Controllable Cu0-Cu+ Sites for Electrocatalytic Reduction of Carbon Dioxide

Article abstract of DOI:10.1002/anie.202105118

Cu-based electrocatalysts facilitate CO₂ electrochemical reduction (CO₂ER) to produce multi-carbon products. However, the roles of Cu⁰ and Cu⁺ and the mechanistic understanding remain elusive. This paper describes the controllable construction of Cu⁰-Cu⁺ sites derived from the well-dispersed cupric oxide particles supported on copper phyllosilicate lamella to enhance CO₂ER performance. 20 % Cu/CuSiO₃ shows the superior CO₂ER performance with 51.8 % C₂H₄ Faraday efficiency at ?1.1 V vs reversible hydrogen electrode during the 6 hour test. In situ attenuated total reflection infrared spectra and density functional theory (DFT) calculations were employed to elucidate the reaction mechanism. The enhancement in CO₂ER activity is mainly attributed to the synergism of Cu⁰-Cu⁺ pairs: Cu⁰ activates CO₂ and facilitates the following electron transfers; Cu⁺ strengthens *CO adsorption to further boost C?C coupling. We provide a strategy to rationally design Cu-based catalysts with viable valence states to boost CO₂ER.

Full text of DOI:10.1002/anie.202105118

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Accepted Article
Title: Controllable Cu0-Cu+ Sites for Electrocatalytic Reduction of
Carbon Dioxide
Authors: Jinlong Gong
This manuscript has been accepted after peer review and appears as an
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.202105118
Link to VoR: https://doi.org/10.1002/anie.202105118

Angewandte Chemie International Edition
10.1002/anie.202105118
COMMUNICATION
0
+
Controllable Cu -Cu Sites for Electrocatalytic Reduction of
Carbon Dioxide
Xintong Yuan, Sai Chen, Dongfang Cheng, Lulu Li, Wenjin Zhu, Dazhong Zhong, Zhi-Jian Zhao,
Jingkun Li, Tuo Wang, and Jinlong Gong*[a]
Abstract: Cu-based electrocatalysts can effectively facilitate carbon
2 4
C H with Faraday efficiency (FE) of 60% at -1.6 vs reversible
hydrogen electrode (RHE). Additionally, the copper oxychloride
[
8]
dioxide electrochemical reduction (CO
2
ER) to produce multi-carbon
0
+
products. However, the roles of Cu and Cu and the mechanistic
understanding remain elusive. This paper describes the controllable
sol-gel material shows sluggish reduction kinetics of copper and
+
stabilized Cu , leading to a FE of 54% for C
2
H
4
and C
2
H
5
OH (C
2
)
0
+
at -1.2 V vs RHE.[4a] However, Cu+ alone cannot guarantee
excellent CO ER performance. CO is a thermodynamically
stable molecular with a standard formation enthalpy of -393.5 kJ
construction of Cu -Cu sites derived from the well-dispersed cupric
oxide supported on copper phyllosilicate lamella to enhance CO ER
performance. Specifically, 20% Cu/CuSiO shows the superior
CO ER performance with 51.8% C Faraday efficiency at -1.1 V vs
2
2
2
3
-1 [9]
2
H
2 4
mol . Thus, another essential thermodynamic problem, i.e., how
to reduce the energy barrier of CO activation, need to be resolved
during CO
ER.[10] According to density function theory (DFT)
calculations, CO activation and CO dimerization comes from the
synergism between active Cu and Cu sites.
reversible hydrogen electrode (RHE) during the 6 hours-test. In situ
attenuated total reflection infrared spectra and density functional
theory calculations were employed to elucidate the reaction
2
2
2
0
+
0
+
[11]
2
mechanism over Cu -Cu sites. The enhancement in CO ER activity
0
+
0
This paper designs the catalysts with tunable Cu+ and Cu0
pairs, and elucidates their individual and synergic roles via in situ
experiments and DFT calculations. We synthesized cupric oxide
is mainly attributed to the synergistic effect of Cu -Cu pairs: The Cu
site activates CO
2
and facilitates the following electron transfers; while
+
the Cu site strengthens the *CO adsorption to further boost C-C
coupling. This paper provides an efficient strategy to rationally design
particles supported on copper
phyllosilicate lamella
Cu-based catalysts with viable valence states to boost CO
2
ER.
(CuO/CuSiO ) via ammonia evaporation hydrothermal method
3
2
+
(
AEM). During the initial electroreduction process, Cu sites in
0
+
). Cu0
Electrocatalytic CO reduction (CO ER) is of great
2
2
3 3
CuO/CuSiO are reduced to Cu and Cu sites (Cu/CuSiO
significance to complete the carbon cycle and solve the energy
and environmental crisis.[1] Particularly, Cu-based catalysts are of
promotes the activation of CO
activation barrier, while Cu enhances *CO adsorption, and thus
the kinetics of C-C coupling. The Cu+ species stably exist as
2
by reducing the thermodynamic
+
great interest for CO
2
ER since Cu is in favor of binding *CO
intermediate and converting it into multi-carbon products.
efficient active sites to increase CO
2
ER activity as evidenced by
[
2]
Specially, oxide-derived Cu (OD-Cu) catalyst has been widely
studied due to its excellent CO ER performance towards valuable
in situ infrared spectroscopy. By adjusting the Cu loading, the ratio
0
+
2
of Cu -Cu is controlled to further regulate the binding energy of
reaction intermediates. Particularly, 20% Cu/CuSiO shows a FE
(-1.1 vs RHE) of 51.8% and 82% toward and
carbonaceous products (C +C ), respectively. This is among the
competitive CO ER performances over Cu-based catalysts for
production in H-cell (Table S1).
The copper phyllosilicate lamella can boost the well-
multi-carbon products.[3] Electronic structures[3c, 4] and geometric
structures[2b, 5] have been extensively studied to increase the
reactivity. Nevertheless, the reaction mechanism and real active
site of OD-Cu are still unclear, mainly due to that copper oxide is
reduced rapidly during the reduction process and then reoxidized
rapidly once the applied potential is stopped. Recently, studies
3
V
2 4
C H
1
2
2
2 4
C H
0
+
show that Cu is the active site toward CO
2
ER, since Cu cannot
dispersion of CuO particles and enhance metal-support
interaction markedly, which originates from its characteristic
preparation method. By adding ammonium hydroxide to adjust pH,
be stably present in OD-Cu during the electroreduction process.[
However, in both electrocatalysis and traditional catalysis,
6]
Ⅱ
+
0 [4a, 4b, 7]
*
CO is more strongly adsorbed over Cu than Cu ,
which
≡SiOCu monomer is formed via the reaction of the silanol
groups with the Cu2 complex through hydrolytic adsorption.
+
[12]
solves the vital dynamics problem in CO
2
ER, i.e., enhancing
adsorption of *CO to facilitate *CO-*CO dimerization. Hence, it is
extremely meaningful to stabilize Cu for enhancing the selectivity
of multi-carbon products. Numerous studies have been carried
Then the target structure is obtained by hydrothermal
polymerization and calcination (Figure 1a). The copper
phyllosilicate and copper hydroxide could be discriminated by
Fourier transform infrared for their structural OH groups (Figure
S1). For the sample before calcination, the peaks appearing at
+
+
out to stabilize Cu and improve CO
2
ER performance. For
N structure is reported to
to
-
example, N
3
+
in the perovskite-type Cu
stabilize Cu , and the Cu plays the key role for converting CO
3
+
937 and 690 cm-1 are attribute to δOH bands from Cu(OH) .[13] The
2
2
appearance of νSiO shoulder at 1040 cm-1 and δOH vibration at 670
cm-1 arises from copper phyllosilicate,[14] suggesting the complete
decomposition of Cu(OH)
phyllosilicate in CuO/CuSiO
2
to CuO and the existence of copper
. With the increasing amount of Cu
[
a]
X. Yuan, S. Chen, D. Cheng, L. Li, W. Zhu, D. Zhong, Prof. Dr. Z. J.
Zhao, Prof. Dr. J. Li, Prof. Dr. J. Gong
3
Key Laboratory for Green Chemical Technology of Ministry of
Education, School of Chemical Engineering and Technology,
Collaborative Innovation Center of Chemical Science and
Engineering
Tianjin University
Weijin Road 92, Tianjin, 300072 (China)
E-mail:jlgong@tju.edu.cn
precursor, the amount of copper silicate reaches the maximum
and the amount of CuO gradually increases, thus adjusting the
ratio of Cu and Cu . 20% CuO/CuSiO means the mass feed ratio
3
of copper precursor is 20%, and the like. There is a ~3-4 nm layer
of well-dispersed CuO particles supported on the copper
3
phyllosilicate lamella in 20% CuO/CuSiO (Figure 1b-c). The
0
+
Supporting information for this article is given via a link at the end of the
document.
elemental mapping images (Figure 1d) highlight the existance of
CuO particles and display the uniform dispersion of Cu, Si and O
3
in CuSiO . The Cu 2p3/2 peaks at ~933.1-935.8 eV and 2p→3d
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Angewandte Chemie International Edition
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COMMUNICATION
satellite peak at ~943.9 eV in X-ray photoelectron spectroscopy
(
LMM X-ray Excited Auger spectroscopy (XEAS), indicating the
XPS) indicate the existence of Cu2+ with a d9 electron
maintenance of Cu and Cu (Figure 1e). The strong interaction
between Cu ions and SiO
prepared by AEM method[12] can
supply stable Cu and Cu and remain intact even after intense
electrochemical process, thus, guaranteeing the superior CO ER
0
+
configuration in 20% CuO/CuSiO
3
(Figure 1e). The asymmetry of
2
0
+
the Cu 2p3/2 binding energy values (~935.8 and ~933.1 eV) shows
2
+
the existence of two different Cu , ascribing to copper
phyllosilicate and CuO.[14a] Because of the amorphous structure
2
performance. Besides, linear sweeping voltammetry (LSV)
(Figure 2e) and electrochemical impedance spectroscopy (Figure
S5) demonstrates the preferable catalytic performance and
of copper silicate, X-ray diffraction (XRD) patterns only
demonstrate weak peaks of SiO
2
and CuO (Figure S2).[ It’s
12]
clear that as the Cu loading increases, the peaks of CuO gradually
become more obvious, indicating there are more CuO particles.
charge transfer resistance of 20% Cu/CuSiO
3
.
Figure 2. (a) FE and (b) stability test of 20% Cu/CuSiO
elemental mapping of 20% Cu/CuSiO
best C +C FE of different loadings of Cu/CuSiO
3
. (c) TEM image and (d)
after 6 h reaction. (e) LSV and (f) the
Figure 1. (a) Schematic illustration of the synthetic process, (b-c) transmission
electron microscopy (TEM) image, (d) elemental mapping, and (e) Cu 2p XPS
3
1
2
3
.
spectra of 20% CuO/CuSiO
3
. The inset in (e) shows Cu LMM XEAS spectrum
of 20% Cu/CuSiO after 6 h reaction.
3
In situ attenuated total reflection infrared (ATR-IR)
spectroscopy is employed to investigate the adsorbed CO at
conditions closely mimicking real reaction environments. The
To explore the origin of CO
2
ER reactivity, catalytic
performances over Cu/CuSiO with different loadings were further
3
2
0% Cu/CuSiO
3
shows two stretching bands of linear-bonded
investigated (Figure 2a, S3). All catalysts exhibit a structure of
copper phyllosilicate lamella with well-dispersed CuO particles
[15]
*
CO in the 2040-2100 cm-1 range
(Figure 3a), which are
attributed to CO adsorption on Cu and Cu0 sites.[16] This
+
(
Figure S4), eliminating the influence of morphology on CO
activity. Particularly, 20% Cu/CuSiO demonstrates a notably
enhanced catalytic activity, i.e., 51.8% C FE and 82% C +C
FE at -1.1 V vs RHE, which is stable during the 6 h reaction
2
ER
phenomenon could not be attributed to surface reconstruction
3
since there is no such phenomenon in Ar-saturated 0.1 M KHCO
3
2
H
4
1
2
solution (Figure S6). Besides, the low frequency band gradually
increases with the increase of applied potential, which is not
consistent with previous studies.[17] Simultaneously, DFT
(
Figure 2a-b). According to the change of lattice spacing, surface
0
CuO particles are reduced to Cu particles and the support still
keeps the uniform dispersion of Cu, O and Si (Figure 2c, d) after
+
calculations (Figure S7) predict the frequency of CO over Cu and
0
-1
-1
Cu is 2115 cm and 2023 cm , respectively, agreeing well with
the in situ ATR-IR results taking into consideration of the error of
simulation and the peak shifts due to Stark effect.[18] In situ ATR-
6
h reaction. Also, the Cu 2p peak around 943.9 eV disappeared
and two overlapping peaks appeared at 919.0 and 916.2 eV in Cu
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Angewandte Chemie International Edition
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COMMUNICATION
IR spectra of Cu/CuSiO
demonstrate that the proportion of Cu increases gradually with
the increase of Cu loading, which is consistent with the XRD trend. well as Cu -Cu sites are favorable in forming the *COCOH,
3
with different loadings (Figure 3b, S8)
energy of *COCOH, the key intermediate in the C
the descriptor of the C
2
pathway, as
0
activity,[21] and discovered that Cu as
0
2
0
+
0
+
Thus, the proper proportion of Cu -Cu sites in 20% Cu/CuSiO
the key to obtain superior CO ER performance. As the potential
increases, the proportion of Cu gradually increases, indicating
3
is
leading to the formation of C
activity over Cu sites is hindered by the low *CO coverage due
to weak *CO adsorption. Thus, Cu -Cu sites with sufficient *CO
coverage and relatively low *COCOH formation energy is most
2
rather than CO. However, the C
2
0
2
0
0
+
+
0
that more Cu is reduced to Cu with the higher reduction energy
+
input. However, even if the stability of Cu is relatively different
under different potentials, Cu remains stable at 10% at -1.1 V vs
2
preferable for C-C coupling and the further production of C .
+
RHE for 60 min (Figure S9, Table S3). This demonstrates the
stable existence of Cu+ that is responsible for the excellent
CO ER performance at -1.1 V vs RHE (Figure 3a). Of course, the
2
reconstruction of Cu is inevitable under the fierce electrochemical
environment. The defective sites and roughened morphology
produced therein may also lead to significantly enhanced
performance, which will require more investigation with careful in
situ measurements further.[19]
The catalytic performance of Cu/CuSiO
loadings was investigated to explore the roles of Cu and Cu in
CO ER. Serious hydrogen evolution reaction (HER) occurs for 2%
Cu/CuSiO
(Figure S3a) with ~40% Cu species exist as Cu+ in
copper phyllosilicate. As Cu loading increases to 20%, the
proportion of Cu0 increases gradually, and the C
+C FE of
CO ER reaction increases from 24.9% to 84.9% (Figure 2a, S3).
Thus, the increase of Cu gradually turns on CO
3
with different Cu
0
+
2
3
1
2
2
0
2
ER reaction, and
2
0% Cu/CuSiO
S10). This suggests that CO
the CO
Goddard et al.[11] As the Cu loading increase to 30%, C
3
exhibits the best CO
2
ER performance (Figure 2f,
Figure 3. In situ ATR-IR of (a) 20% Cu/CuSiO
Cu/CuSiO with different loadings at -1.1 V vs. RHE. The correlation of (c) C
FE, (d) C +C
3
at different potentials, and (b)
0
3
2 4
H
2
is activated over Cu , which initiates
0
0
+
1
2 1 2
FE and (e) CO/(C +C ) with Cu /(Cu +Cu ).
2
ER reaction. This agrees well with the results from
FE
2
H
4
declines and the overpotential of C
2
H
4
production increases
+
(
Figure S3c) because there is almost no enough Cu to promote
0
0
+
C-C coupling. Then we correlate Cu /(Cu +Cu ) from in situ ATR-
IR (Table S2) with CO
FE show volcano trends as the ratio of Cu increases (Figure 3c,
2
ER performance. The C
2
H
4
FE and C
1
+C
2
0
d), indicating a strong dependence of CO
2
ER activity on the ratio
0
+
0
+
of Cu -Cu and unbalanced ratio of Cu -Cu can cause serious
HER. Particularly, the volcano peaks reach the maximum when
the proportion of Cu0 accounts for ~86%. Furthermore, the
proportion of CO in C
1
+C
2
is higher with increasing Cu0 ratio
0
(
Figure 3e), which suggests Cu improves the selectivity of CO.
Thus, it is inferred that Cu0 initially activates CO , while Cu+
2
enhances *CO adsorption to promote subsequent *CO-*CO
dimerization.
2
Figure 4. (a) Proposed pathway for *CO-*CO dimerization to C , (b) optimized
0
+
0
+
model representing Cu -Cu sites and inset shows Bader charge for Cu -Cu
sites, (c) the formation energy of *COCOH and adsorption energy of *CO on
DFT calculations were further conducted to elucidate the
mechanism over Cu -Cu+ sites. According to XPS results[10a]
0
+
0
+
Cu , Cu and Cu -Cu sites.
