Phosphate Boosts Catalytic Hydrodeoxygenation by Facilitating Proton/Electron Transfer at the Metal–Support Interface

Catalytic hydrogenation and deoxygenation of oxygenated compounds play an essential role in the synthesis. Despite the development of numerous hydrodeoxygenation (HDO) reactions, many reactions still rely on stoichiometric reducing agents, resulting in undesirable byproducts and a low atomic efficiency. H₂ has emerged as an environmentally friendly alternative, but its efficient utilization remains challenging under mild conditions. In this study, the straightforward phosphate modification of Pt/TiO₂ led to a remarkable ∼250-fold enhancement in the sulfoxide HDO activity. Owing to the presence of the Ti-PO₄-Pt interface, the Pt/Ti(HPO₄)₂ catalyst exhibited an impressive ∼280 times higher productivity than pristine Pt/TiO₂, surpassing other homogeneous and heterogeneous catalysts by orders of magnitude. The critical roles of coordinatively unsaturated Ti³⁺ sites, interfacial phosphate, and platinum were elucidated at the atomic scale, highlighting the significance of facilitated proton/electron transfer at the interface. This work offers a promising strategy for sustainable catalytic hydrogenation processes with broad applicability in organic synthesis.