Manipulating C-C coupling pathway in electrochemical CO2 reduction for selective ethylene and ethanol production over single-atom alloy catalyst

Manipulation C-C coupling pathway is of great importance for selective CO 2 electroreduction but remain challenging. Herein, two model Cu-based catalysts, by modifying Cu nanowires with Ag nanoparticles (AgCu NW) and Ag single atoms (Ag 1 Cu NW), respectively, are rationally designed for exploring the C-C coupling mechanisms in electrochemical CO 2 reduction reaction (CO 2 RR). Compared to AgCu NW, the Ag 1 Cu NW exhibits a more than 10-fold increase of C 2 selectivity in CO 2 reduction to ethanol, with ethanol-to-ethylene ratio increased from 0.41 over AgCu NW to 4.26 over Ag 1 Cu NW. Via a variety of o perando /in-situ techniques and theoretical calculation, the enhanced ethanol selectivity over Ag 1 Cu NW is attributed to the promoted H 2 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 2+ product and shed light on the rational design of efficient CO 2 RR catalysts with paired active sites. Manipulating the carbon-carbon coupling pathway in CO 2 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.