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Communication

Oxide-Derived Copper Nanowire Bundles for Efficient CO2 Reduction to Multi-Carbon Products

by
Dong Xu
1,†,
Minfang Wu
2,†,
Yan Huang
3,
Yongzheng Gu
4,
Guiwen Wang
3,
Long Yang
3,
Yongping Liu
3,
Tengfei Gao
1,*,
Shoujie Li
5,
Wei Wei
5,
Wei Chen
5 and
Xiao Dong
5,*
1
CHN Energy New Energy Technology Research Institute Co., Ltd., Beijing 102209, China
2
Center for Chemistry of High-Performance & Novel Materials, Institute of Analytical Chemistry, Department of Chemistry, Zhejiang University, Hangzhou 310058, China
3
CHN Energy Jinjie Energy Co., Ltd., Yulin 719319, China
4
GD Power Development Co., Ltd., Beijing 100101, China
5
CAS Key Laboratory of Low-Carbon Conversion Science and Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
*
Authors to whom correspondence should be addressed.
†
These authors contributed equally to this work.
Catalysts 2023, 13(9), 1278; https://doi.org/10.3390/catal13091278
Submission received: 8 August 2023 / Revised: 30 August 2023 / Accepted: 4 September 2023 / Published: 5 September 2023
(This article belongs to the Section Electrocatalysis)
Browse Figures
Versions Notes

Abstract

:
Cu-based catalysts for efficient C2+ production from CO2 electrocatalytic reduction reaction (CO2ERR) exhibit significant promise, but still suffer from ambiguous mechanisms due to the intrinsic structure instability during electroreduction. Herein, we report an oxide-derived copper nanowire bundle (OD-Cu NWB) for efficient CO2ERR to C2+ products. OD-Cu NWBs with a well-preserved nanowire bundle morphology lead to promoted multi-carbon production compared to commercial copper powders. The formation of OD-Cu NWBs shows a great dependence on the precipitation/calcination temperatures and per-reduction potentials, which further influence the ultimate CO2ERR performance correspondingly. The optimized preparation parameters for the formation of a well-ordered nanowire bundle morphology are found, leading to a preferred C2+ production ability. Besides the nanowire bundle morphology, the oxide-derived Cu essence of OD-Cu NWBs with stabilized Cu+ species from per-reduction also promotes the CO2ERR activity and facilitates the C-C coupling of key intermediates for C2+ production. This work provides a facile strategy and inspiration for CO2ERR catalyst developments targeting high-valued multi-carbon products.

