(544b) Computationally Aided Design of Two-Dimensional Composites As Alternatives to Metallic Copper for Catalyzing the Carbon Dioxide Reduction Reaction

In the present study, we performed the computationally aided design of a series of candidates for electrochemical catalysts that are potential alternatives to metallic copper for the carbon dioxide reduction reactions (CO₂RR) that lead to multi-carbon species. These catalysts were formulated as supported copper−nonmetal composites where small copper clusters were incorporated into the defects of the selected two-dimensional nonmetallic materials with graphene-like structures, with the aim of achieving higher efficiency and stronger selectivity compared to the pristine metallic copper. CO₂ molecules were adsorbed on the non-metallic parts of these materials and transported to the copper clusters, where they were catalytically reduced to multi-carbon molecules through carbon−carbon (C−C) coupling reactions. Using a combination of density functional theory, basic statistical mechanics, and the classical linearized Poisson−Boltzmann model [J. D. Goodpaster, A. T. Bell, and M. Head-Gordon, J. Phys. Chem. Lett. 2016, 7, 1471], we constructed a chemical reaction network that includes all thermodynamically and kinetically viable surface reaction paths in the presence of the solvent, electrolyte, and applied electric potential, starting from the adsorption of CO₂ and ending with the production of two-carbon (C₂) [A. J. Garza, A. T. Bell, and M. Head-Gordon, ACS Catal. 2018, 8, 1490] and three-carbon (C₃) molecules. Based on this information, we were able to predict the efficiency and selectivity of our designed materials and to propose potential candidates for follow-up experimental measurements.