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 > 300 mA 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.