Probing the Local Environment of Active Sites during 2-Propanol Oxidation to Acetone on the Co₃O₄ (001) Surface: Insights from First-Principles O K-Edge XANES Spectroscopy

We use theoretical X-ray absorption near-edge spectroscopy (XANES) to investigate the electronic structure of active sites on Co3O4 (001) surface during 2-propanol oxidation acetone in humid conditions. In gas phase, O K-edge spectra and acetone, as well that 2-propoxide considered a reaction intermediate, present no pre-edge peaks. Upon adsorption at Co site surface, spectrum presents distinct peak preceded by bump region, both due dipole transitions from 1s 2p states hybridized with 3d empty states. The formation leads two peaks increase A further increment these is observed when formed rather ascribed new contributions carbon occurring region. changes along were correlated configuration hybridization cobalt atom directly bonded alcohol. variation electron densities was also monitored for all atoms including ones which molecular water dissociated are adsorbed. PDOS analysis crystal field theory showed does not change state +3, while OH groups have an +4. Löwdin charges shows pronounced cooperative effects between last step corresponds decomposition acetone.