Electrochemically reconstructed perovskite with cooperative catalytic sites for CO2-to-formate conversion

Perovskites are the promising catalysts for various reactions, yet their structure evolutions and the composition-function relation in the carbon dioxide reduction reaction (CO2RR) are not fully explored. In this study, we report that the reconstructed BaBiO3 (BBO) perovskite is able to facilitate CO2-to-formate (FA) conversion by both A- (Ba) and B- (Bi) site elements through the cooperative but distinct catalytic mechanisms. Specifically, the electrochemical reductions of BBO trigger the complete rearrangement of atoms with rapid kinetics at catalytically relevant voltages, giving rise to electricity-induced Bi metallene (eBBO) that efficiently generates FA with high selectivity and partial current densities. Moreover, the reconstructed BBO simultaneously enables Ba2+ release to the electrolyte, and the time-resolved FTIR and in situ Raman analysis collectively reveal that the Ba2+ adsorption enables easier CO2 adsorption, thereby leading to enhanced CO2-to-FA conversion. This work is of direct significance in elucidating the cooperative catalysis between A- and B- site elements in perovskites for room-temperature CO2RR.