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Electrochemistry Communications 102 (2019) 72–77

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Electrochemistry Communications
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A strategy to eliminate carbon deposition on a copper electrode in order to T


enhance its stability in CO2RR catalysis by introducing crystal defects
Kaisong Xianga, Fangfang Zhua, Yucheng Liua, Yifan Pana, Xiaoyang Wanga, Xu Yana,b,
Hui Liua,b,

a
School of Metallurgy and Environment, Central South University, 932 South Lushan Rd, Changsha, Hunan 410083, China
b
Chinese National Engineering Research Center for Control & Treatment of Heavy Metal Pollution, 932 South Lushan Rd, Changsha, Hunan, 410083, China

ARTICLE INFO ABSTRACT

Keywords: Cu is the only electrocatalyst that converts CO2 into appreciable quantities of hydrocarbons. However, it usually
CO2 electroreduction suffers from poor catalytic stability. In this work we propose a strategy of introducing crystal defects to change
Cu electrode the reaction pathway and avoid accumulation of carbon on the Cu electrode surface, thus preventing its deac-
Catalytic stability tivation. Our experimental results show that carbon accumulation vanished and catalytic stability improved after
Carbon accumulation
crystal defects had been introduced into nano Cu electrodes. The correlation between the two rules: (1) crystal
Crystal defects
defects facilitate C2H4 formation while suppress CH4 generation; (2) crystal defects improve catalytic stability,
reveals that the C2H4 formation pathway bypasses the carbon deposition associated with CH4 formation and
results in stable catalytic performance. In particular, the Cu catalyst prepared according to this principle per-
formed with good stability for 6 h almost without any change in Faradaic efficiency. This work may provide a
new approach to stable CO2RR catalysis by managing the reaction pathway.

1. Introduction reduction [12]. This method provided an approach to avoid the effects
of deposited carbon by burying it beneath the surface, but does not
The concentration of CO2 in the atmosphere is increasing year by eliminate the deposited carbon. This means that the deactivation will
year and the resulting greenhouse effects have attracted global atten- occur again when the surface refresh stops as the Pd or Rh lose their
tion [1,2]. In recent years, the concept of carbon neutrality has been affinity to the surface Cu atoms due to the increased Cu thickness. To
gradually accepted, in which converting CO2 to useful chemicals or date, no studies have reported an approach which eliminates carbon
fuels play an important role. A number of commodity chemicals, in- deposition during the CO2RR.
cluding carbon monoxide, formic acid, methane, ethylene and ethanol, As previously reported, the carbon formation pathway is correlated
have been successfully synthesized through electrochemical reduction with the products of CO2RR [13]. Some researchers have suggested that
of CO2 by various catalysts [3]. Among these catalysts, Cu has excellent a carbon intermediate could be formed during the CH4 formation
performance in converting CO2 to hydrocarbons [4,5], and has been pathway [14,15]. Switching the CH4 formation pathway to a parallel
widely studied for this reason. pathway to generate C2H4 may avoid carbon formation and accumu-
A large number of studies have aimed to design a high-performance lation. It has been reported that the important step in C2H4 formation,
Cu catalyst, but these have mainly focused on improving product se- CO-CO dimerization, occurs more easily on Cu atoms at crystal defects
lectivity [6–8]. By contrast, the deactivation of the Cu electrode has not due to the stronger adsorption towards CO intermediates [16]. There-
received as much attention as it deserves [9–11]. The reason for the fore, guiding the CO2RR pathway by introducing defects into a Cu
catalytic instability of Cu electrodes is still controversial. Recent studies electrode opens the possibility of preventing deactivation. In this work,
have suggested that deactivation of Cu electrodes originates with the we present the pathway-guided tactics of avoiding carbon formation
deposition of carbon species during the CO2 reduction reaction (CO2RR) and accumulation on a Cu electrode in order to obtain good catalytic
[12]. For this reason, Weng et al. utilized foreign atoms (Pd, Rh) to stability.
induce the restructuring of the Cu surface, which constantly refreshed
the catalyst surface and thus maintained its catalytic properties for CO2


Corresponding author.
E-mail address: leolau@csu.edu.cn (H. Liu).

https://doi.org/10.1016/j.elecom.2019.04.001
Received 22 February 2019; Received in revised form 30 March 2019; Accepted 1 April 2019
Available online 03 April 2019
1388-2481/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/BY-NC-ND/4.0/).
K. Xiang, et al. Electrochemistry Communications 102 (2019) 72–77

Fig. 1. (a) Schematic illustration of treatments to eliminate or increase the amount of defects in Cu NNs. The corresponding morphology characterized by (b) SEM
and (c) TEM (I. annealed CuNNs; II. CuNNs; III. OT-CuNNs). (d) XRD patterns and XPS analysis of (e) Cu2p and (f) O1s of the CuNNs before and after annealing and
oxidation/reduction treatments.

