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 CC 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 CC bond cleavage by fixating bidentate oxalate species at the Au-TiO2 interfacial perimeter with parallel CC bonds to the TiO2 surface.