Multimetallic Synergy‐Dominated Catalysis in Ce‐MOF‐Supported Pd‐Cu Catalysts for Oxidative Carbonylation of Glycerol: Structure Regulation and Electronic Modulation

Rational construction of multimetallic MOF catalysts provides an effective strategy to regulate electronic structures and catalytic behavior in glycerol oxidative carbonylation. Using Ce‐MOF as the structural framework, a series of Pd‐Cu‐Ce multimetallic MOF catalysts were constructed by regulating the introduction sequence and loading modes of Pd and Cu. The structure–property–performance relationships among structural characteristics, electronic properties, and catalytic behavior were systematically investigated. Comprehensive characterization results indicate that, in Pd‐Cu/Ce‐MOF, Pd and Cu are co‐doped into the Ce‐MOF framework, forming a stable synergistic structure and significantly modulating the electronic environment of the metal sites. X‐ray photoelectron spectroscopy (XPS) analysis reveals increased Ce 3+ content, surface‐adsorbed oxygen, and oxygen vacancy concentration, while the coupled Pd 2+ /Pd 0 and Cu 2+ /Cu + redox pairs effectively optimize the electronic structure of Pd active centers. Despite its relatively low surface area, Pd–Cu/Ce‐MOF exhibits the highest activity and selectivity in glycerol oxidative carbonylation, indicating that multimetallic synergy dominates catalytic performance. Kinetic studies suggest an Eley–Rideal mechanism, in which glycerol adsorbs on the catalyst surface and gaseous CO directly participates in glycerol carbonate formation. This study provides experimental evidence for the rational design and application of MOF‐based multimetallic synergistic catalysts.