Electrocatalytic reduction of CO2 with enhanced C2 liquid products activity by the synergistic effect of Cu single atoms and oxygen vacancies

doi:10.1016/S1872-2067(23)64587-5

Abstract

Abstract:

Electrochemical conversion of CO₂ to high energy density multi-carbon liquid phase fuels such as ethanol offers a promising strategy to realize carbon neutrality. However, the selectivity of value-added C₂ liquid products is still deemed unsatisfactory currently due to the high overpotential, poor selectivity, and the difficulty of the C-C coupling process. Herein, we report that Cu single atoms (SAs) on hydrogen reduced UIO66-NH₂ (named Cu SAs/UIO-H₂) achieve C₂ liquid products Faraday efficiency (FE) of 58.62% and ethanol FE of 46.28% at a low potential of -0.66 V versus the reversible hydrogen electrode. The ethanol FE of Cu SAs/UIO-H₂ is 9.61 times higher than UIO66-NH₂. Moreover, the experimental results and theoretical calculations demonstrate that Cu SAs and oxygen vacancies (OVs) synergistically promote the generation of *HCCOH intermediate, thus accelerating the formation of ethanol. This work offers deeper understanding at the atomic scale for designing high-performance electrocatalysts for CO₂conversion to valuable liquid fuels.

Key words: Cu single atoms catalyst, Oxygen vacancies, Electrocatalysis, CO₂ conversion, Ethanol synthesis

Quanquan Bie, Haibo Yin, Yunlong Wang, Haiwei Su, Yue Peng, Junhua Li. Electrocatalytic reduction of CO₂ with enhanced C₂ liquid products activity by the synergistic effect of Cu single atoms and oxygen vacancies[J]. Chinese Journal of Catalysis, 2024, 57: 96-104.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64587-5

https://www.cjcatal.com/EN/Y2024/V57/I2/96

Figures/Tables 4

Fig. 1. (a) Synthesis process of Cu SAs/UIO-H2. Cu (green), Zr (blue), N (light blue), C (gray), O (red), H (pink). HAADF-STEM (b,c) and high-resolution HAADF-STEM (d) images of Cu SAs/UIO-H2. Cu SAs are highlighted with yellow circles. (e) TEM image and EDS mappings of Cu SAs/UIO-H2.

Fig. 2. XANES (a) and FT-EXAFS (b) spectra of Cu SAs/UIO-H2, Cu SAs/UIO, and reference samples (Cu foil, CuO and Cu2O) at Cu K-edge. WT-EXAFS spectra of CuO (c), Cu2O (d), Cu foil (e), Cu SAs/UIO (f) and Cu SAs/UIO-H2 (g). EXAFS fitting curves of Cu SAs/UIO-H2 at R-space (h) and K-space (i).

Fig. 3. (a) LSV curves of Cu SAs/UIO-H2, Cu SAs/UIO, UIO-H2 and UIO. FEs of CO2RR products of Cu SAs/UIO (b), UIO-H2 (c), and Cu SAs/UIO-H2 (d) at different potentials, respectively. (e) Comparison of FE and activities between Cu SAs/UIO-H2 and Cu-based catalysts for CO2RR to C2H5OH. (f) Stability test and the FEs of C2H5OH over Cu SAs/UIO-H2 at -0.66 V (vs. RHE) for 12 h.

Fig. 4. (a) Time-dependent in-situ DRIFTS spectra of Cu SAs/UIO-H2 for CO2RR in KHCO3 electrolyte from 2 to 90 min. (b) Calculated activation energy for CO2-to-C2H5OH and HER. (c) Schematic pathway of the CO2RR process toward ethanol synthesis. (d) Calculated free energy diagram of CO2 reduction to intermediates over the samples.

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Electrocatalytic reduction of CO₂ with enhanced C₂ liquid products activity by the synergistic effect of Cu single atoms and oxygen vacancies

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