Bismuth Oxides with Enhanced Bismuth–Oxygen Structure for Efficient Electrochemical Reduction of Carbon Dioxide to Formate

Abstract

Electrochemical conversion of carbon dioxide (CO2) into high-value chemical products has become a dramatic research area because of the efficient exploitation of carbon resources and simultaneous reduction of atmospheric CO2 concentration. Herein, we report the bismuth-based catalyst in the efficient electroconversion of CO2 for the formation of formate with a maximum Faradaic efficiency of 91% and partial current density of ∼8 mA cm–2 at −0.9 V vs RHE. Experimental and theoretical results show that the bismuth–oxygen structure of bismuth oxides is beneficial for a higher adsorption of CO2 and the rate-determining route switching from the initial fast pre-equilibrium of electron transfer process to the subsequent hydrogenation step, accompanied by a lower free energy of intermediate. This work may offer valuable insights into crystal structure engineering to achieve efficient electrocatalysts for selective CO2 reduction toward generation of valuable products.