Rich Bismuth‐Oxygen Bonds in Bismuth Derivatives from Bi2S3 Pre‐Catalysts Promote the Electrochemical Reduction of CO2

Abstract The greenhouse effect and climate change caused by carbon dioxide (CO 2 ) have become global challenges. Electrochemical reduction is one of the most promising paths to convert CO 2 into a feedstock such as formate for the synthesis of value‐added chemicals and fuels. We first performed theoretical calculations to predict the activity of bismuth oxide (Bi 2 O 3 ) for CO 2 electroreduction. The analysis of the reaction energetics indicates that the increased number of Bi−O bonds lowers the formation energy of the key *OCHO intermediate, and thus improves the production of formate. The Bi/Bi 2 O 3 electrocatalyst rich in Bi−O bonds was experimentally prepared from a nanorod‐like Bi 2 S 3 pre‐catalyst, which shows electrocatalytic activity to generate formate with a Faradaic efficiency of over 80 % at −1.0 V vs. the reversible hydrogen electrode (RHE) and durability for more than 20 h. This research opens up avenues for the rational design of selective Bi‐based CO 2 ‐to‐formate electrocatalysts.