Steering Acid‐base Site Distribution and Hydrophobicity of Bioresourced Bifunctional Hybrid Materials for Direct Synthesis of γ‐Valerolactone from Biomass‐based Furfural

The direct production of value‐added chemicals from biomass via multiple conversion processes with a sole renewable solid catalyst is promising for carbon‐neutral development while challenging. Herein, a series of novel bioresourced organic‐inorganic hybrid materials were synthesized from bio‐based ascorbic acid (Vc), zirconium chloride (ZrCl4) and p‐toluenesulfonic acid (p‐TSA) through a facile solvothermal process. The as‐prepared Zr‐Vc‐3 catalyst with Vc, ZrCl4, and p‐TSA in the 1:1:0.5 molar ratio displayed outstanding performance in direct furfural‐to‐γ‐valerolactone (GVL) transformation, giving an ultrahigh GVL yield of 76.2%, with an ideal activation energy (55.46 kJ mol–1), outperforming state‐of‐the‐art catalysts. The superior performance of Zr‐Vc‐3 could be ascribed to its good reusability, relatively large pore size, suitable amount of acid‐base sites, and good hydrophobicity. Mechanistic studies unveiled that Lewis acid‐base sites facilitate the conversion of furfural to furfuryl alcohol and isopropyl levulinate (IPL) to 4‐hydroxypentanoate via transfer hydrogenation process, while Brønsted acid sites are instrumental in the ring‐opening of furfuryl alcohol to IPL and the lactonization of 4‐hydroxypentanoate to GVL, overall contributing to the multi‐step conversion of furfural to GVL in a single pot. This work provides a valuable reference for precisely constructing bio‐based OIHMs with tailored functionalities for one‐pot valorization of biomass feedstocks via tandem reactions.