Sargent, Nat. Commun., 2018, 9, 3828. Energy Mater., 2018, 1, 883-890.
5. F. S. Roberts, K. P. Kuhl and A. Nilsson, Angew. Chem. Int. Ed., 41. B. J. Plowman, L. A. Jones and S. K. Bhargava, Chem. Commun.,
015, 54, 5179-5182. 2015, 51, 4331-4346.
6. S. Sen, D. Liu and G. T. R. Palmore, Acs. Catal., 2014, 4, 3091- 42. X. Lu and C. Zhao, Nat. Commun., 2015, 6, 6616.
1
1
1
1
1
2
2
2
3
095.
7. C. W. Li and M. W. Kanan, J. Am. Chem. Soc., 2012, 134, 7231-
234.
43. P. Ganesan, A. Sivanantham and S. Shanmugam, ACS. Appl.
Mater. Inter., 2017, 9, 12416-12426.
44. Q. Zhu, X. Sun, D. Yang, J. Ma, X. Kang, L. Zheng, J. Zhang, Z.
Wu and B. Han, Nat. Commun., 2019, 10, 3851.
45. T. Takashima, T. Suzuki and H. Irie, Electrochim. Acta, 2017,
229, 415-421.
46. J. Resasco, L. D. Chen, E. Clark, C. Tsai, C. Hahn, T. F. Jaramillo,
K. Chan and A. T. Bell, J. Am. Chem. Soc., 2017, 139, 11277-
11287.
7
8. Z. Tan, T. Peng, X. Tan, W. Wang, X. Wang, Z. Yang, H. Ning, Q.
Zhao and M. Wu, ChemElectroChem, 2020, 7, 2020-2025.
9. Y. Zheng, A. Vasileff, X. Zhou, Y. Jiao, M. Jaroniec and S. Z.
Qiao, J. Am. Chem. Soc., 2019, 141, 7646-7659.
0. C. Chen, X. Sun, L. Lu, D. Yang, J. Ma, Q. Zhu, Q. Qian and B.
Han, Green. Chem., 2018, 20, 4579-4583.
1. S. Ma, M. Sadakiyo, M. Heima, R. Luo, R. T. Haasch, J. I. Gold, 47. A. S. Varela, W. Ju, T. Reier and P. Strasser, Acs. Catal., 2016, 6,
M. Yamauchi and P. J. Kenis, J. Am. Chem. Soc., 2017, 139, 47-
0.
2. Y. Zhou, F. Che, M. Liu, C. Zou, Z. Liang, P. De Luna, H. Yuan, J.
2136-2144.
5
48. M. R. Singh, Y. Kwon, Y. Lum, J. W. Ager, 3rd and A. T. Bell, J.
Am. Chem. Soc., 2016, 138, 13006-13012.
2
Li, Z. Wang, H. Xie, H. Li, P. Chen, E. Bladt, R. Quintero- 49. J. Fu, W. Zhu, Y. Chen, Z. Yin, Y. Li, J. Liu, H. Zhang, J. J. Zhu and
Bermudez, T. K. Sham, S. Bals, J. Hofkens, D. Sinton, G. Chen
and E. H. Sargent, Nat. Chem., 2018, 10, 974-980.
3. J. Du, S. Li, S. Liu, Y. Xin, B. Chen, H. Liu and B. Han, Chemical
Science, 2020, 11, 5098-5104.
4. H. Ning, X. Wang, W. Wang, Q. Mao, Z. Yang, Q. Zhao, Y. Song
and M. Wu, Carbon, 2019, 146, 218-223.
5. H. Mistry, A. S. Varela, C. S. Bonifacio, I. Zegkinoglou, I. Sinev,
Y. W. Choi, K. Kisslinger, E. A. Stach, J. C. Yang, P. Strasser and
B. R. Cuenya, Nat. Commun., 2016, 7, 12123.
S. Sun, Angew. Chem. Int. Ed., 2019, 58, 14100-14103.
2
2
2
2
2
6. D. Ren, Y. Deng, A. D. Handoko, C. S. Chen, S. Malkhandi and B.
S. Yeo, Acs. Catal., 2015, 5, 2814-2821.
7. J.-C. Lee, J.-Y. Kim, W.-H. Joo, D. Hong, S.-H. Oh, B. Kim, G.-D.
Lee, M. Kim, J. Oh and Y.-C. Joo, J. Mater. Chem. A., 2020, 8,
1
1632-11641.
8. D. Raciti, K. J. Livi and C. Wang, Nano. Lett., 2015, 15, 6829-
835.
2
6
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins