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In situ probing the dynamic reconstruction of

Cite this: Nanoscale, 2022, 14, 8944
copper–zinc electrocatalysts for CO2 reduction†
Yen-Po Huang,‡a Ching-Wei Tung,‡a Tai-Lung Chen,a Chia-Shuo Hsu, a

Mei-Yi Liao,*b Hsiao-Chien Chen*c,d and Hao Ming Chen *a,e

Unravelling the dynamic characterization of electrocatalysts during the electrochemical CO2 reduction
reaction (CO2RR) is a critical factor to improve the production efficiency and selectivity, since most pre-
electrocatalysts undergo structural reconstruction and surface rearrangement under working conditions.
Herein, a series of pre-electrocatalysts including CuO, ZnO and two different ratios of CuO/ZnO were
systematically designed by a sputtering process to clarify the correlation of the dynamic characterization
of Cu sites in the presence of Zn/ZnO and the product profile. The evidence provided by in situ X-ray
absorption spectroscopy (XAS) indicated that appropriate Zn/ZnO levels could induce a variation in the
Received 17th March 2022, coordination number of Cu sites via reversing Ostwald ripening. Specifically, the recrystallized Cu site with
Accepted 2nd June 2022
a lower coordination number exhibited a preferential production of methane (CH4). More importantly, our
DOI: 10.1039/d2nr01478e findings provide a promising approach for the efficient production of CH4 by in situ reconstructing Cu-
rsc.li/nanoscale based binary electrocatalysts.

Introduction To date, Cu series catalysts such as oxide-derived Cu remain

the most active catalysts for CO2 reduction owing to the variety of
The excessive use of fossil fuels and massive emissions of carbon their products and C2+ products based on the moderate binding
dioxide (CO2) have led to an energy crisis and severe climate energy between the Cu metal and the intermediates.11,12
change.1 Attention to energy- and environment-related issues has However, they exhibit poor selectivity towards hydrocarbons and
driven significant efforts in CO2 conversion technologies.2–4 The normally produce CH4 at a high cathodic potential. The pathway
electrochemical CO2 reduction reaction (CO2RR) is emerging as a of reducing CO2 to CH4 should efficiently execute the protonation
viable method to consume excess carbon dioxide in the atmo- of CO under moderate binding energy, since weak binding
sphere and store chemical energy in value-added chemicals.5–7 energy results in the desorption of CO without any protonation
Therefore, efforts have been devoted to exploring efficient electro- process and strong binding energy causes significant overpoten-
catalysts with high selectivity for the CO2RR because CO2 can be tial. To this end, various Cu-based series of electrocatalysts had
converted into formate, methanol (CH3OH), methane (CH4), been investigated in terms of their particle size,13 crystal
ethylene (C2H4) ethanol (C2H5OH), etc. Among these, due to its orientation,14,15 surface morphology,16,17 and oxidation state.3,18
relatively clean combustion in combustion engines,8 high energy Additionally, the strategy of preparing Cu-based alloys by introdu-
density and suitability to the present infrastructure for natural cing foreign particles into Cu tunes the binding energy between
gas storage and transport,9,10 the product of methane has shown the intermediates and catalysts and thus alters the CH4
significant economic benefits. distribution.19
Recently, a study on the in situ X-ray absorption spec-
troscopy (XAS) of Cu-based electrocatalysts suggested that the
a
Department of Chemistry, National Taiwan University, Taipei 106, Taiwan. oxidation state of Cu electrocatalysts significantly influenced
E-mail: haomingchen@ntu.edu.tw the CO2RR pathway and product distribution.3,18 In this, the
b
Department of Applied Chemistry, National Pingtung University, Pingtung 90003,
production of C2+ hydrocarbons is highly correlated with the
Taiwan. E-mail: myliao@mail.nptu.edu.tw
c
Center for Reliability Science and Technologies, Chang Gung University, Taoyuan mixed Cu+ and Cu0 chemical state. Evidently, metallic Cu0
33302, Taiwan. E-mail: hc_chen@mail.cgu.edu.tw favors methane production. However, Cu-based electrocatalysts
d
Kidney Research Center, Department of Nephrology, Chang Gung Memorial are prone to self-oxidation in electrolytes and cannot get com-
Hospital, Linkou, Taoyuan 33305, Taiwan pletely reduced to Cu metal even at high potentials. The pres-
e
National Synchrotron Radiation Research Center, Hsinchu 300, Taiwan
ence of oxidized Cu-based electrocatalysts suppresses the pro-
† Electronic supplementary information (ESI) available. See DOI: https://doi.org/
10.1039/d2nr01478e duction of C1+ hydrocarbons as well as reduces their selectivity.
‡ These authors contributed equally. A previous study demonstrated that a Cu–Ag alloy prepared via

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the atomic interdiffusion of Ag into Cu nanowires stabilized the Cu target and 150 W to the ZnO target showed a particle
metallic Cu0 during the CO2RR as well as inhibited its spon- size of around 500 nm (Fig. 1b). The EDS mapping and
taneous reoxidation.20 Besides, expanding the Cu–Cu distance elemental composition results further confirm that Cu and Zn
through interdiffusion induced a stronger interaction with elements are homogeneously distributed on a gas diffusion
*CHO and thus accelerated CH4 production.21 In addition to layer (GDL) with an elemental composition ratio of 1 : 3
the oxidation state, the Cu-based electrocatalyst coordination without noticeable phase separation (Fig. S1†); we thus named
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number also influences the product profile, which corresponds the sample s-Cu1Zn3Ox. Similarly, the sample with a rough
to the binding strength of the intermediate on the Cu nano- surface from a sputtering power of 150 W to the Cu target and
particle surface.22 A Cu electrocatalyst with a low coordination 50 W to the ZnO target showed an elemental composition ratio
number inhibits C–C coupling; therefore, C1 products domi- of 5 : 1, and was named s-Cu5Zn1Ox (Fig. 1c). The crystalline
nate the product profile. As the coordination number of the structures of the deposited film were investigated by XRD
Cu electrocatalyst gets close to 9, CH4 is formed preferen- (Fig. S2†). Sputtering Zn (s-ZnO) with a power of 200 W
tially.23 However, recent investigations involving in in situ XAS showed diffraction peaks at 2θ = 33.4° and 35.4°, corres-
measurement have demonstrated that the coordination ponding to hexagonal wurtzite ZnO (JCP2) (card number, 003-
number of pre-electrocatalysts can change during electro- 0888). For sputtering Cu (s-CuO) with a power of 200 W, the
catalytic reactions such as water splitting and the CO2RR.24–30 characteristic diffraction peaks at 2θ = 34.7° and 37.7° were
This finding means that the correlation between the product ascribed to the (−111) and (100) planes of cubic-structured
and the coordination number of the electrocatalysts cannot be CuO. The complete transformation of the metals to the metal-
accurately confirmed if the electrocatalyst characterizations lic oxides ZnO and CuO was attributed to the exposure to the
under working conditions cannot be captured immediately. atmosphere after the sputtering process. Additionally, only the
In this work, to unravel the effect of the dynamic coordi- crystal features of ZnO and CuO were observed in s-Cu1Zn3Ox
nation number of Cu on the selectivity of the CH4 product in and s-Cu5Zn1Ox, respectively, due to the lower mobility of the
the duration of the CO2RR, a Cu–Zn nanocomposite with adatoms sputtered on the surface, which decreased the crystal-
various ratios was prepared via a sputtering process. The linity.31 Furthermore, the diffraction peaks of the bimetallic
results indicate that the introduction of Zn in the optimal ratio compounds monotonously shifted towards higher angles than
significantly improved the production efficiency of CH4. those of s-ZnO and s-CuO. This phenomenon could show that
Furthermore, the in situ XAS results show that the dynamic the lower sputtering power of Cu in s-Cu1Zn3Ox and Zn in
coordination number of Cu sites strongly dominates the s-Cu5Zn1Ox induced lower compressive stress and lower lattice
product profile, in which a decrease in the coordination distortions.32
number of the Cu sites is associated with an increase in the The chemical state and local structure of the sputtering
production efficiency of CH4. samples were further probed by XAS, including X-ray absorp-
tion near-edge structure (XANES) and extended X-ray absorp-
tion fine structure (EXAFS). Fig. 2a shows the Zn K-edge
Results and discussion XANES of s-ZnO, s-Cu1Zn3Ox and s-Cu5Zn1Ox along with the
Zn foil and ZnO reference spectra. Compared with Zn foil, the
Characterization of sputtering Cu–Zn nanocomposites
Zn K-edge XANES of s-ZnO, s-Cu1Zn3Ox and s-Cu5Zn1Ox
Fig. 1(a) shows a schematic diagram of the co-sputtering shifted to a higher energy. The oxidation states of s-ZnO,
system with a Cu and ZnO target. Two conditions for preparing s-Cu1Zn3Ox and s-Cu5Zn1Ox were obtained from the maximum
the Cu–Zn nanocomposites were adopted, wherein the total value of the first derivative of their respective XANES (Fig. 2b).
sputtering power was fixed at 200 W. The obtained samples The energies of the maximum values of s-ZnO and s-Cu1Zn3Ox
were inspected by SEM-EDS to confirm the ratio of Cu and Zn. were close to that of the ZnO standard sample. Conversely, the
The sample obtained from a co-sputtering power of 50 W to value of s-Cu5Zn1Ox is located between those of Zn foil and
ZnO. According to the valency of zinc (either Zn(0) or Zn(II)),
the extent of the oxidation state could be estimated using a
mixture of Zn and ZnO in different proportions. However, the
Fourier-transformed k3-weighted EXAFS spectra of the Zn
K-edge of s-ZnO, s-Cu1Zn3Ox and s-Cu5Zn1Ox only showed a
Zn–O bond distance of 1.55 Å and a second coordination shell
Zn–Zn bond distance of 2.87 Å without any Zn–Zn metallic
bond, indicating that the value of s-Cu5Zn1Ox being between
those of Zn foil and ZnO was not caused by the mixed valency
of Zn(0) and Zn(II) (Fig. 2c). This result also demonstrated that
the Zn species existed in the form of ZnO in s-Cu5Zn1Ox. The
fact that ZnO appeared to be below the oxidation state of +2
Fig. 1 (a) A schematic diagram of the co-sputtering system. SEM and can be attributed to oxygen vacancies.33,34 Additionally, no
EDS mapping of (b) s-Cu1Zn3Ox and (c) s-Cu5Zn1Ox. metallic bond of Zn–Cu was observed, implying that the co-

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Fig. 2 (a) XANES spectra of the Zn K-edge, (b) their first derivative spectra and (c) their EXAFS spectra. (d) XANES spectra of the Cu K-edge, (e) their
average oxidation states of Cu from the XANES spectra and (f ) their EXAFS spectra.

sputtering samples did not form any alloy. Moreover, the Cu those of s-ZnO and s-CuO, the coordination number of co-
K-edge XANES of the sputtering samples shifted to a higher sputtered ZnO/CuO was lower. Therefore, it could be deduced
energy compared with that of Cu foil (Fig. 2d). By adopting a that the coordination number of the Cu site and Zn site could
fitting procedure utilizing a linear combination of Cu, Cu2O be reduced concurrently via the co-sputtering process.
and CuO references (Fig. S3†), the oxidation states of Cu in the
sputtering samples were all found to be +2, which was ascribed Electrochemical performance for the CO2RR
to the CuO structure (Fig. 2e). Besides, the co-sputtering The electrocatalytic behaviors of the sputtering materials on
samples showed the first and second coordination shells of the GDL for the CO2RR were studied using linear sweep vol-
the Cu–O and Cu–Cu scattering paths without observing a Cu– tammetry (LSV) in a 1.0 M KOH solution under the flow of CO2
Zn bond. The results of XANES and R space analyses demon- (Fig. S5†). s-CuO/GDL achieved a CO2RR current density
strated that the co-sputtering Cu–Zn samples exhibited mixed higher than those of the other sputtering samples, implying
structures of ZnO and CuO without forming any alloy. that s-CuO/GDL had the highest CO2RR activity. However, the
Additionally, the co-sputtering of ZnO and CuO could avoid activity decreased in the presence of ZnO. Fig. 3 and Fig. S6†
the aggregation or overgrowth of individual metal oxides, show the product faradaic efficiency (FE) as a function of the
which could afford well-dispersed smaller CuO and ZnO nano- applied iR-corrected potentials for various sputtering samples,
particles on the GDL. To clarify the coordination number with with the corresponding product partial currents shown in
and without the co-sputtering process, EXAFS fitting of the Fig. S7.† In addition to hydrogen evolution, the C1 products of
prepared samples was carried out (Fig. S4†). Tables S1 and S2† CO and formate are the major products for s-ZnO, which is
show the structural parameters of the sputtered samples consistent with common ZnO nanoparticles or foil.7 On the
extracted from the Zn and Cu K-edge EXAFS. Compared with contrary, for s-CuO, the C2+ products of C2H4 and C2H5OH

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CO2RR was confirmed by the variation in current at an applied

potential of −1.86 V. As shown in Fig. S8,† no significant changes
were observed over 50 h, indicating good electrocatalyst stability
and good adhesion of the electrocatalyst on the GDL.
Furthermore, the structural characterization of the electrocatalyst
at 5 and 50 h of working time was performed by XPS. Although
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the in situ XAS demonstrated that the Cu site at −1.86 V was in

the form of Cu0, copper oxide and hydroxide were detected by
the XPS spectrum of Cu 2p at both 5 h and 50 h, which could be
ascribed to the effect of the alkaline electrolyte and the atmos-
pheric environment. However, the Cu structure did not change
between the sampling times of 5 and 50 h. This result shows that
the electrocatalyst under working conditions was stable, leading
Fig. 3 Faradaic efficiency as a function of potential for various CO2RR
products. to the stable current.

In situ XAS probing of the dynamic electrocatalyst structure

dominated the reduction current in the range of −0.71 V and It has been demonstrated that the oxidation state of Cu electro-
−2.16 V. However, the introduction of a small amount of ZnO catalysts inevitably undergoes dynamic changes as well as
(s-Cu5Zn1Ox) inhibited the activity of CuO, especially for the structural reconfigurations as the CO2RR proceeds.18,35 To
C2+ products. Compared with s-CuO, the total FE of the C2+ reveal the correlation of the chemical state and the coordi-
products dropped sharply and was replaced by CO as the main nation environment to the product profile during the CO2RR,
product, which was similar to the CO2RR behavior of s-ZnO. in situ XAS of s-Cu5Zn1Ox and s-Cu1Zn3Ox was conducted
Additionally, the FE of CH4 on s-Cu5Zn1Ox slightly increased at (Fig. S9†). The Cu K-edge XANES of both s-Cu5Zn1Ox and
the applied potential from −1.56 V to −2.16 V compared with s-Cu1Zn3Ox did not change while they were immersed in the
that on s-CuO, indicating that the introduction of Zn could electrolyte. By applying a potential of −1.06 V, the shift of
improve the CH4 production at an applied potential from energy towards a lower position was observed. The first deriva-
−1.56 V to −2.16 V compared with that on s-CuO. This tive of XANES for both samples indicated that CuO was
phenomenon was significantly amplified while the content of Zn reduced and since then there was no further shift as the catho-
increased to 75% in s-Cu1Zn3Ox, in which the production of C2+ dic potential increased (Fig. 5a and S7a†). Fig. 5b shows the
products was strongly inhibited (Fig. 4a and b), and the partial cathodic potential-dependent oxidation states of Cu in
current of CH4 increased sharply (Fig. 4c). Fig. 4d clearly shows s-Cu5Zn1Ox and s-Cu1Zn3Ox. The oxidation state of both
that the partial current ratio of C2+ products to CH4 increased sig- samples immediately decreased from +2 to 0 when a potential
nificantly with the increase in cathodic potential with the
s-Cu1Zn3Ox electrocatalyst. The stability of s-Cu1Zn3Ox during the

Fig. 5 (a) The first derivative spectra of the in situ Cu K-edge XANES of
s-Cu1Zn3Ox. (b) The oxidation states of Cu in s-Cu1Zn3Ox and
s-Cu5Zn1Ox under applied cathodic potential. (c) The first derivative
Fig. 4 (a) C2H4, (b) C2H5OH and (c) CH4 partial current densities for spectra of the in situ Zn K-edge XANES of s-Cu1Zn3Ox. (d) The oxidation
s-CuO, s-Cu5Zn1Ox and s-Cu1Zn3Ox at different potentials. (d) CH4/C2+ states of Zn in s-Cu1Zn3Ox and s-Cu5Zn1Ox under applied cathodic
ratio as a function of potential for each sample. potential.

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was applied at −1.06 V, which meant that the samples trans- potential increased from −1.06 V to 1.86 V. Furthermore,
formed from CuO to metallic Cu. However, the production of in situ XRD was used to further characterize the structural
C2+ products was still observed at −1.6 V, even above this change of s-Cu1Zn3Ox during the CO2RR. As shown in
potential (Fig. 3). This result could be attributed to the spon- Fig. S14,† the diffraction peaks of both CuO and ZnO dis-
taneous re-oxidation of Cu sites to maintain the oxidation appeared accompanied by the formation of peaks at 2θ = 43.2°
state between 0 and +1, although the in situ XAS did not reveal and 50.1°, which were ascribed to Cu (JCPDS No. 003-1018),
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this phenomenon. It should be noted that the potential- indicating that CuO was electrochemically reduced to metallic
induced changes in the oxidation state of Zn showed dramati- Cu. Besides, the peak at 2θ = 43.2° was assigned to the metallic
cally different results (Fig. 5c, d and S10b†). The average oxi- Zn (101) facet (JCPDS No. 87-0713). This result was consistent
dation state of s-Cu5Zn1Ox decreased to +0.9 at −1.06 V and with the XAS observations for the Cu2+ to Cu0 transition. These
did not change further at higher cathodic potentials, indicat- peaks of metallic Cu still existed without forming alloy peaks,
ing that most of ZnO was reduced to metallic Zn. However, while the potential increased to −1.56 V and −1.86 V. However,
ZnO in s-Cu1Zn3Ox was hardly reduced to metallic Zn at −1.06 these peaks became broader with the increase in potential,
V, which could be due to the fact that the Zn sites spon- meaning that the particle size of metallic Cu was reduced.
taneously underwent another reduction reaction at this catho- Previous reports have shown that Cu atomic diffusion occurs
dic potential and induced auto-oxidation. during the CO2RR. Both the dissolution of Cu from pristine
To further verify the changes in the local atomic environ- nanoparticles and the electrochemical reduction of dissolved
ment of s-Cu5Zn1Ox and s-Cu1Zn3Ox during the CO2RR, the Cu lead to particle size reduction. Furthermore, the compari-
Fourier-transformed k3-weighted EXAFS spectra were recorded, son of the particle size of s-Cu1Zn3Ox before and after the
and the structural parameters extracted from the in situ Cu CO2RR at −1.86 V for 2 h was performed via TEM (Fig. S15†).
and Zn K-edge EXAFS are summarized in Tables S3 to S6.† As Overall, the particle size of s-Cu1Zn3Ox decreased slightly. The
mentioned previously, the most intense peak at ∼1.9 Å was results of the in situ XAS, in situ XRD and TEM analyses reveal
attributed to a single scattering path of the Cu–O bond in that the reconstruction of s-Cu1Zn3Ox occurred during the
s-Cu5Zn1Ox and s-Cu1Zn3Ox. This peak disappeared at −1.06 V, CO2RR through the dissolution–recrystallization of Cu, which
and a new peak was observed at ∼2.5 Å, which was assigned to reduced the coordination number as well as the particle size.
the first coordination shell of the Cu–Cu bond, indicating that This phenomenon could be described by reversing Ostwald
the CuO structure in both samples was reduced to metallic Cu ripening,35,36 as shown in Fig. 7. The in situ XANES of the Zn
(Fig. S11 and S12†). Notably, no Cu–Zn bond was observed in k-edge showed that the white line intensity became stronger as
both s-Cu5Zn1Ox and s-Cu1Zn3Ox during the CO2RR, cathodic potential was applied, which was attributed to the
suggesting that the effect of the alloy structure on the product generation of oxygen defect structures. This n-type ZnO semi-
profile did not need to be considered. Moreover, Fig. 3 shows conductor improved the electron mobility of s-Cu1Zn3Ox,37
that the s-ZnO sample only produced CO and formate in the which acted as the surfactant passivating surface of the Cu
CO2RR, which meant that the active site responsible for CH4 nanoparticles. Therefore, the surface energy of the Cu nano-
production was the Cu site. The Cu–Cu and Zn–Zn distances particles was decreased to negative.38–40 In this case, the Cu
of both samples increased negligibly with increasing potential nanoparticles exhibited a trend of increasing surface area-to-
(Fig. S13†). For the coordination environment of s-Cu5Zn1Ox, volume ratio with the dissolution of the larger size of the Cu
the coordination number of the Cu site slightly increased from site. Meanwhile, the cathodic potential was applied during the
11.9 to 12.1 (Fig. 6a), and that of the Zn site remained CO2RR process, which was sufficient to electrochemically
unchanged (Fig. 6b). It is worth noting that the applied poten- reduce the dissolved Cu ions. Additionally, similar to the reac-
tial showed a strong correlation with changes in the coordi- tion mechanism of zinc–copper batteries,41 partially reduced
nation environment of the Cu and Zn sites of s-Cu1Zn3Ox, metallic Zn acted as a reducing agent to reduce Cu ions, thus
especially the Cu site, wherein the coordination number of the inducing the aforementioned auto-oxidation of the reduced
Cu site observably decreased from 11.9 to 10.9, while the Zn. Under these conditions, the recrystallization reaction of Cu
was triggered, and the particle size of the newly formed Cu
nanoparticles was forced to eventually reach a critical size.
These processes caused a decrease in the coordination
number of the Cu sites, which was consistent with the result

Fig. 6 Coordination number of the (a) Cu–Cu path and (b) Zn–Zn path Fig. 7 Schematic process of the reconstruction of Cu sites during the
as a function of potential for s-Cu1Zn3Ox and s-Cu5Zn1Ox. CO2RR.

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of the in situ EXAFS. Besides, the EXAFS of the Cu and Zn 25 cm2 to reach an almost 150 nm thickness. The sputtering
K-edge of s-Cu1Zn3Ox after an applied potential of −1.86 V power supply used four different factors (ZnO : Cu = 200 : 0,
were recorded. The EXAFS of the Cu and Zn K-edges of the 150 : 50, 50 : 150, 0 : 200) kept at a total of 200 W DC in an
post-electrocatalyst were similar to those at −1.86 V (Fig. S16†). atmosphere combined with 40 sccm Ar and 10 sccm O2.
Furthermore, the fitting results of the EXAFS showed ignorable
changes in the coordination number and bond distance Electrochemical measurements
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(Tables S3 and S5†), indicating that potential-induced dynamic Electrochemical data were collected using a potentiostat
reconstruction ceased when the potential was stopped. It also (Autolab PGSTAT302N, Metrohm Autolab). In addition, we
showed that the potential-induced structure was stable. used a flow cell with three components composed of gas,
As the cathodic potential increased, a significant decrease cathode and anode chambers. The cathode and anode
in the coordination number of the Cu sites was noted along chambers were separated by an anion-exchange membrane
with a corresponding increase in CH4 products and a decrease (Fumasep FAA-3-PK-130, FuMA-Tech). Ag/AgCl (3 M KCl) was
in C2+ products. This tendency is in agreement with a previous used as the reference electrode. Nickel foam was used as
report that indicates that a lower coordination number of the the anode. We chose 1 M KOH (ACROS) as the electrolyte.
Cu electrocatalyst suppresses the C–C coupling involved in C2+ The catholyte and anolyte, both 40 ml, were circulated using
products and improves the production of C1+ products.22 a peristaltic pump at a rate of 30 rpm. To keep the cell in a
However, a slight decrease in the coordination number of CO2 (Shen-Yi Gas Co.) environment, we used a mass flow
s-Cu1Zn3Ox was also observed. According to the reaction meter (F-111BI, Bronkhorst High-Tech BV) to control the flow
mechanism of zinc–copper batteries, metallic Zn self-oxidizes rate at 30 sccm. The product distribution was analyzed at
into Zn ions while reducing Cu. This reaction also occurred in various potentials by chronoamperometry. Linear sweep
s-Cu1Zn3Ox during the CO2RR, where the reduced Zn site was voltammetry (LSV) was carried out at a scan rate 10 mV s−1,
converted into Zn ions at the same time as the dissolved Cu and potentiostatic electrochemical impedance spectroscopy
ions were reduced, subjecting Zn to a recrystallization process (PEIS) was used to determine the uncompensated solution
and slightly lowering the coordination number. With the resistance (Ru).
assistance of the reduction potential and the reducing ability
of metallic Zn, the oxidation state of the active Cu sites could CO2 reduction reaction product analysis
be maintained at 0, which facilitated the production of CH4. The gaseous products were analyzed by online gas chromato-
