Density functional theory and 3D-RISM-KH molecular theory of solvation studies of CO2 reduction on Cu-, Cu2O-, Fe-, and Fe3O4-based nanocatalysts

Abstract

Using OpenMX quantum chemistry software for self-consistent field calculations of electronic structure with geometry optimization and 3D-RISM-KH molecular theory of solvation for 3D site distribution functions and solvation free energy, we modeled the reduction of CO₂+H₂ in ambient aqueous electrolyte solution of 1.0-M KH₂PO₄ into (i) formic acid HCOOH and (ii) CO H₂O on the surfaces of Cu-, Fe-, Cu₂O-, and Fe₃O₄-based nanocatalysts. It is applicable to its further reduction to hydrocarbons. The optimized geometries and free energies were obtained for the pathways of adsorption of the reactants from the solution, successive reduction on the surfaces of the nanocatalysts, and then release back to the solution bulk.

Keywords: 3D-RISM-KH molecular theory of solvation; CO2 reduction to HCOOH, CO; Cu, Cu2O, Fe, Fe3O4 nanocatalysts; KH2PO4 ambient aqueous solution; OpenMX quantum chemistry.