(726h) Mechanistic Insights into Electrochemical CO(2) Reduction on Copper and Copper-Based Bimetallic Catalysts

Electrochemical carbon dioxide/monoxide (CO₂/CO) reduction is a potential candidate for sustainable energy conversion and storage. Copper (Cu)-based materials are the only catalysts capable of producing more reduced hydrocarbons and alcohols, yet the high overpotential and poor selectivity still remain a huge challenge, which require mechanistic insights into the reaction mechanism and active site identification. Here we present microkinetic studies for CO₍₂₎ reduction on different coppers facets with different terrace/step site ensembles based on energetics estimated from density functional theory (DFT) based models. Our microkinetic models unveils the key reaction steps and site identities that dictate the C₁/C₂/C₃ and hydrocarbon/oxygenate selectivity. The simulation gives reasonable agreement with the experimental observation and provides some theoretical insights into the design principles of practical Cu and Cu-based catalysts under reaction conditions.