Restraining Interfacial Cu2+ by using Amorphous SnO2 as Sacrificial Protection Boosts CO2 Electroreduction.

Abstract

The electrochemical carbon dioxide reduction reaction (CO2 RR) to formate is of great interest in the field of electrochemical energy. Cu-based material is an appealing electrocatalyst for the CO2 RR. However, retaining Cu2+ under the high cathodic potential of CO2 RR remains a great challenge, leading to low electrocatalytic selectivity, activity, and stability. Herein, inspired by corrosion science, a sacrificial protection strategy to stabilize interfacial crystalline CuO through embedding of active amorphous SnO2 (c-CuO/a-SnO2 ) is reported, which greatly boosts the electrocatalytic sensitivity, activity, and stability for CO2 RR to formate. The as-made hybrid catalyst can achieve superior high selectivity for CO2 RR to formate with a remarkable Faradaic efficiency (FE) of 96.7%, and a superhigh current density of over 1 A cm-2 that far outperforms industrial benchmarks (FE > 90%, current density > 300mA cm-2 ). In situ X-ray absorption spectroscopy (XAS) and X-ray diffractionexperimental and theoretical calculation results reveal that the broadened s-orbital in interfacial a-SnO2 offers the lower orbital for extra electrons than Cu2+ , which can effectively retain nearby Cu2+ , and the high active interface significantly lowers the energy barrier of the limited step (* CO2 → * HCOO) and enhances the selectivity and activity for CO2 RR to formate.