Graphical Abstract

1. Introduction

The CO2 electrocatalytic reduction reaction (CO2ERR) motivated by sustainable energy to convert CO2 into fuels and chemicals is of great importance to confront the increasing threat of massive CO2 emissions from fossil fuel consumption [1,2,3]. The development of stable and cost-effective electrocatalysts with high selectivity and efficiency is quite critical and has been extensively studied [4,5,6]. Although the electroreduction of CO2 to C1 products (CO and formate) with high activity and selectivity has been proven to be much easier to implement over various kinds of electrocatalysts [7,8,9], the transformation of CO2 to C2+ products such as ethylene and ethanol is still limited to copper-based materials due to their moderate *CO binding [10,11,12,13]. And so far, the generation of value-added C2+ products is still suboptimal regarding activity and selectivity due to the sluggish C-C coupling kinetics [14,15,16].
Extensive studies of Cu-based electrocatalysts have revealed that their CO2ERR activity and product distribution are highly dependent on electrode morphologies [17,18], compositions [19,20] and surface structures [21,22]. For instance, compared to the Cu(111) surface which promotes CH4 formation, the Cu(100) surface is believed to facilitate C-C coupling to yield C2+ products [23]. In addition, Cu-nanowire-based catalysts (NW) are considered as more selective and efficient catalysts for the CO2ERR towards C2+ production due to the five exposed (100) planes in their five-twinned surface structures [24,25,26]. Despite the fact that most of the works on Cu-NW-based catalysts elevated the CO2ERR activity only towards CO and formate production [27,28,29,30,31,32,33,34], Ma et al. first reported a 32.6% C2+ faradaic efficiency over a CuO-derived Cu NW array and demonstrated the relevance of nanowire lengths and densities for C2+ selectivities [35]; Zhu et al. optimized a CuxAuy NW array and achieved the highest ethanol faradaic efficiency of 48% [36]; and Zhang et al. investigated a CuCl-derived Cu NW, obtaining a C2+ faradaic efficiency of 60% via catalyzing the reduction of CO rather than CO2 [37]. Although improvements in the CO2ERR performance of Cu-NW-based electrocatalysts have been made, the insufficient CO2ERR activity and C2+ selectivity [38] as well as the structure reconfiguration of Cu-based catalysts during electroreduction [39,40] led the demand for further investigations towards more efficient CO2ERR electrocatalyst designs.
Herein, oxide-derived copper nanowire bundles (OD-Cu NWBs) were fabricated for efficient CO2ERRs to multi-carbon products. Evolutions of sample morphology and structure during the preparation procedures were studied. The CO2ERR performance and electrochemical properties of obtained OD-Cu NWBs were compared with commercial copper powders. Both the performance and structure stability of OD-Cu NWB catalysts during electroreduction were also examined. We further investigated the optimum precipitation/calcination temperature and per-reduction potential for the formation of nanowire bundle structures. The relationship between the nanowire bundle morphology features and their CO2ERR performance was also explored to reveal the origin of the elevated multi-carbon production kinetics.

