Interfacial Reverse Charge Transfer Enabling Near 100% Selectivity of Glycerol Photooxidation into Formate over Schottky’s Au/TiO 2

Photooxidation of organic is a promising approach to upgrade low-value feedstocks into value-added chemicals, yet its product uniformity faces a formidable challenge due to uncontrollable oxidation pathways and depths. Here, we tune the Schottky’s interface by a strong metal–support interaction (SMSI) that induces a reverse charge transfer from TiO 2 to Au, resulting in the formation of electron-rich Au δ− species and Au δ− –O v –Ti 3+ interfacial sites. Using glycerol (GLY) photooxidation as a model reaction, the oxidation product is nearly 100% formate (FA) with a production rate of 2.15 mmol g –1 h –1, which is 21.6-fold higher than that of conventional Schottky’s Au/TiO 2 . The impressive performance can be ascribed to that the Au δ− selectively activates GLY via C–H bond adsorption rather than the conventional O–H bond cleavage to generate ·CH 2 OH intermediates, while O 2 is activated at the Au δ− –O v –Ti 3+ interface for ·O 2 – generation. The spatially decoupled activations of GLY and O 2 favor one-step C–C bond cleavage and oxygenation, thereby achieving high selectivity of FA product. Overall, this SMSI-induced reverse charge transfer strategy provides a potential approach to enhance product uniformity in biomass upgrading.