2. Experiments temperature was set at 500 °C for 3 h. For the oxidation treatment, the
Ar was replaced by air with other procedures remaining the same (re-
The Cu nanocatalyst was prepared as follows. 1 mL Cu(NO3)2 sulting material denoted as OT-Cu). The chemicals were purchased
(5 mM) was pipetted into 20 mL concentrated NaOH solution (15 M) in from Sinopharm Chemical Reagent Co., Ltd.
a glass flask under magnetic stirring at a rate of 250 rpm for 5 min. Then X-ray diffraction spectra were obtained with a Rigaku TRIII. SEM
0.1 mL ethylenediamine (EDA) was added to the above solution. The images were acquired with a JEOL IT300 Scanning Electron
solution was heated to 70 °C, and 10.5 μL N2H4 solution (35 wt% in Microscope. High-resolution transmission electron microscopy
water) was added to the solution with magnetic stirring at a rate of (HRTEM) was performed using a JEM-2100F (JEOL Ltd., Japan). XPS
500 rpm. The temperature and stirring were maintained for another measurements were performed with an Escalab 250Xi (Thermo Fisher
60 min, then the solid and liquid were separated using a piece of filter Scientific) using a monochromatic 1486.7 eV Al Kα X-ray source.
membrane (0.45 μm) and a vacuum filtration setup. Plenty of purified Raman spectroscopy (Renishaw inVia) with a 532-nm pump laser was
water was used to wash the reddish-brown solid left on the filter used to detect the carbon species on the Cu electrodes before and after
membrane. The reddish-brown solid was collected and followed by electrolysis. For the Raman tests, the catalysts were dispensed on a
vacuum drying at 60 °C for 8 h. This was followed by an annealing 1 × 1 cm clean Cu foil instead of a glassy carbon substrate without
treatment. The as-prepared copper nanoneedles (CuNNs) were placed in adding Nafion as binder, to make it easier to transfer samples and to
a tube furnace under high purity Ar flowing at a rate of 30 mL/min (the avoid the interference of external carbon sources.
resulting material is referred to as annealed Cu). The annealing All electrochemical tests were performed using a three-electrode cell

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K. Xiang, et al. Electrochemistry Communications 102 (2019) 72–77