2. Results and Discussion

2.1. Characterization and Performance of OD-Cu NWBs

The aforementioned OD-Cu NWB was fabricated from the precipitation, calcination and electroreduction of a Cu(OH)2 NWB [41]. Figure 1 shows the detailed preparation procedures, as well as the morphologies and structures of the samples obtained during preparation. The obtained precipitate exhibited the morphology of a bundle of nanowires, and the XRD pattern was consistent with those of Cu(OH)2 (JCPDS NO. 13-420) with no peaks from other phases, indicating the well-crystallized nanowire bundle structure of the Cu(OH)2 NWB (Figure 1a) [42]. After calcination, the obtained sample maintained the nanowire bundle feature, and possessed the characteristic XRD pattern of CuO (JCPDS NO. 48-1548), suggesting the complete conversion of the Cu(OH)2 NWB to a CuO NWB (Figure 1b) [42]. The XRD patterns of the carbon-paper-supported sample with further electroreduction exhibited a combination of the characteristic peaks of metallic Cu and C (JCPDS NO. 04-0836 and NO. 41-1487), revealing the transformation of CuO to metallic Cu, along with the unchanged nanowire bundle morphology of the OD-Cu NWB (Figure 1c). Note that trace amounts of the Cu2O phase (JCPDS NO. 65-3288) were also observed in the OD-Cu NWB, which may be stabilized via the higher oxygen affinity due to the elevated surface energy originating from the high specific surface area morphology features of nanowire bundles [41,43]. Raman structural characterization of all samples also revealed the phase transition from a Cu(OH)2 NWB (with a characteristic peak at 482 cm–1) to a CuO NWB (with a characteristic peak at 295 cm−1), and the final Cu NWB contained a small amount of Cu2O species (with a characteristic peak at 210 cm−1), as shown in Figure S1 [44,45].
Figure 2 shows the CO2ERR performance of the OD-Cu NWB and reference Cu powder in detail. As shown in Figure 2a, the reference Cu powder exhibited activity for only C1 products (CO, formate, etc.) in the potential range of ≤−0.8 V vs. RHE, while C2+ products were detected until −0.9 V. The FEs of formate and CO reached the maximum at the potentials of −1.0 and −1.1 V, respectively. Then, the FEs of C2+ products increased to about 20% in the further elevated potential range. The FE of H2 from the competitive hydrogen evolution reaction decreased monotonously from 80% to over 40%, indicating the unsatisfying CO2ERR performance of untreated Cu powder. In contrast, the OD-Cu NWB (Figure 2b) possessed the maximum FEs for formate and CO at potentials as low as −0.7 and −0.8 V, respectively, as well as a lower H2 FE of ~30 % over the entire potential range, indicating a more favorable CO2ERR activity. In addition, C2+ products could also be detected at potentials as low as −0.7 V, and the FE of C2+ products increased continuously at elevated potentials, reaching the maximum of 45% at −1.4 V, suggesting the preferable C-C coupling ability of the OD-Cu NWB. In addition, C2H4 was the main C2+ product at all tested potentials and became the dominant CO2ERR product at potentials of ≥−1.2 V.
Additionally, the current densities as well as the electrochemically active surface area (derived from the cyclic voltammetry curves in Figure S2) of the OD-Cu NWB were doubled compared to those of the reference Cu powder, as shown in Figure 2c,d. The electrochemical behavior of the OD-Cu NWB in 0.1 M KHCO3 with Ar or CO2 reflected the recoverable oxide-derived Cu before −0.6 V vs. RHE, and also more favorable CO2ERR activities compared with the HER (Figure S3). Both the performance stability and recycling tests of the OD-Cu NWB at −1.4 V vs. RHE suggested a good performance stability of the OD-Cu NWB (Figure 2e and Figure S4). Additionally, the XPS and Auger spectra of the OD-Cu NWB before and after electrocatalytic reaction also demonstrated good structure stability, with the presence of trace Cu+ species (Figure S5). In summary, the C2+ production performance of the OD-Cu NWB is comparable to that of Cu-NW-based catalysts reported in the literature recently (Figure 2f and Table S1) [35,36,46,47,48,49,50]. It is believed that oxide-derived Cu would show a better CO2ERR performance with a preferable C2+ production ability compared to non-oxide-derived Cu catalysts, due to the increased exposure of defects and grain boundaries during in situ reconstruction [51,52,53]. Moreover, the well-preserved nanowire bundle morphology features of the OD-Cu NWB could also provide more active edge and step sites with a higher surface energy to stabilize the Cu+ species, which would facilitate C-C coupling kinetics [41,42].
Catalysts 13 01278 g002
Figure 2. CO2ERR performance and electrochemical properties of the as-prepared OD-Cu NWB. Faradaic efficiencies for each reduction product and for C1/C2/C3 products at different applied potentials over (a) Cu powder and (b) OD-Cu NWBs. (c) The current densities and (d) the electrochemically active surface area of both samples. (e) Performance stability of the OD-Cu NWB at −1.4 V vs. RHE. (f) C2+ production performance comparison of the OD-Cu NWB with Cu-NW-based catalysts reported in the recent literature [35,36,47,48,49,50].
Figure 2. CO2ERR performance and electrochemical properties of the as-prepared OD-Cu NWB. Faradaic efficiencies for each reduction product and for C1/C2/C3 products at different applied potentials over (a) Cu powder and (b) OD-Cu NWBs. (c) The current densities and (d) the electrochemically active surface area of both samples. (e) Performance stability of the OD-Cu NWB at −1.4 V vs. RHE. (f) C2+ production performance comparison of the OD-Cu NWB with Cu-NW-based catalysts reported in the recent literature [35,36,47,48,49,50].
Catalysts 13 01278 g002
To further investigate the impact of nanowire bundle morphology features on the CO2ERR performance of OD-Cu NWB catalysts, more detailed studies were conducted on the effects of the precipitation/calcination temperature and per-reduction potential on the formation of nanowire bundles and their corresponding CO2ERR performance.

