The Role of Atomic Carbon in Directing Electrochemical CO(2) Reduction to Multicarbon Products

Electrochemical reduction of carbon-dioxide/carbon-monoxide (CO (2) R) to fuels and chemicals presents an attractive approach for sustainable chemical synthesis, but also poses a serious challenge in catalysis. Understanding the key aspects that guide CO (2) R towards value-added multicarbon (C 2+ ) products is imperative in designing an efficient catalyst. Herein, we identify the critical steps toward C 2 products on copper through a combination of energetics from density functional theory and micro-kinetic modeling. We elucidate the importance of atomic carbon in directing C 2+ selectivity and how it introduces surface structural sensitivity on copper catalysts. This insight enables us to propose two simple thermodynamic descriptors that effectively describe C 2+ selectivity on metal catalysts beyond copper and hence it identifies an intelligible protocol to screen for materials that selectively catalyze CO (2) to C 2+ products.