Geometric Modulation of Local CO Flux in Ag@Cu 2 O Nanoreactors for Steering the CO 2 RR Pathway toward High-Efficacy Methane Production.

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.
(© 2021 Wiley-VCH GmbH.)