2.2. Effects of Precipitation Temperature

The effects of precipitation temperature were studied based on a series of OD-Cu NWB samples precipitated at 0 °C, 20 °C, 40 °C and 60 °C (denoted as OD-Cu NWB-x, where x is the temperature for precipitation), respectively. The formation of CuO NWBs is affected by the precipitation temperature, and thus the structure of corresponding OD-Cu NWB samples will be influenced [42]. Although there are no obvious bulk structure distinctions between CuO NWBs (Figure S6), Figure 3 displays the differences in SEM images and CO2ERR performance for the corresponding OD-Cu NWB-x samples. It is clearly shown that at the precipitation temperature of 0 °C, ordered nanowire bundle morphology features form (Figure 3a), and with a rise in precipitation temperature, the morphology of these obtained samples was more disordered. Precipitation at 20 and 40 °C still led to nanowire morphological features (Figure 3b,c), while the sample precipitated at 60 °C cannot be recognized as a nanowire any more (Figure 3d).
As for their CO2ERR performance, although all samples exhibited the capability to convert CO2 into C2+ products, the OD-Cu NWB-0 sample stood out for the relatively fewer competitive HERs, higher FEs for C2+ products and higher current densities (Figure 4a and Figure S7). Additionally, with an elevation in precipitation temperature, not only did the FEs for C2+ products drop, but the FE for H2 also increased (Figure 4b–d). It is interesting that the OD-Cu NWB-0 sample also possessed the highest selectivity for CO in C1 products, while other samples had a higher proportion of formate in their C1 products. It is believed that CO is the key intermediate in the CO2ERR in C2+ production; therefore, the ordered nanowire bundle morphology features of the OD-Cu NWB-0 sample not only facilitate the formation of CO, but also lead to more favorable C-C coupling kinetics of CO for C2+ production [43]. The failure to form nanowire bundle structures hindered CO production and the further dimerization into C2+ products.

2.3. Effects of Calcination Temperature

The effects of the calcination temperature were also studied based on a series of OD-Cu NWB samples calcinated at 200 °C, 300 °C, 400 °C and 500 °C (denoted as OD-Cu NWB-y, where y is the temperature for calcination), respectively. The formation of CuO NWBs will be affected, and this will influence the final structure of the subsequent OD-Cu NWB samples [42]. Despite the consistent bulk structure of CuO NWBs (Figure S8), Figure 5 displays the distinctions in SEM images and the CO2ERR performance of these OD-Cu NWB-y samples. It is shown that with calcination temperatures of as low as 200 °C, the ordered nanowire bundle morphology features are well preserved (Figure 5a). Additionally, with an increase in the calcination temperature, the nanowire bundles in these samples start to sinter together, resulting in bundles of nanoparticles. Calcination at 300 °C still resulted in nanowire morphology features (Figure 5b), while for the samples calcinated at 400 and 500 °C, these nanowires broke into large nanoparticles and sintered with each other (Figure 5c,d).
For their CO2ERR performance, all samples exhibited the capability to convert CO2 into C2+ products with similar current densities (Figure S9), while the OD-Cu NWB-200 and OD-Cu NWB-300 samples exhibited a relatively lower selectivity for the HER and higher FEs for C2+ products (Figure 6a,b). Additionally, for the sintered samples of OD-Cu NWB-400 and OD-Cu NWB-500, not only did the FEs for C2+ products decrease, but also the FE for H2 was elevated (Figure 6c,d). Note that, although the OD-Cu NWB-500 sample possessed the highest selectivity for CO in C1 products, it still showed a relatively low C2+ production selectivity (Figure 6d), which suggests that these sintered nanoparticles from nanowire bundles had favorable kinetics for CO formation, but not a sufficient ability to further dimerize this CO into C2+ products [43]. Therefore, the ordered nanowire bundle morphology features preserved in the OD-Cu NWB-200 and OD-Cu NWB-300 samples were beneficial for C-C coupling in C2+ production, while the sintered nanoparticles subjected to a high calcination temperature lost active edge and step sites and possessed a lower surface energy, resulting in an unsatisfactory CO dimerization activity [53].

