Hydrogenolysis of Aromatic Oxygenates Over Pt/WO₃-ZrO₂ in a Water/Decane Biphasic System

The hydrogenolysis of lignin-derived aromatic oxygenates into aromatic hydrocarbons under mild conditions remains a significant challenge due to competing over-hydrogenation of the aromatic ring. Here, we report a highly active and water-tolerant Pt/WO₃-ZrO₂ catalyst that enables the conversion of a broad range of aromatic oxygenates into aromatic hydrocarbons in a water/decane biphasic system at 90 °C under ambient pressure with a H₂ partial pressure of only 0.1 atm. The biphasic environment efficiently suppresses side reactions by continuously extracting the arene products into the organic phase, thereby minimizing further hydrogenation of the aromatic ring. Kinetic analysis shows that C(sp²)-OMe cleavage precedes C(sp²)-OH cleavage in the hydrogenolysis of 4-ethylguaiacol, while mechanistic studies reveal that the strong Brønsted acidity and redox properties of the WO₃-ZrO₂ support enable hydrogenolysis under exceptionally mild conditions. The catalyst exhibits broad substrate scope, high selectivity for aromatic products, and good reusability, providing an efficient platform for producing aromatic hydrocarbons from lignin-derived oxygenates.