Two-Electron-Two-Proton Transfer from Colloidal ZnO and TiO₂ Nanoparticles to Molecular Substrates

Transfers of multiple electrons and protons are challenging yet central to many energy-conversion processes and other chemical and biochemical reactions. Semiconducting oxides can hold multiple redox equivalents. This study describes the 2e^-/2H⁺ transfer reactivity of photoreduced ZnO and TiO₂ nanoparticle (NP) colloids with molecular 2e^-/2H⁺ acceptors, to form new O-H, N-H, and C-H bonds. The reaction stoichiometries were monitored by NMR and optical spectroscopies. Faster 2e^-/2H⁺ transfer rates were observed for substrates forming O-H or N-H bonds, presumably due to initial hydrogen bonding at the oxide surface. Chemically reduced ZnO NPs stabilized by Na⁺ or Ca²⁺ also engage in 2e^-/2H⁺ transfer reactivity, showing that protons transferred in these processes are inherent to the oxide nanoparticles and do not exclusively stem from photoreduction. These results highlight the potential of ZnO and TiO₂ for multiple proton-coupled electron transfer (PCET) reactions.