Electric-field promoted C-C coupling over Cu nanoneedles for CO2 electroreduction to C2 products

doi:10.1016/S1872-2067(21)63866-4

Abstract

Abstract:

Cu-based catalysts are the most promising candidates for electrochemical CO₂ reduction (CO₂RR) to multi-carbon (C₂) products. Optimizing the C-C coupling process, the rate-determining step for C₂ product generation, is an important strategy to improve the production and selectivity of the C₂ products. In this study, we determined that the local electric field can promote the C-C coupling reaction and enhance CO₂ electroreduction to C₂ products. First, finite-element simulations indicated that the high curvature of the Cu nanoneedles results in a large local electric field on their tips. Density functional theory (DFT) calculations proved that a large electric field can promote C-C coupling. Motivated by this prediction, we prepared a series of Cu catalysts with different curvatures. The Cu nanoneedles (NNs) exhibited the largest number of curvatures, followed by the Cu nanorods (NRs), and Cu nanoparticles (NPs). The Cu NNs contained the highest concentration of adsorbed K ⁺, which resulted in the highest local electric field on the needles. CO adsorption sensor tests indicated that the Cu NNs exhibited the strongest CO adsorption ability, and in-situ Fourier-transform infrared spectroscopy (FTIR) showed the strongest *COCO and *CO signals for the Cu NNs. These experimental results demonstrate that high-curvature nanoneedles can induce a large local electric field, thus promoting C-C coupling. As a result, the Cu NNs show a maximum FE_C2 of 44% for CO₂RR at a low potential (-0.6 V vs. RHE), which is approximately 2.2 times that of the Cu NPs. This work provides an effective strategy for enhancing the production of multi-carbon products during CO₂RR.

Key words: Electric-field effect, C-C coupling, Cu nanoneedle, C₂ products, CO₂ electroreduction

HuangJingWei Li, Huimin Zhou, Yajiao Zhou, Junhua Hu, Masahiro Miyauchi, Junwei Fu, Min Liu. Electric-field promoted C-C coupling over Cu nanoneedles for CO₂ electroreduction to C₂ products[J]. Chinese Journal of Catalysis, 2022, 43(2): 519-525.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63866-4

https://www.cjcatal.com/EN/Y2022/V43/I2/519

Figures/Tables 5

Fig. 1(a) shows the distribution of the electric field intensity on the surface of the Cu catalysts exhibiting different curvatures. The radii at the tips of the NNs, NRs, and NPs were set to 10, 50, and 150 nm, respectively. The corresponding electric field intensities (shown in Fig. 1(b)) at the tips of the Cu NNs, Cu NRs, and Cu NPs are 8.12, 5.36, and 2.01 kV/m, respectively. These results indicate that the Cu NNs, which are more curved, exhibit the strongest electric field.

Fig. 1. (a) Simulated electric field distribution on the surfaces of the Cu NNs, Cu NRs, and Cu NPs with different curvatures; (b) Electric field intensity at the tips of the Cu NNs, Cu NRs, and Cu NPs; (c) Simulated K+ concentrations at the tips of the Cu NNs, Cu NRs, and Cu NPs; (d) DFT calculated reaction barriers of the C-C coupling reaction on the surface of Cu(100) under different electric field intensities; (e) Schematic diagram of the C-C coupling reaction on the surface of Cu(100) with and without an applied electric field.

Fig. 2. (a) Schematic of the preparation process for the Cu-based catalysts with different curvatures; (b) XRD patterns of the Cu NPs, Cu NRs, and Cu NNs after electrochemical reduction at 10 mA cm-2 for 1000 s in a CO2-saturated solution; (c-e) Corresponding SEM images of the Cu NPs, Cu NRs, and Cu NNs; (f-h) Enlarged SEM images of the Cu NPs, Cu NRs, and Cu NNs.

Fig. 3. (a) The measured K+ concentration in the Cu NPs, Cu NRs, and Cu NNs; (b) The current density differences of the Cu NPs, Cu NRs, and Cu NNs under CO atmosphere and under vacuum at 0, 0.1, and 0.2 V; (c) The in-situ FTIR spectra of the Cu NNs, Cu NRs, and Cu NPs between 1540 and 1610 cm-1.

Fig. 4. (a) Product distribution of the Cu NNs, Cu NRs, and Cu NPs at -0.6 V vs. RHE; FEC2 (b) and current density (c) of the Cu NNs, Cu NRs, and Cu NPs at different potentials; (d) Stability test of the Cu NNs, Cu NRs, and Cu NPs at -0.6 V vs. RHE.

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Electric-field promoted C-C coupling over Cu nanoneedles for CO₂ electroreduction to C₂ products

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