Manipulating C-C coupling pathway in electrochemical CO<sub>2</sub> reduction for selective ethylene and ethanol production over single-atom alloy catalyst.

Wang, Shifu; Li, Fuhua; Zhao, Jian; Zeng, Yaqiong; Li, Yifan; Lin, Zih-Yi; Lee, Tsung-Ju; Liu, Shuhui et al. · Nat Commun · 2024

basic_science · Level V

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Abstract

Manipulation C-C coupling pathway is of great importance for selective CO<sub>2</sub> electroreduction but remain challenging. Herein, two model Cu-based catalysts, by modifying Cu nanowires with Ag nanoparticles (AgCu NW) and Ag single atoms (Ag<sub>1</sub>Cu NW), respectively, are rationally designed for exploring the C-C coupling mechanisms in electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). Compared to AgCu NW, the Ag<sub>1</sub>Cu NW exhibits a more than 10-fold increase of C<sub>2</sub> selectivity in CO<sub>2</sub> reduction to ethanol, with ethanol-to-ethylene ratio increased from 0.41 over AgCu NW to 4.26 over Ag<sub>1</sub>Cu NW. Via a variety of operando/in-situ techniques and theoretical calculation, the enhanced ethanol selectivity over Ag<sub>1</sub>Cu NW is attributed to the promoted H<sub>2</sub>O dissociation over the atomically dispersed Ag sites, which effectively accelerated *CO hydrogenation to form *CHO intermediate and facilitated asymmetric *CO-*CHO coupling over paired Cu atoms adjacent to single Ag atoms. Results of this work provide deep insight into the C-C coupling pathways towards target C<sub>2+</sub> product and shed light on the rational design of efficient CO<sub>2</sub>RR catalysts with paired active sites.