Interfacial Reverse Charge Transfer Enabling Near 100% Selectivity of Glycerol Photooxidation into Formate over...

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 TiO₂ to Au, resulting in the formation of electron-rich Au^δ- species and Au^δ--O_v-Ti³⁺ 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/TiO₂. 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 ·CH₂OH intermediates, while O₂ is activated at the Au^δ--O_v-Ti³⁺ interface for ·O₂^- generation. The spatially decoupled activations of GLY and O₂ 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.