Metrics & MoreArticle Recommendations CONSPECTUS: Photocatalysis, a process involving light absorption (band gap excitation), charge separation, interfacial charge transfer, and surface redox reactions, has attracted intensive attention because of the potential applications in solar to fuel conversion. Despite the great efforts devoted to the design of materials and optimization of charge separation and overall efficiency, the molecular mechanism of photocatalytic reactions, for example, water oxidation, is still unclear, mainly because of the complexity of powder catalysts and the aqueous environment which prevent the direct experimental detection of adsorption sites, surface species, and charge/energy transfer dynamics. Without direct evidence, the charge transfer and elementary reaction steps remain elusive, and misleading conclusions are sometimes drawn. For instance, the positively charged 5-fold coordinated Ti sites (Ti 5c s) on TiO 2 surfaces are argued to propel holes and therefore cannot be active sites for oxidative reactions, regardless of the demonstration by scanning tunneling microscopy (STM). Direct site-specific measurements are thus highly demanded. Surface science studies, which rely on well-defined single crystals and ultrahigh vacuum based techniques, can identify the active sites and active species at the catalyst surfaces and measure the interfacial electronic structure and energy of desorbing species for charge transfer analysis, providing direct evidence for investigating the photocatalytic reaction mechanism at the molecular level.In this Account, the elementary photocatalytic chemistry of methanol and water on TiO 2 , which are investigated by surface science techniques such as atom-resolved STM, ensemble-averaged mass spectrometer based temperature-programmed desorption/time-offlight spectroscopy, and photoelectron spectroscopy in combination with theoretical calculations, will be described. Both methanol and water can be photocatalytically oxidized at Ti 5c s, producing adsorbed formaldehyde and gaseous • OH radicals, respectively, under ultraviolet (UV) light irradiation. The photocatalytic activity shows salient adsorption structure including adsorption site (terminal/bridging), adsorption state (molecular/dissociative) and adsorption configuration (monomer/cluster) dependence, which comes from the ability to generate terminal anions which are capable of capturing photogenerated holes and exhibit superior photocatalytic activity over their parent molecules. These studies reveal the origin of the correlation between photocatalytic activity and adsorption structure of CH 3 OH and H 2 O on TiO 2 surfaces and suggest that the simple criteria widely used to analyze the feasibility of charge transfer, i.e., the relative position of the band edges and the molecular orbitals of adsorbates, should be replaced by the change of Gibbs free energy of the charge trapping reaction from the thermodynamic point of view. These results contribute to the fundamental understanding of photocatalysis. Base...