on an electrochemical work station (CHI 760D, Shanghai, China). A be seen in Fig. 2a. The Faradaic efficiency for H2 obviously increased
platinum plate 2 × 2 cm in size was employed as the counter electrode over time, while the Faradaic efficiencies for CO, CH4 and C2H4 fluc-
and Ag/AgCl (in 3 M KCl solution) soaked in a Luggin capillary was tuated. By contrast, very stable Faradaic efficiencies for gaseous pro-
used as the reference electrode. The cathode compartment and anode ducts were achieved on CuNNs and OT-CuNNs electrodes over the
compartment were separated by a piece of proton exchange membrane whole electrolysis process (Fig. 2(b,c)). In particular, the Faradaic ef-
(Nafion 117, DuPont) to prevent re-oxidation of the products. The ficiency of C2H4 increased to 15% on the CuNNs electrode and 52% on
cathode compartment was gas-tight and connected with a gas chro- OT-CuNNs respectively, which is much higher than on the annealed
matograph (GC, Shimadzu GC2010). 0.5 M KHCO3 solution was used as CuNNs. The Faradaic efficiency of CH4 decreased from 7% for annealed
the electrolyte. The electrolysis cell had a volume of 100 mL in each CuNNs to 4% and 1.8% for CuNNs and OT-CuNNs, respectively. The
compartment, and 60 mL electrolyte was used for each electrolysis test. change in Faradaic efficiency for CO on the Cu electrode was consistent
Before the CO2 electroreduction tests, the electrolyte was bubbled with with that of CH4. The i-t curves also revealed that the catalytic beha-
high purity CO2 (30 mL/min) for at least 30 min. The Cu electrodes viour on the annealed CuNNs is not stable, as also shown by the ex-
were prepared by the following procedures: 5 mg powder (for CuNNs change current density decaying from 10 to 4.5 mA/cm2 within 3 h.
and annealed CuNNs), or 7.5 mg (for CuO NNs) and 40 μL Nafion so- However, the CuNNs and OT-CuNNs performed in a stable way during
lution (5 wt%) were dispersed in 500 μL DI water and 500 μL absolute the long-term electrolysis. Further, we investigated the relationship
ethyl alcohol by sonication to form a homogenous ink. 50 μL of the between the density of crystal defects and catalytic stability by estab-
dispersed ink was then dropped on the glassy carbon electrode lishing a correlation between the standard deviation of the products'
(1 × 1 cm). Faradaic efficiency versus electrolysis time. In this representation, the
During the chronoamperometric electrolysis, the gaseous products higher the value of the standard deviation, the worse the stability
(H2, CO and hydrocarbons) were detected by gas chromatography (GC performance. This demonstrated that the catalytic stability of Cu elec-
2010, Shimadzu; SH-Rt-Q-BOND PLOT column) equipped with a trodes was correlated positively with the density of crystal defects
Barrier Discharge Ionization Detector (BID, Shimadzu). After a 3 h (Fig. 2e), revealing the key role of crystal defects in stabilizing catalytic
electrolysis, the electrolyte was sampled and analysed by ion chroma- activity and selectivity, and endorsing our proposed strategy to obtain a
tography (IC, Metrohm 883 Basic IC plus) and headspace gas chroma- stable Cu electrode.
tography (GC 2010, Shimadzu; InertCap FFAP capillary column). In previous studies, deactivation of the Cu electrode was explained
by poisoning due to carbon or organic products. This was deduced from
3. Results and discussion the C signal in the XPS analysis [24]. However, the XPS results could
not distinguish where the carbon really came from (bicarbonate elec-
To test the predictions experimentally, we prepared a couple of Cu trolyte or internal standard). Raman spectroscopy is a sensitive method
electrodes with different levels of crystal defects but with same nano- of analyzing carbon, especially graphitized carbon, and so this tech-
needle morphology. First, we prepared Cu nanoneedles (CuNNs, Fig. nique was employed to detect the carbon signal on the Cu surface [25]
S1) with a 1D structure due to their easy formation of crystal defects (Fig. 2f). Peaks at 1347 and 1596 cm−1, which are consistent with the
[17–19]. These CuNNs showed initial signs of catalytic stability re- characteristic Raman signal of graphitized carbon [26], showed an