2.4. Effects of Per-Reduction Potential

The effect of per-reduction potentials was investigated based on a series of OD-Cu NWB samples per-reduced at −0.8 V, −1.0 V, −1.2 V and −1.4 V (denoted as OD-Cu NWB@z, where z is the potential for per-reduction), respectively. Figure 7 displays the SEM images and XRD patterns of these OD-Cu NWB samples. All samples exhibited stable nanowire bundle morphological features (Figure 7a–d), while only OD-Cu NWB@−1.4 V showed the presence of Cu2O cubes (Figure 7d), suggesting the variation in per-reduction potentials does not affect the nanowire bundle morphology. Moreover, the XRD patterns of all samples showed a combination of the characteristic peaks of metallic Cu and C (JCPDS NO. 04-0836 and NO. 41-1487), as well as trace amounts of the Cu2O phase (JCPDS NO. 65-3288) (Figure 7e) [43]. Both results indicated that the nanowire bundle morphology is well preserved during electrochemical pre-treatments, and the OD-Cu NWB could be easily obtained from the electroreduction of CuO NWBs.
CO2ERR tests were further conducted on these per-reduced OD-Cu NWB@z samples at the working potential of −1.4 V (Figure 7f,g). The results show that the per-reduction conditions led to no obvious distinctions in CO2ERR performance over these OD-Cu NWB@z samples, showing a consistent C2+ production of over 50% FE, ~20% FE for C1 products and ~30% FE for H2 with similar current densities (Figure S10). These results imply that the well-preserved nanowire bundle morphology of the OD-Cu NWB after per-reduction treatment not only promotes the CO2ERR activity but also facilitates the C-C coupling of key intermediates to form C2+ products. Additionally, the oxide-derived Cu essence of the OD-Cu NWB with stabilized Cu+ species contributes to the elevated CO2ERR performance toward C2+ production [54].

2.5. Discussion

The above results indicate that the OD-Cu NWB possessed a well-preserved nanowire bundle morphology during the preparation procedures as well as the CO2 electroreduction reactions, and promoted multi-carbon production compared with commercial copper powders. In addition, the nanowire bundle structure formation of the OD-Cu NWB shows a great dependence on the precipitation/calcination temperatures and per-reduction potentials, and further influences the final CO2ERR performance correspondingly. The relatively lower precipitation temperature of 0 °C and calcination temperature of 200 °C are the optimized preparation conditions for the formation of a well-ordered nanowire bundle morphology of the OD-Cu NWB, leading to a preferable C2+ production ability. On one hand, oxide-derived Cu electrocatalysts have always been thought to have a better CO2ERR performance with promoted C2+ production compared to that of non-oxide-derived Cu catalysts. Additionally, the more exposed defects and grain boundaries formed during in situ reconstruction are considered to provide faster CO2ERR and C-C coupling kinetics [51,52,53]. On the other hand, the nanowire bundle morphology features of OD-Cu NWBs also provide more active edge and step sites for a boosted CO2ERR. Moreover, Cu+ species are believed to have great effects on C2+ formation for Cu-based electrocatalysts, and thus many attempts have been made to stabilize these Cu+ species in Cu-based electrocatalysts. The aforementioned unsaturated sites and defects in OD-Cu NWBs possess a much higher surface energy, which helps stabilize trace Cu+ species in the catalysts, further facilitating the C-C coupling kinetics for elevated multi-carbon production [41,42].

3. Materials and Methods

3.1. Chemicals, Reagents and Materials

Anhydrous cupric chloride (CuCl2), sodium hydroxide (NaOH), potassium bicarbonate (KHCO3) and citric acid were purchased from Sinopharm Chemical Reagent Co., Ltd. (Shanghai, China). Nafion solution (5%) in ethanol and Nafion 117 proton exchange membranes (PEMs) with an average thickness of 183 µm were purchased from DuPont (Wilmington, DE, USA). All chemicals were used as received, and all solutions were prepared using ultrapure water (18.2 MΩ) from water purification systems (Master-S30UVF, HHitech, Shanghai, China).

