Multipronged Validation of Oxalate C-C Bond Cleavage Driven by Au-TiO₂ Interfacial Charge Transfer Using Operando DRIFTS

We devised a multipronged approach to validate the mechanism of oxalate C-C bond cleavage and the role of Au/TiO₂ interfacial interaction via (i) selective photodriven electronic transfer and (ii) tempering of the electronic interaction by alloying Au with Cu, which serves as an electron sink. This approach allows us to speed up, slow down, impede, and bypass the interfacial electronic transfer. The multipronged approach led to a singular conclusion: Au-TiO₂ electronic interaction played a critical role in C-C bond cleavage by fixating bidentate oxalate species at the Au-TiO₂ interfacial perimeter with parallel C-C bonds to the TiO₂ surface.