flected by the stable current density (Fig. S2). Based on this platform, obvious increase on the annealed CuNNs after 3 h electrolysis. How-
we further managed the amount of crystal defects in the CuNNs by ever, no obvious increase in the carbon signal was observed on the OT-
annealing in an Ar atmosphere and using oxidation/reduction processes CuNNs after 3 h electrolysis. It should be noted that the typical gra-
to eliminate and increase the level of defects, respectively (illustrated in phitized carbon signal shows that the carbon species is derived from the
Fig. 1a). Fig. 1(b,c) shows the SEM and TEM images of the CuNNs reduction process rather than carbon contamination. As previously re-
before and after annealing or oxidation/reduction, demonstrating the ported, the carbon accumulation on Cu may subsequently contribute to
consistency in morphology with 100–200 nm diameter and 3–5 μm increased H2 evolution and decreased CO2RR performance [15], which
length. The XRD patterns in Fig. 1d indicate that the treatment does not is consistent with the trend of Faradaic efficiency changes on the an-
change the phase of the material (Cu0, JPCDS 85-1362), but the grain nealed CuNNs (Fig. 2a). Taking these together, it was speculated that
sizes varied from 48.6 to 34.3 nm (Fig. S3). A previous study has shown carbon accumulation on the surface of the annealed CuNNs lead to a
that a smaller grain size is associated with more defects [20]. That deterioration in catalytic stability.
means that the concentration of defects may be different due to grain The variation in Faradaic efficiency between the various Cu elec-
size changes [21,22]. Notably, the Cu2p of XPS in Fig. 1e shows that the trodes revealed that the different treatment of CuNNs leads to a dif-
OT-CuNNs sample was vulnerable to oxidation, and the O1s spectrum ferent distribution of products, especially C2H4. Notably, an obvious
demonstrated that the adsorbed O species (Oad at 531.2 eV) ratio in- improvement in Faradaic efficiency for C2H4 was obtained when the
creased in the following order: annealed CuNNs < CuNNs < OT- amount of crystal defects in the Cu electrode increased. However, in
CuNNs. Previous studies have shown that crystal defects such as grain contrast, the Faradaic efficiency for CH4 decreased. We analysed the
boundaries can act as nucleation sites to adsorb O species (Oad) to ac- electrochemically active area (ECSA, derived from Fig. S5 and Table S1)
celerate the oxidation of the Cu surface [23]. Therefore, the increasing normalized current for C2H4 and CH4 on the different Cu electrodes
concentration of defects could explain the increased ratio of Oad in studied (Fig. 3a). The increased jC2H4 means higher turnover frequency
annealed Cu, CuNNs and OT-CuNNs. (TOF) for C2H4, which is consistent with the variation of crystal defects
To test the catalytic behaviour of the CuNNs towards CO2 reduction, in the annealed CuNNs, CuNNs and OT-CuNNs, while the situation is
the as-prepared Cu electrodes were tested electrochemically. The elec- just the opposite for CH4. Therefore, the defects provide specific se-
trochemical characterization was carried out by potentiostatic electro- lectivity towards C2H4 formation, while suppressing the formation of
lysis at a potential of −1.4 V (versus Ag/AgCl) in CO2-saturated 0.5 M CH4. To investigate the reason for this phenomenon, a CO electro-
KHCO3 solution electrolyte. The gaseous products were measured by adsorption test was performed because CO is a very important inter-
online gas chromatography at intervals of 30 min during the electro- mediate in CO2RR. It is known that the CO2RR pathway is sensitive to
lysis, while the liquid products could only be identified when the the CO adsorption state. It has been suggested that the surface coverage
electrolysis was complete (Fig. S4). Therefore, the investigation of of CO* determines the distribution of products [27,28]. Recent theo-
catalytic stability will be based on the gaseous products. During the retical studies have shown that the CO dimerization step is rate-de-
electrolysis process, an obvious deactivation of the annealed CuNNs can termining, and higher coverage of CO is beneficial for CO dimerization

