Heterogeneous catalytic conversion of biomass-derived methyl levulinate (ML) to γ-valerolactone (GVL) is highly attractive as a sustainable route to mitigating the dependence on nonrenewable fossil resources. However, this route is limited by its low selectivity toward GVL and severe reaction conditions. Here, we present a synergistic catalytic process that offers exclusive GVL selectivity with complete ML conversion under mild conditions (80 °C, 0.5 MPa of H₂ pressure). This is achieved over a dual-functionalized catalyst of Ru nanoparticles (Ru-NPs) and Brønsted acid SO₃H groups in a Cr-based metal-organic framework (MIL-101). The Ru-NPs served as metal sites for the hydrogenation of ML to methyl-3-hydroxyvalerate (MHV) and the acidic SO₃H moieties promoted the cyclization of MHV to generate GVL via lactonization. In contrast, GVL production was significantly suppressed over the physically mixed congener (2.0 wt% Ru/MIL-101 + MIL-101-SO₃H). This result demonstrates an unrivalled advantage of the dual integration of metal/acid sites in a single MOF crystal, and the relative amount of sulfonic acid groups in the catalyst can exert significant influence on the overall catalytic performances. The activation energies for the hydrogenation and lactonization steps with the developed catalyst were 29.5 and 42.1 kJ/mol, respectively, which are much lower than those observed with the traditional 5.0 wt% Ru/AC catalyst.

生物质衍生的乙酰丙酸甲酯（ML）异质催化转化为γ-戊内酯（GVL）作为缓解对不可再生化石资源的依赖的可持续途径极具吸引力。然而，该途径受到其对GVL的低选择性和苛刻的反应条件的限制。在这里，我们介绍了一种协同催化过程，该过程在温和条件下（80°C，H ₂压力为0.5 MPa ）可提供独家的GVL选择性和完全的ML转化率。这是通过在基于Cr的金属有机骨架（MIL-101）中将Ru纳米颗粒（Ru-NPs）和布朗斯台德酸SO ₃ H基团双官能化的催化剂实现的。Ru-NPs可作为金属加氢将ML加氢成3-羟基戊酸甲酯（MHV）和酸性SO ₃H部分促进了MHV的环化以通过内酯化产生GVL。相反，与物理混合的同类物（2.0 wt％Ru / MIL-101 + MIL-101-SO ₃ H）相比，GVL的产生被显着抑制。该结果证明了在单个MOF晶体中金属/酸位点的双重整合具有无与伦比的优势，并且催化剂中磺酸基团的相对含量会对整体催化性能产生重大影响。用开发的催化剂进行氢化和内酯化步骤的活化能分别为29.5和42.1 kJ / mol，远低于传统的5.0 wt％Ru / AC催化剂所观察到的活化能。