graphy (Agilent 7890A, Agilent Technologies) using a thermal
conductivity detector (TCD) for H2 and CO quantitation and a
Conclusions flame ionization detector (FID) for CH4 and C2H4 quantitation.
HCOOH and ethanol were analyzed by NMR (Bruker AVIII
In summary, a series of sputtering electrocatalysts were prepared HD-400 MHz NMR).
to perform the CO2RR. Although the introduction of s-ZnO into
s-CuO decreased its activity in the CO2RR, it significantly Characterization
changed the product profile. Under optimal conditions, the pro- Scanning electron microscopy (SEM, JEOL JEM-2100F) was
duction efficiency of CH4 was clearly improved, and the C2+ pro- used to characterize the surface morphology of the different
ducts were suppressed. Furthermore, the results of in situ XAS Cu/Zn ratio GDEs, and energy-dispersive X-ray spectroscopy
reveal that CH4 production was strongly dominated by the coordi- (EDX) line scans were conducted using an Oxford INCAx-act
nation number of the Cu sites, wherein the lower coordination system to analyze the ratio of copper and zinc. X-ray diffraction
number of the Cu sites formed CH4 preferentially. The variation (XRD, Bruker D2 Phaser) was used to obtain the crystalline
in the coordination number of Cu was attributed to the contri- structure using Cu Kα radiation (λ = 1.54 Å).
bution of the Zn site, which triggered reversing Ostwald ripening
during the CO2RR. Meanwhile, besides the cathodic potential, In situ quick-scanning X-ray absorption spectroscopy
the reduced Zn site also acted as a reducing agent to reduce dis- The Cu and Zn K-edge absorption were measured using a TPS
solved Cu ions to carry out the recrystallization of the Cu sites. 44A, Hsinchu, Taiwan. The corresponding data were recorded
This work first unravelled the effect of the reversing Ostwald in the total-fluorescence-yield mode. To obtain a high-quality
ripening/dynamic coordination number of Cu-based electrocata- spectrum, we applied the Quick-XAS mode with a time resolu-
lysts for selective CH4 production in the CO2RR. tion of 5 seconds. The X-ray absorption experimental data were
collected in the total-fluorescence-yield mode, in which the
metallic Cu and Zn foil were taken as references for energy
Experimental calibration.
Preparation of the gas diffusion electrodes (GDEs)
GDEs were fabricated by sputter deposition (oxide sputter). We Conflicts of interest
used two targets (ZnO and Cu, 99.9% purity) sputtered using a
Sigracet 39 BB GDL (Fuel Cell Store) with a surface area of There are no conflicts to declare.

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Acknowledgements 18 S. C. Lin, C. C. Chang, S. Y. Chiu, H. T. Pai, T. Y. Liao,

C. S. Hsu, W. H. Chiang, M. K. Tsai and H. M. Chen, Nat.
We acknowledge support from the Ministry of Science and Commun., 2020, 11, 3525.
Technology, Taiwan (Contracts No. MOST 108-2628-M-002-004- 19 X. Wang, P. Ou, J. Wicks, Y. Xie, Y. Wang, J. Li, J. Tam,
RSP, MOST 110-2113-M-153-001 and MOST 109-2222-E-182- D. Ren, J. Y. Howe, Z. Wang, A. Ozden, Y. Z. Finfrock, Y. Xu,
002-MY3). Y. Li, A. S. Rasouli, K. Bertens, A. H. Ip, M. Graetzel,
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D. Sinton and E. H. Sargent, Nat. Commun., 2021, 12, 3387.

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