RESUMEN
Polymeric carbon nitride (PCN) is a promising class of materials for solar-to-chemical energy conversion. The increase of the photocatalytic activity of PCN is often achieved by the incorporation of heteroatoms, whose impact on the electronic structure of PCN remains poorly explored. This work reveals that the local electronic structure of PCN is strongly altered by doping with sulfur and iron using X-ray absorption spectroscopy (XAS) and resonant inelastic X-ray scattering (RIXS). From XAS at the carbon and nitrogen K-edges, sulfur atoms are found to mostly affect carbon atoms, in contrast to iron doping mostly altering nitrogen sites. In RIXS at the nitrogen K-edge, a vibrational progression, affected by iron doping, is evidenced, which is attributed to a vibronic coupling between excited electrons in nitrogen atoms and C-N stretching modes in PCN heterocycling rings. This work opens new perspectives for the characterization of vibronic coupling in polymeric photocatalysts.
RESUMEN
Isothermal molecular beam experiments on the methanol oxidation over the stepped Au(332) surface were conducted under well-defined ultra-high vacuum conditions. In the measurements, a continuous flux of methanol at excess in the gas phase and pulses of atomic oxygen were provided to the surface kept at 230 K. The formation of the partial oxidation product methyl formate under the applied conditions was evidenced by time-resolved mass spectrometry, and accumulation of formate species, which resulted in a deactivation of the surface for methyl formate formation, was followed by in situ Infrared Reflection Absorption Spectroscopy measurements. The results suggest a different reactivity of oxygen accumulated during the oxygen pulses and atomic oxygen for the competing reaction pathways in the oxidation of methanol to the desired partial and the unwanted overoxidation products.