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.