Understanding the dynamic evolution of atomically dispersed Cu catalyst for CO2 electrochemical conversion using integrated XANES analysis and mechanistic studies

Direct electrochemical conversion of CO2 to ethanol (CH3CH2OH) offers a promising strategy to lower CO2 emission while storing energy from renewable electricity. Our recent study reported a carbon-supported atomically dispersed Cu catalyst that achieved the highest reported selectivity for CH3CH2OH formation (91%) at a relatively low potential (-0.6 V), however, the active site structure that is responsible for such high activity and selectivity has yet to be understood. In this paper, we demonstrate a computational investigation combining X-ray absorption near edge structure (XANES) simulations and a mechanistic study via density functional theory (DFT) to understand the catalyst structures of this Cu catalyst during electrocatalysis and the corresponding reaction mechanisms of the key products. An integrated computational and experimental XANES analysis depicted the dynamic evolution of the catalytic site during electrocatalysis. The as-prepared, atomically dispersed Cu catalyst aggregates and forms metallic clusters/nanoparticles under electrochemical condition, which then break down to smaller oxidized clusters after electrocatalysis. The formed Cu clusters/nanoparticles showed distinct catalytic activity and selectivity as a function of particle size based on the mechanistic investigation using DFT, which is consistent with experimental observations for catalyst samples with different Cu loadings. This comprehensive study which combines experimental and computational XANES investigation, mechanistic study via DFT calculations, and experimental performance of the catalysts, provides unprecedented dynamic and mechanistic insights into the supported atomically dispersed metal catalysts for CO2 reduction. Such strategy and details gained can further guide discovery of novel catalyst materials for CO2 electrochemical reduction.