Steering electrochemical carbon dioxide reduction to alcohol production on Cu step sites

doi:10.1016/S1872-2067(23)64508-5

Abstract

Abstract:

Electrochemical CO₂ reduction is a sustainable method for producing multicarbon alcohols. However, the selectivity of alcohols is limited owing to the favorable side reaction to convert the key intermediate of *CH₂CHO into ethylene. This study describes the design of a Cu electrocatalyst with abundant step sites to suppress the deoxygenation of *CH₂CHO to ethylene, thereby promoting alcohol production. A Faradic efficiency of 40.5% and partial current density of 56.3 mA/cm² for alcohols are achieved. Moreover, the alcohols/C₂H₄ ratio in the products reaches approximately 2.2. In-situ infrared spectrum characterizations and theoretical calculations reveal that the step sites facilitate C-C coupling and direct the reaction pathway to promote the formation of alcohols by inhibiting the cleavage of the C-O bond in *CH₂CHO. Therefore, the proposed strategy is efficient for designing active sites to steer reaction pathways in CO₂ electroreductions and produce alcohols.

Key words: Electrocatalysis, CO₂ reduction, Copper, Step sites, Alcohol

Hui Gao, Gong Zhang, Dongfang Cheng, Yongtao Wang, Jing Zhao, Xiaozhi Li, Xiaowei Du, Zhi-Jian Zhao, Tuo Wang, Peng Zhang, Jinlong Gong. Steering electrochemical carbon dioxide reduction to alcohol production on Cu step sites[J]. Chinese Journal of Catalysis, 2023, 52: 187-195.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(23)64508-5

https://www.cjcatal.com/EN/Y2023/V52/I9/187

Figures/Tables 4

Fig. 1. Characterization of COD-Cu and HOD-Cu. (a) XRD patterns of CuO, COD-Cu, and HOD-Cu. (b) In-situ Raman spectra of COD-Cu under different potentials. SEM images of HOD-Cu (c) and COD-Cu (d). TEM images of HOD-Cu (e) and COD-Cu (f). (g) ATR-SEFTIRS characterization of COD-Cu under different potentials with peak fitting results.

Fig. 2. Electrochemical CO2RR performance of COD-Cu. (a) Products distributions between -1.4 and -0.8 V in 1.0 mol/L KOH. (b) Faradic efficiency of EtOH and n-PrOH. (c) Partial current density of EtOH and n-PrOH. (d) Alcohols/C2H4 ratio of COD-Cu in the potential range between -1.4 and -0.8 V. (e) Stability test in 1.0 mol/L KOH at -1.1 V. (Color should be used in print).

Fig. 3. In-situ ATR-SEFTIRAS spectroscopic investigations. In-situ ATR-SEFTIRAS spectra of COD-Cu (a) and HOD-Cu (b) under different potentials. (c) Correlation between wavenumbers of *COL with respect to the applied potential for COD-Cu and HOD-Cu. In-situ ATR-SEFTIRAS spectra of COD-Cu (d) and HOD-Cu (e) in Ar gas purge experiment. (f) Relative area of the peak corresponding to *COL as a function of purge duration for COD-Cu and HOD-Cu.

Fig. 4. Correlation between alcohol selectivity and ratio of step sites. (a) Peak fitting results of *COL at -0.4 V for COD-Cu after annealing treatments at different temperatures. (b) Linear relationship between Faradic efficiency of alcohols and step sites ratio. (c) Energy profile to form C2H4 (black line) and EtOH (red line) on Cu (100) without step sites and on Cu (211) with step sites.

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