3.2. Preparation of OD-Cu NWBs

In brief, the OD-Cu NWB was fabricated from the precipitation, calcination and electroreduction of copper hydroxide nanowire bundles (Cu(OH)2 NWBs) [41].
Firstly, 2.26 g of CuCl2 and 0.5 g of citric acid were dissolved in 200 mL of deionized water and the solution was placed in an ice water bath. An amount of 13.3 g of NaOH was then added into the solution with stirring to form a Cu(OH)2 precipitate. The obtained precipitate was filtered and washed with deionized water and ethanol three times, and then dried in a vacuum oven at 80 °C overnight to obtain Cu(OH)2 NWBs.
Secondly, the Cu(OH)2 NWB was calcined at 200 °C for 2 h in air to obtain CuO nanowire bundles (CuO NWBs). An amount of 10 mg of CuO NWB was mixed with 600 μL of 0.5 wt% Nafion ionomer solution and sonicated for 30 min to form a uniform slurry ink. Then, the CuO-NWB-loaded working electrode was obtained via loading 30 μL of slurry ink onto 1 × 1 cm2 carbon paper (0.5 mg cm−2) and dried at 40 °C for 12 h in a vacuum oven.
Finally, the OD-Cu NWB was formed by in situ electroreduction of CuO NWBs on the working electrode in a home-made H-cell. A pre-reduction potential of −1.2 V vs. RHE (reversible hydrogen electrode) was applied to the working electrode in CO2-saturated 0.1 M KHCO3 solutions (pH 6.8) for 10 min to obtain the OD-Cu NWB.
For comparison, commercial Cu powders purchased from Xiangtian Nanomaterials Co., Ltd. (Shanghai, China) were also loaded onto the carbon paper and subjected to the same pre-reduction procedure as the reference sample.

3.3. Characterization and Electrochemical Measurements

A SUPRRATM 55 scanning electron microscope (SEM) (Zeiss, Oberkochen, German) was used to observe the surface morphologies of the aforementioned samples with an accelerating voltage of 5.0 kV. An Ultima 4 X-ray diffractometer (XRD) (Rigaku, Tokyo, Japan) was employed to investigate the sample structures from 5° to 90° with a scanning speed of 2° min−1 at 40 kV and 40 mA using a Cu Kα radiation source (λ = 1.54056 Å). A VMP3 potentiostat (Biologic, Seyssinet-Pariset, France) was employed to conduct electrochemical measurements in a home-made H-cell. The quartz glass electrolysis cell comprises two symmetrical compartments separated by a Nafion 117 membrane and is equipped with an Ag/AgCl reference electrode (KCl saturated) as well as a platinum wire counter electrode. For electrochemical measurements, the electrolysis cell was filled with 30 mL of 0.1 M KHCO3 solutions (pH 6.8) in each chamber and 10 mL·min−1 CO2 was supplied to the cathode side continuously. The current densities were normalized to the geometrical electrode area of 1 cm−2, and the potentials recorded versus the Ag/AgCl electrode were converted to versus RHE.

3.4. Product Quantifications and Calculations

Gas phase hydrocarbons, CO and H2 were tested via an online GC-2014 gas chromatograph (Shimadzu, Kyoto, Japan) using a Shincarbon ST80/100 column and a Porapak-Q80/100 column. Liquid phase alcohols and aldehydes were analyzed using an offline capillary column (GC-2014) via a Supelco OVI-G43 headspace injector (Merck, Darmstadt, German), while nuclear magnetic resonance (NMR) was used to quantify organic acids via a JNM-ECZ500R (JEOL, Tokyo, Japan). All faradaic efficiencies (FEi, %) reported were based on at least three different tests and calculated as follows:
F E i ( g a s ) = α i × c i × v × F × t / Q × 100 %
F E i ( l i q u i d ) = α i × c i × V × F / Q × 100 %
where αi is the number of electrons transferred to form the corresponding reduction product i, ci (mol∙L−1) is the concentration of the reduction product i, v (L∙h−1) is the CO2 flow rate, V (L) is the catholyte volume, F is the Faraday constant (96485 C∙mol−1), t (h) is the length of reaction and Q (C) is the amount of charge transferred during the electrochemical reaction at each applied potential.

