Control of Selectivity through a New Hydrogen-Transfer Mechanism in Photocatalytic Reduction Reactions: Electronically Relaxed Neutral H and the Role of Electron-Phonon Coupling

摘要

Controlling the fate of hydrogen in photocatalytic synthesis reactions has been an ongoing challenge in CO2 reduction by H2O and nitrogen fixation efforts. Our studies have identified catalysts (SiC) that exhibit dramatically improved selectivity toward hydrogenation and a photocatalytically active ground-state neutral H that is transferred via vibrational excitation through electronic-vibrational coupling with excited states. This new species and mechanism have been directly connected to the fate of H by comparing GaN and SiC and purposefully manipulated over a single catalyst (SiC) to illustrate generality. Studies included surface reaction modeling using density functional theory (DFT), experimental performance, H-1 NMR spectroscopy, and deuterium kinetic isotope effect. The discovery of this mechanism may have considerable impact on the direction of photocatalytic synthesis, the understanding of the coupling of thermal and photoelectrochemical reaction steps, and electronic-vibrational spectrum coupling in energy sequestration.