Adjusting Local CO Confinement in Porous-Shell Ag@Cu Catalysts for Enhancing C-C Coupling toward CO2 Eletroreduction

Tuning the local confinement of reaction intermediates is of pivotal significance to promote C-C coupling for enhancing the selectivity for multicarbon (C2+) products toward CO2 electroreduction. Herein, we have gained insights into the confinement effect of local CO concentration for enhanced C-C coupling over core-shell Ag@Cu catalysts by tuning the pore diameters within porous Cu shells. During CO2 electroreduction, the core-shell Ag@Cu catalysts with an average pore diameter of 4.9 nm within the Cu shells (Ag@Cu-p4.9) exhibited the highest Faradaic efficiency of 73.7% for C2+ products at 300 mA cm(-2) among the three Ag@Cu catalysts. Finite-element-method simulations revealed that the pores with a diameter of 4.9 nm in Cu conspicuously enhanced the local CO concentration. On the basis of in situ attenuated total reflection surface-enhanced infrared absorption spectroscopy measurements, Ag@Cu-p4.9 exhibited the highest surface coverage of adsorbed CO intermediates with a linear adsorption configuration due to the confinement effect, thus facilitating C-C coupling.

Automated summary

The study focused on tuning the local confinement of CO concentration within Cu shells to enhance C-C coupling over Ag@Cu core-shell catalysts, leading to increased selectivity for C2+ products during CO2 electroreduction. The catalyst with an average pore diameter of 4.9 nm exhibited the highest Faradaic efficiency for C2+ products at 300 mA cm(-2) due to the enhanced local CO concentration and linear adsorption configuration of CO intermediates facilitated by the confinement effect.