4. Conclusions

In summary, a facile strategy was adopted to synthesize OD-Cu NWBs with a good structural stability during electroreduction for an efficient CO2ERR towards C2+ production. Detailed studies conducted on the effects of the precipitation/calcination temperature and per-reduction potential on the formation of nanowire bundles and their corresponding CO2ERR performance revealed that a relatively low precipitation temperature of 0 °C and a calcination temperature of 200 °C contribute to the formation of well-ordered nanowire bundles of OD-Cu, leading to preferable C2+ production kinetics. The well-preserved nanowire bundle morphology of the OD-Cu NWB after per-reduction not only promotes CO2ERR activity but also facilitates the C-C coupling of key intermediates to form C2+ products. Moreover, the oxide-derived Cu essence of the OD-Cu NWB with stabilized Cu+ species can be linked to the elevated CO2ERR performance toward C2+ production. In addition, this work provides insights into the relationship between hydrocarbon formation and the nanowire bundle morphology, presenting an inspiration for high-value-product-targeted CO2ERR catalyst designs.

Supplementary Materials

The following supporting information can be downloaded at: https://www.mdpi.com/article/10.3390/catal13091278/s1. Figure S1: Raman structural characterization of the Cu(OH)2 NWB, CuO NWB and OD-Cu NWB samples. Figure S2: The electrochemically active surface areas of (a) Cu powder and (b) as-prepared OD-Cu NWB, which were determined by measuring the double-layer capacitance (Cdl), derived from the cyclic voltammetry curves at scan rates of 5, 10, 20, 50, 80 and 100 mV s−1. Figure S3: Cyclic voltammograms of OD-Cu NWB in 0.1 M KHCO3 with Ar or CO2. Figure S4: Recycling performance stability of the OD-Cu NWB electrode at −1.4 V vs. RHE. Figure S5: XPS and Auger spectra of the Cu NWB catalyst before and after electrocatalytic reaction. Figure S6: Effects of precipitation temperature on bulk structures of CuO NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C. Figure S7: Effects of precipitation temperature on current densities of CO2ERR performance over OD-Cu NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C. Figure S8: Effects of calcination temperature on bulk structures of CuO NWBs calcinated at 200 °C, 300 °C, 400 °C and 500 °C. Figure S9: Effects of calcination temperature on current densities of CO2ERR performance over OD-Cu NWBs calcinated at 200 °C, 300 °C, 400 °C and 500 °C. Figure S10: Effects of per-reduction potentials on current densities of CO2ERR performance over OD-Cu NWBs per-reduced at −0.8 V, −1.0 V, −1.2 V and −1.4 V. Table S1: C2+ production performances over Cu NW-based catalysts reported in the literature.

Author Contributions

Conceptualization, X.D.; investigation, D.X. and M.W.; resources, W.W. and W.C.; data curation, D.X., M.W., Y.H., Y.G., G.W., L.Y., Y.L., T.G., S.L. and X.D.; writing—original draft preparation, D.X.; writing—review and editing, M.W., T.G. and X.D.; supervision, T.G., W.W., W.C. and X.D. All authors have read and agreed to the published version of the manuscript.

Funding

This work was financially supported by CHN Energy Investment Group Co., Ltd. (GJNY-21-51; GJNY-22-99; XNYY-ZC-2023-31); Shanghai Excellent Principal Investigator (No. 23XD1404400); the Foundation of Key Laboratory of Low-Carbon Conversion Science & Engineering, Shanghai Advanced Research Institute, Chinese Academy of Sciences (No. KLLCCSE-202207Z, SARI, CAS).

