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

Lin, Z., University of California - Berkeley
Jiang, K., Rowland Institute at Harvard, Harvard University
Garza, A. J., The Dow Chemical Company
Bell, A. T., University of California
Head-Gordon, M., University of California - Berkeley
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.