(738c) Tuning CO2 Reduction over Single Rh Atom on Fe3O4(001) Via Surface Hydroxylation
Searching for the catalytic reductive transformation of carbon oxides (CO, CO2) into value-added chemicals, has always been of broad interest due to the need to meet global energy demand and to decrease greenhouse gas emission. Single metal atoms are rapidly emerging as a new family of promising catalysts, demonstrating remarkable performance towards hydrogenation, water-gas shift, oxidation and other industrially essential reactions. In this study, we provide mechanistic insights into CO2 reduction over single Rh atom supported on Fe3O4(001) using density functional theory (DFT) calculations. Single Rh atom is determined to be positioned at the under-coordinated octahedral positions of Fe3O4 surface. A structural accuracy of surface DFT models is confirmed by simulating the extended X-ray absorption fine structure (EXAFS) and comparing the theoretical spectra against the experimental spectra. Importantly, the level of surface hydroxylation on Fe3O4(001) is found to be a key to stabilize the important reaction intermediates to maintain CO2 reduction cycle.