Defect-Regulated Pt-WO x Interfacial Microenvironment Enables Deep Hydrogenation of Polycyclic Aromatic Hydrocarbons

Abstract Defect engineering of metal-oxide interfaces offers a powerful approach for regulating catalytic hydrogenation, yet its role in the deep hydrogenation of polycyclic aromatic hydrocarbons remains elusive. Herein, we synthesize a series of two-dimensional WOx nanosheets with tunable oxygen vacancy concentrations through a glucose-assisted hydrothermal strategy and construct defect-engineered Pt/D1-WOx catalysts for PAHs hydrogenation. The Ov-rich Pt/D1-WOx catalyst exhibits remarkably enhanced deep hydrogenation performance toward decalin formation compared with defect-free Pt/WO3, achieving a nearly 2.5-fold increase in TOFNA (162.7 gNA gPt–1 h–1). Experimental measurements and theoretical calculations reveal that Ov fundamentally reconstructs the Pt-WOx interfacial microenvironment by strengthening electronic metal-support interactions and stabilizing interfacial Ptδ+–O–W5+ configurations. Meanwhile, Ov adjacent to Pt functions as a hydrogen reservoirs that facilitate hydrogen spillover and maintain high local hydrogen chemical potential around interfacial active sites, which is critical for continuous aromatic ring hydrogenation. The cooperative interplay among interfacial electronic modulation, hydrogen spillover, and substrate activation establishes a hydrogen-enriched catalytic interface for efficient PAHs deep hydrogenation. These findings provide mechanistic insights into defect-regulated metal-oxide interfacial catalysis in aromatic hydrogenation.