0
(
Figure S11) and previous work,[12] 20% Cu/CuSiO
3
were rich in
surface hydroxyl, thus we adjusted the number of hydroxyls to
modify the valence of Cu (Figure 4b). *CO is an important
In summary, we design copper phyllosilicate lamella with well-
+
0
dispersed CuO particles which could be reduced to Cu and Cu
intermediate of CO
pathways for CO and C
intermediate.[4a] Desorption of *CO leads to the formation of CO,
2
ER to multi-carbon products as the reaction
sites. Controllable Cu -Cu0 sites is obtained by synthesizing a
+
2
H
4
deviate at the adsorbed *CO
series of CuO/CuSiO
enhancement in the CO
Cu/CuSiO , achieving a C
as well as stability up to 6 h at -1.1 V vs RHE. In situ ATR-IR and
3
with different Cu loadings. A notably
ER activity is observed on 20%
FE of 51.8% and a C +C FE of 82%,
[
20]
2
while dimerization of two *CO leads to the formation of C
2
.
For
3
2
H
4
1
2
the goal of producing multi-carbon products, it’s necessary to
establish enough *CO coverage to favor the kinetics of C-C
0
+
DFT calculations elucidates the roles of Cu and Cu : the former
initiates the CO activation, while the latter strengthens the *CO
adsorption and promotes C-C coupling. This synergistic effect of
0
+
coupling (Figure 4a). Adsorption energy of *CO on Cu , Cu and
0
+
0
+
+
2
Cu -Cu sites (Figure 4c) indicate Cu -Cu and Cu sites have
0
relatively stronger *CO adsorption energy than Cu sites, which
0
+
Cu and Cu breaks the thermodynamic and kinetic limitations of
CO ER. This work offers a novel strategy to the rational design of
enhances the *CO coverage and promotes the subsequent *CO-
CO dimerization.[4b] Furthermore, we calculated the formation
2
*
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Angewandte Chemie International Edition
10.1002/anie.202105118
COMMUNICATION
Cu-based catalysts to boost CO
to elucidate the distribution of Cu and Cu in the Cu/CuSiO . By
3
2
0
ER. However, this paper failed
[8] Z. Yin, C. Yu, Z. Zhao, X. Guo, M. Shen, N. Li, M. Muzzio, J.
+
Li, H. Liu, H. Lin, J. Yin, G. Lu, D. Su, S. Sun, Nano Lett. 2019,
the aid of more advanced in situ technology to explore and clarity
the CO2ER reaction mechanism is one of the future research
directions.
1
9, 8658-8663.
9] H. Dong, L. Zhang, L. Li, W. Deng, C. Hu, Z. J. Zhao, J. Gong,
Small 2019, 15, e1900289.
10] a) W. Zhu, R. Michalsky, O. Metin, H. Lv, S. Guo, C. J. Wright,
X. Sun, A. A. Peterson, S. Sun, J. Am. Chem. Soc. 2013, 135,
6833-16836; b) A. Alvarez, M. Borges, J. J. Corral-Perez, J. G.
[
[
Acknowledgements
1
We acknowledge the National Key Research and Development
Program of China (2016YFB0600901), the National Science
Foundation of China (21525626, 22038009, 51861125104), and
the Program of Introducing Talents of Discipline to Universities
Olcina, L. Hu, D. Cornu, R. Huang, D. Stoian, A. Urakawa,
Chemphyschem 2017, 18, 3135-3141.
[
11] H. Xiao, W. A. Goddard, 3rd, T. Cheng, Y. Liu, Proc. Natl.
Acad. Sci. U.S.A. 2017, 114, 6685-6688.
12] J. Gong, H. Yue, Y. Zhao, S. Zhao, L. Zhao, J. Lv, S. Wang,
(
BP0618007) for financial support.
[
0
+
Keywords: CO electrochemical reduction, Cu -Cu pairs, CO
2
2
X. Ma, J. Am. Chem. Soc. 2012, 134, 13922-13925.
activation, C-C coupling, synergistic effect
[13] F. C. Zhiwei Huang, Jingjing Xue, Jianliang Zuo, Jing Chen,
and Chungu Xia, J. Phys. Chem. C 2010, 114, 16104–16113.
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[
3
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Angewandte Chemie International Edition
10.1002/anie.202105118
COMMUNICATION
COMMUNICATION
Controllable Cu -Cu+ pairs derived
from the well-dispersed cupric oxide
supported on copper phyllosilicate
lamella can break thermodynamic and
0
Xintong Yuan, Sai Chen, Dongfang
Cheng, Lulu Li, Wenjin Zhu, Dazhong
Zhong, Zhi-Jian Zhao, Jingkun Li, Tuo
Wang, and Jinlong Gong*
kinetic limitations of CO
reaction and achieve the superior CO
electronreduction performance.
2
reduction
Page No. – Page No.
2
0
+
Controllable Cu -Cu Sites for
Electrocatalytic Reduction of Carbon
Dioxide
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