Data Availability Statement

The data presented in this study are available on request from the corresponding author.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. Preparation procedures and SEM images/XRD patterns of (a) Cu(OH)2 NWB, (b) CuO NWB and (c) OD-Cu NWB.
Figure 1. Preparation procedures and SEM images/XRD patterns of (a) Cu(OH)2 NWB, (b) CuO NWB and (c) OD-Cu NWB.
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Figure 3. Effects of precipitation temperature on the morphology of OD-Cu NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C.
Figure 3. Effects of precipitation temperature on the morphology of OD-Cu NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C.
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Figure 4. Effects of precipitation temperature on CO2ERR performance for OD-Cu NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C, including faradaic efficiencies for each reduction product and for C1/C2/C3 products.
Figure 4. Effects of precipitation temperature on CO2ERR performance for OD-Cu NWBs precipitated at (a) 0 °C, (b) 20 °C, (c) 40 °C and (d) 60 °C, including faradaic efficiencies for each reduction product and for C1/C2/C3 products.
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Figure 5. Effects of the calcination temperature on morphology for OD-Cu NWBs calcinated at (a) 200 °C, (b) 300 °C, (c) 400 °C and (d) 500 °C.
Figure 5. Effects of the calcination temperature on morphology for OD-Cu NWBs calcinated at (a) 200 °C, (b) 300 °C, (c) 400 °C and (d) 500 °C.
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Figure 6. Effects of calcination temperature on CO2ERR performance for OD-Cu NWBs calcinated at (a) 200 °C, (b) 300 °C, (c) 400 °C and (d) 500 °C, including faradaic efficiencies for each reduction product and for C1/C2/C3 products.
Figure 6. Effects of calcination temperature on CO2ERR performance for OD-Cu NWBs calcinated at (a) 200 °C, (b) 300 °C, (c) 400 °C and (d) 500 °C, including faradaic efficiencies for each reduction product and for C1/C2/C3 products.
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Figure 7. Effects of per-reduction potentials on the morphology, composition and CO2ERR performance of OD-Cu NWBs. SEM images of OD-Cu NWBs per-reduced at (a) −0.8 V, (b) −1.0 V, (c) −1.2 V and (d) −1.4 V. (e) XRD patterns, as well as faradaic efficiencies (at the working potential of −1.4 V) for (f) each reduction product and for (g) C1/C2/C3 products of these OD-Cu NWB catalysts.
Figure 7. Effects of per-reduction potentials on the morphology, composition and CO2ERR performance of OD-Cu NWBs. SEM images of OD-Cu NWBs per-reduced at (a) −0.8 V, (b) −1.0 V, (c) −1.2 V and (d) −1.4 V. (e) XRD patterns, as well as faradaic efficiencies (at the working potential of −1.4 V) for (f) each reduction product and for (g) C1/C2/C3 products of these OD-Cu NWB catalysts.
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MDPI and ACS Style

Xu, D.; Wu, M.; Huang, Y.; Gu, Y.; Wang, G.; Yang, L.; Liu, Y.; Gao, T.; Li, S.; Wei, W.; et al. Oxide-Derived Copper Nanowire Bundles for Efficient CO2 Reduction to Multi-Carbon Products. Catalysts 2023, 13, 1278. https://doi.org/10.3390/catal13091278

AMA Style

Xu D, Wu M, Huang Y, Gu Y, Wang G, Yang L, Liu Y, Gao T, Li S, Wei W, et al. Oxide-Derived Copper Nanowire Bundles for Efficient CO2 Reduction to Multi-Carbon Products. Catalysts. 2023; 13(9):1278. https://doi.org/10.3390/catal13091278

Chicago/Turabian Style

Xu, Dong, Minfang Wu, Yan Huang, Yongzheng Gu, Guiwen Wang, Long Yang, Yongping Liu, Tengfei Gao, Shoujie Li, Wei Wei, and et al. 2023. "Oxide-Derived Copper Nanowire Bundles for Efficient CO2 Reduction to Multi-Carbon Products" Catalysts 13, no. 9: 1278. https://doi.org/10.3390/catal13091278

APA Style

Xu, D., Wu, M., Huang, Y., Gu, Y., Wang, G., Yang, L., Liu, Y., Gao, T., Li, S., Wei, W., Chen, W., & Dong, X. (2023). Oxide-Derived Copper Nanowire Bundles for Efficient CO2 Reduction to Multi-Carbon Products. Catalysts, 13(9), 1278. https://doi.org/10.3390/catal13091278

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