Cooperation of PtO2 and Adjacent Pt1 on In2O3 Photocatalysts for Unity-Selective Propane Dehydrogenation.

Solar-driven direct propane dehydrogenation (PDH) represents a promising strategy to overcome the high-temperature demands and selectivity limitations of conventional thermocatalysis, yet the identification of effective photoactive phases remains challenging. Herein, we demonstrate that photoactivated PtO2 enables regenerable and highly selective PDH over a PtO2/Pt1-In2O3 catalyst under mild conditions. Under simulated sunlight without external heating, the catalyst achieves a propylene formation rate of 1322.35 µmol g-1 h-1 with unity selectivity, while remaining inactive under comparable thermocatalytic conditions. In situ spectroscopic analyses combined with density functional theory calculations reveal a photoactivated dual-site mechanism, in which PtO2 nanoparticles function as oxidation centers for hole-driven C─H bond activation, whereas neighboring interfacial Pt single atoms act as electron-accepting sites to promote H2 evolution, enabling efficient spatial separation and utilization of photogenerated charge carriers. Catalyst deactivation arises from partial reduction of PtO2, which can be exactly regenerated via a facile oxidative annealing process in air, affording excellent reusability. These findings identify photoactivated PtO2 as a distinct active phase for selective PDH and provide a design principle for solar-driven alkane valorization.