C ₆₀ Fullerene as the Active Site for CO ₂ Electroreduction

Abstract

Abstract Fullerene (C 60 ) was considered as a catalyst promoter in various electrochemical reactions, yet its catalytic role in enhancing catalytic performance beyond electron transfer remains a puzzle to chemists. Traditional simulations imply C 60 ’s inertness in CO 2 reduction reaction (CO 2 RR) due to weak interaction with COOH* intermediates. Here, according to a pH‐field coupled microkinetic model at reversible hydrogen electrode (RHE) scale, we demonstrate that C 60 acts as molecular active sites to facilitate the CO 2 RR toward CO through a strong binding to COOH* in the electrochemical conditions. This binding is mainly due to the unique structure of C 60 that induces large dipole moment changes to stabilize COOH* intermediates across different pH conditions. By detailed comparison of experimental CO 2 RR observations and quantitative pH‐dependent modeling, this work provides new insights on C 60 ‐based catalysts, highlighting the large dipole moment change upon adsorption at curved surfaces should not be dismissed when analyzing the pH‐dependent binding strength and electrocatalytic activity.