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K. Xiang, et al. Electrochemistry Communications 102 (2019) 72–77

Fig. 2. Faradaic efficiencies for different Cu electrodes: (a) annealed CuNNs; (b) CuNNs; (c) OT-CuNNs and (d) the corresponding current density vs time curves. (e)
Correlation between the standard deviation of the Faradaic efficiency for various gaseous products on the studied Cu electrodes and the amount of defects. (f) Raman
spectra of the annealed CuNNs and OT-CuNNs before and after electrolysis.

leading to C2H4 formation [29,30]. The CO electroadsorption tests reported that the COH path is favoured over the CHO path by a se-
(Fig. 3b) show that the OT-CuNNs have a more positive potential lectivity factor of around 2000 at 300 K, and the COH pathway to form
(−1.41 V v.s −1.48 V) to adsorb CO and larger integral area in the CH4 will follow: COH → C → CH → CH2 → CH3 → CH4 [13]. At the
voltammetry curves compared to untreated CuNNs, though the ECSA of same time, a CO dimerization process to form C2H4 as discussed above
the OT-CuNNs is smaller. This indicates that crystal defects are bene- is also possible. Therefore, two pathways may coexist in the CO2RR
ficial for CO adsorption, which ensures sufficient CO for the dimeriza- (depicted in Fig. S8): the CO dimer pathway towards C2H4 and the COH
tion process to form C2H4 [16]. This proposition is also supported by pathway towards CH4. The opposite trend of jC2H4 and jCH4 on different
the work of Boon Siang Yeo, which demonstrated that the adsorption of Cu electrodes implies that the two pathways are competitive due to the
intermediates, including CO, is significantly enhanced on Cu2O-derived shared CO intermediate. Because the crystal defects in the Cu electrode
Cu with smaller crystallite sizes (actually, more defects such as grain could enhance CO adsorption, CuNNs with more crystal defects tend to
boundaries and particle junctions) to form C2+ products [20]. For this take the CO dimer pathway to form C2H4 and suppress the COH
reason, the OT-CuNNs, which have more crystal defects, performed pathway to produce CH4. This behaviour reduces carbon formation in
better in converting the CO intermediate into C2H4 in the CO2RR pro- the CO2RR process, thus prolonging the durability of the electrode
cess. (Fig. 3c-I). With fewer crystal defects, Cu electrodes favouring CH4
Taking these results together, a rule could be formulated that the formation tend to be unstable in CO2RR due to the deposition of carbon
preferred C2H4 formation on crystal-defect-rich Cu electrodes con- during the CH4 formation process, which is in good agreement with the
tributes to better catalytic stability. Cu electrodes with fewer defects character of the COH pathway to form a C intermediate. As the catalysis
(annealed CuNNs) have low C2H4 selectivity but higher CH4 conversion continues, the active sites for CO2RR are covered by deposited carbon,
ability and are prone to catalytic instability. It is inferred that the leading to deactivation and enhanced hydrogen evolution (Fig. 3c-II).
carbon deposition causing deactivation can be ascribed to the CH4 Previous work has reported that catalytic performance in the CO2RR
formation pathway. To verify the speculation regarding instability on may be greatly influenced by nanoneedle morphology [32]. To test
Cu electrodes, Cu foil, which is considered as a good platform for whether this specific morphology accounts for the catalytic stability, in
generating CH4, was used. As expected, the Cu foil deactivates rapidly another experiment we used Cu nanoparticles (CuNPs) and OT-CuNPs
in the first hour (Fig. S6). Meanwhile, the surface of the Cu foil was also for comparison (Fig. S9). The similar catalytic stability and Faradaic
covered with detectable amounts of carbon after a 3 h electrolysis, as efficiencies of the OT-CuNNs and OT-CuNPs strongly suggests that the
revealed by the Raman spectra (Fig. S7). This supports the assertion stability was not due to the sharp-tip enhancement effect but rather
that the CH4 pathway results in carbon deposition, which is also in good dominated by crystal defects. Meanwhile, this experiment demon-
agreement with the DFT predicted pathway for CH4 formation [13]. strated the generality of the low carbon accumulation pathway in re-
At this point, the reason for the difference in catalytic stability is taining the catalytic stability of Cu electrodes in CO2RR (Table S2). This
clear. The conversion pathway of CO determines whether the electrode strategy may also give us some indications regarding the stable con-
surface is poisoned by carbon deposition or not. According to previous version of CO2 mainly towards C2+ products and suggests a general
DFT studies by Jens K. Nørskov, CO is reduced to form CHO or COH principle for the design of stable electrodes in CO2RR catalysis.
through formation of a CeH or OeH bond [31]. Recently, Nie et al.

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K. Xiang, et al. Electrochemistry Communications 102 (2019) 72–77

Fig. 3. (a) The ESCA normalized current density of C2H4 and CH4 on the annealed CuNNs, CuNNs and OT-CuNNs; (b) Voltammograms of the OT-CuNNs and CuNNs
under CO and CuNNs under N2; (c) Proposed mechanism for (I) deactivation process on a Cu surface without crystal defects and (II) stable catalysis on a Cu surface
containing crystal defects during the CO2RR.

4. Conclusion Research Funds for the Central Universities of Central South University
[2018zzts141].
We present a strategy to induce a CO2RR pathway that could avoid
accumulation of carbon species on a Cu electrode to maintain catalytic Conflict of interest
stability. This strategy could easily be realized by introducing crystal
defects to guide the CO2RR pathway towards the formation of C2H4. The authors have no conflict of interest to declare.
This provides researchers with a new approach to achieving stable
CO2RR catalysis by managing the reaction pathway. Appendix A. Supplementary data

Acknowledgements Supplementary data to this article can be found online at https://


doi.org/10.1016/j.elecom.2019.04.001.
This work was supported by National Key Research and
Development Program of China [2017YFC0210405], National Natural References
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