Enhancing C-O Bond Cleavage in 2,6-Dimethoxy-4-methylphenol Hydrodeoxygenation via Oxygen Vacancy Engineering in Pd-Pt/NiO-FeOx Nanosheets

Achieving selective conversion of lignin-derived phenolic compounds to cycloalkanes under mild conditions remains a significant challenge. Herein, we report a novel iron-incorporated two-dimensional NiO nanosheet supported Pd-Pt alloy catalyst (Pd1.7-Pt0.3/NiO-5FeOx) that is capable of facilitating highly efficient hydrodeoxygenation (HDO) of lignin-derived phenolic model compounds (e.g., 2,6-dimethoxy-4-methylphenol) under mild conditions (250 °C, 5 atm H2). The reaction mechanism was investigated through various characterization techniques and mechanistic studies: introducing FeOx into the NiO support increases the proportion of defect-related oxygen species (Oβ), enhances adsorption of the key hydrogenated alcohol intermediate 4-methylcyclohexanol, and optimizes the acidity distribution of the catalyst, thereby promoting C(sp3)-O bond cleavage (dehydroxylation) toward cycloalkane formation. The catalyst achieved high conversion (>95%) for various lignin-derived phenolics and high selectivity (93.0%) toward methylcyclohexane under mild conditions. This work offers new insights into the design of efficient biomass conversion catalysts under mild conditions and provides an energy-efficient route for the sustainable utilization of lignin resources.