Direct Transformation of Bio‐Based Furfural into γ‐Valerolactone over SO3H‐Functionalized P‐O‐Hf Hybrid Catalysts

γ-Valerolactone (GVL) has great application potential in organic synthesis and biofuels, while its high-efficiency production from easily available bio-based feedstock is challenging. In this work, SO3H-functionalized P-O-Hf hybrid catalysts GPCS-Hf(n:m) were facilely prepared by solvothermal treatment of glucose-containing organic precursors (GPC) and Hf4+ in a mass ratio of n:m. The acid strength and Lewis/Brønsted acid sites of GPCS-Hf(n:m) could be modulated by tuning the GPC/Hf4+ ratio. Among them, GPCS-Hf(1:1.5) with appropriate acid-base properties delivered prominent catalytic activity in the direct upgrading of a bio-based bulk chemical furfural (FF) to GVL with a good yield of 71%, as optimized by response surface methodology. Especially, suitable distribution of Lewis acid (Hf4+), Lewis base (O2-) and Brønsted acid (H+) sites played a synergistic role in cascade transfer hydrogenation, furan ring opening, second hydrogenation, and lactonization. Moreover, the GPCS-Hf(1:1.5) catalyst was unveiled to have a uniform elemental dispersion, relatively large specific surface area and amorphous structure, which might also contribute to its superior efficiency. Recycling experiments showed that GPCS-Hf(1:1.5) could be reused at least five times with almost no decline in activity. The overall bio-derived catalytic conversion system offers a more sustainable manner for biomass valorization.