Highly selective CO2-to-CO electroreduction on multisite coordinated single-atom-modified atomic cluster Cu-based catalyst

doi:10.1016/S1872-2067(23)64632-7

Abstract

Abstract:

Metal single-atom/atomic cluster catalysts (SA/AC) have emerged as effective electrocatalysts for the CO₂ reduction reaction (CO₂RR) due to their high metal atom utilization and controllable metal coordination environments. However, the designing and tuning of the local electronic environments of SA/AC ensembles remain a significant challenge. In this work, we develop a single-atom-modified atomic cluster copper catalyst (Cu SA/ACs) for CO₂RR. The SA/AC-induced modulation of the local electronic structure enhances CO₂ adsorption on the atomic cluster; additionally, the atomic cluster provides abundant active hydrogen for CO₂ protonation by mediating hydrolysis dissociation on the SAs. Consequently, compared to copper single-atom catalysts (Cu SACs), the Cu SA/ACs exhibit significantly improved activity, the current is 3.6 times that of Cu SACs, and the Faradaic efficiency of CO rose from 27.15% to 98.94%. The Cu SA/ACs catalyst can efficiently reduce CO₂ to CO in flow-cell configuration, and the CO selectivity is 93.06% at a current density of 600 mA cm^-2. The maximum energy efficiency of the cathode is 61.9%, which is superior to that of most CO₂-to-CO catalysts. This work provides a new perspective for developing efficient SA/AC catalysts.

Key words: CO₂ reduction reaction, Active site synergism, Single atom, Atomic cluster, Electrocatalysis

Chaochen Wang, Wangxin Ge, Lei Tang, Yanbin Qi, Lei Dong, Hongliang Jiang, Jianhua Shen, Yihua Zhu, Chunzhong Li. Highly selective CO₂-to-CO electroreduction on multisite coordinated single-atom-modified atomic cluster Cu-based catalyst[J]. Chinese Journal of Catalysis, 2024, 59: 324-333.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64632-7

https://www.cjcatal.com/EN/Y2024/V59/I4/324

Figures/Tables 4

Fig. 1. (a) Schematic diagram of the preparation process of Cu SA/ACs. (b) SEM images of Cu SA/ACs. (c) Aberration-corrected HRTEM of Cu SA/SCs. (d-g) Atomic-resolution EDS mapping images of various elements. (h) Cu K edge XANES spectra of Cu foil, CuO, CuPc (copper(II) phthalocyanine), Cu2O, and Cu SA/ACs. (i) Fourier transforms (FT) of k3-weighted Cu K edge EXAFS experimental data for Cu foil, CuO, CuPc, Cu2O, and Cu SA/ACs. (j) Wavelet transform (WT) plot of Cu SA/ACs.

Fig. 2. (a) LSV curves acquired in CO2-saturated (red line) or Ar-saturated (grey line) 0.5 mol L-1 KHCO3 electrolyte. (b) Faraday efficiency of products obtained using Cu SA/ACs in CO2-saturated 0.5 mol L-1 KHCO3 electrolyte. (c) Faraday efficiency of CO obtained using Cu SA/ACs, Cu SACs, NC, and Cu NPs in CO2-saturated 0.5 mol L-1 KHCO3 electrolyte. (d) Partial current densities of CO obtained using Cu SA/ACs, Cu SACs, NC, and Cu NPs in CO2-saturated 0.5 mol L-1 KHCO3 electrolyte. (e) TOF of Cu SA/ACs, Cu SACs and Cu NPs. (f) Summary of the electrocatalytic performances Cu SACs and Cu clusters reported in the literature. Related references are given in the Supporting Information. (g) Long-term Cu SA/ACs stability in electrocatalytic CO2 reduction at -0.4 V versus RHE.

Fig. 3. (a) CO and H2 Faradaic efficiencies of the Cu SA/ACs catalyst in the current density range of 100 to 800 mA cm-2 in the flow cell. (b) Long-term electrolysis under a current density of 200 mA cm-2 in the flow cell. (c) Cathodic energy efficiency of the Cu SA/ACs catalyst in the flow cell (voltages are not iR-corrected) (d) In-situ ATR-SEIRAS spectra of Cu SA/ACs in the range 1200-2150 cm-1 at different potentials. (e) In-situ ATR-SEIRAS spectra of Cu SACs in the range of 1200-2150 cm-1 at varying potentials. (f) Schematic diagram of the improved effect of electric field enhancement on the Cu SA/ACs and Cu SACs catalysts.

Fig. 4. Differential charge density analysis of Cu ACs (a), Cu SA/ACs (b), and Cu SACs (c). (d) PDOS of Cu SA/ACs, Cu SACs and Cu ACs. (e) Gibbs free energy diagrams for the CO2RR on the Cu SA/ACs. (f) Comparison of Gibbs free energy changes during the CO2RR on Cu SA/ACs, Cu SACs, and Cu NPs.

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Highly selective CO₂-to-CO electroreduction on multisite coordinated single-atom-modified atomic cluster Cu-based catalyst

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