Manipulating C-C coupling pathway in electrochemical CO2 reduction for selective ethylene and ethanol production over single-atom alloy catalyst
Shifu Wang, Fuhua Li, Jian Zhao, Yaqiong Zeng, Yifan Li, Zih‐Yi Lin, Tsung-Ju Lee, Shu-Hui Liu, Xinyi Ren, Weijue Wang, Yusen Chen, Sung‐Fu Hung, Ying‐Rui Lu, Yi Cui, Xiaofeng Yang, Xuning Li, Yanqiang Huang, Bin Liu
Abstract
Manipulation C-C coupling pathway is of great importance for selective CO2 electroreduction but remain challenging. Herein, two model Cu-based catalysts, by modifying Cu nanowires with Ag nanoparticles (AgCu NW) and Ag single atoms (Ag1Cu NW), respectively, are rationally designed for exploring the C-C coupling mechanisms in electrochemical CO2 reduction reaction (CO2RR). Compared to AgCu NW, the Ag1Cu NW exhibits a more than 10-fold increase of C2 selectivity in CO2 reduction to ethanol, with ethanol-to-ethylene ratio increased from 0.41 over AgCu NW to 4.26 over Ag1Cu NW. Via a variety of operando/in-situ techniques and theoretical calculation, the enhanced ethanol selectivity over Ag1Cu NW is attributed to the promoted H2O 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 C2+ product and shed light on the rational design of efficient CO2RR catalysts with paired active sites. Manipulating the carbon-carbon coupling pathway in CO2 electroreduction is vital yet challenging. Here, by studying two model copper-based catalysts with distinct ethylene and ethanol selectivity, authors investigate the mechanistic origins for symmetric and asymmetric carbon-carbon coupling.