Geometric Modulation of Local CO Flux in Ag@Cu2O Nanoreactors for Steering the CO2RR Pathway toward High‐Efficacy Methane Production

Abstract The electroreduction of carbon dioxide (CO 2 RR) to CH 4 stands as one of the promising paths for resourceful CO 2 utilization in meeting the imminent “carbon‐neutral” goal of the near future. Yet, limited success has been witnessed in the development of high‐efficiency catalysts imparting satisfactory methane selectivity at a commercially viable current density. Herein, a unique category of CO 2 RR catalysts is fabricated with the yolk–shell nanocell structure, comprising an Ag core and a Cu 2 O shell that resembles the tandem nanoreactor. By fixing the Ag core and tuning the Cu 2 O envelope size, the CO flux arriving at the oxide‐derived Cu shell can be regulated, which further modulates the *CO coverage and *H adsorption at the Cu surface, consequently steering the CO 2 RR pathway. Density functional theory simulations show that lower CO coverage favors methane formation via stabilizing the intermediate *CHO. As a result, the best catalyst in the flow cell shows a high CH 4 Faraday efficiency of 74 ± 2% and partial current density of 178 ± 5 mA cm − 2 at −1.2 V RHE , ranking above the state‐of‐the‐art catalysts reported today for methane production. These findings mark the significance of precision synthesis in tailoring the catalyst geometry for achieving desired CO 2 RR performance.