Pietzsch, A.; Niskanen, J.; Vaz da Cruz, V.; Eckert, S.; Fondell, M.; Jay, R.; Lu, X.; McNally, D.; Schmitt, T.; Föhlisch, A.: Room Temperature Dehydrogenation of Gaseous Methanol over Polycrystalline Gold Triggered and Traced by Oxygen Kedge Xrays. The Journal of Physical Chemistry C early view (2025)
10.1021/acs.jpcc.4c06870
Open Accesn Version
Abstract:
The room temperature conversion of gaseous methanol to carbon monoxide and hydrogen on a polycrystalline Au film at ambient pressure has been triggered and characterized by oxygen K-edge excitation and vibrationally resolved resonant inelastic X-ray scattering. The rate-limiting first methanol dehydrogenation step is driven by ultrafast O–H dissociation and deprotonation of O K-edge excited CH3OH. The Au surface further dehydrogenates the CH3O+ photoradical created by X-rays via electron transfer from the Au surface. With vibrationally resolved resonant inelastic X-ray scattering, we trace the CO molecular potential energy surface along the C–O coordinate. The CO bond softens, and the C–O stretch frequency changes from 2250 to 2065 cm–1 at a CO chemisorption energy of 38–58 kJ/mol. This constitutes weak chemisorption as compared to the transition metals but also stronger bonding than the physisorbed CO species on single-crystal Au surfaces. In liquid methanol, the recombination of the CH3O+ photoradical created by X-rays with protons quenches this conversion