Metal‐Organic Framework‐type NHC‐X‐Pd Complexes for the Selective Oxidation of 5‐HydroxyMethylFurfural to 2,5‐Furandicarboxylic Acid

2,5‐Furandicarboxylic acid (FDCA), a biobased monomer with the potential to replace petroleum‐derived terephthalic acid (PTA), is widely used in eco‐friendly applications such as bioplastics and high‐performance polyesters. In this study, the post‐synthetic ligand exchange (PSLE) strategy was employed to synthesize MOF catalysts functionalized with distinct N‐heterocyclic carbene (NHC) ligands. The successful preparation and elemental composition of the catalysts were confirmed by 1 H nuclear magnetic resonance ( 1 H NMR), X‐ray photoelectron spectroscopy (XPS), and X‐ray powder diffraction (XRD). Under alkaline conditions, UIO‐NHC‐OCH 3 ‐Pd, with the highest electron density on Pd center demonstrated superior catalytic performance, achieving a reaction rate constant ( k = 2.11 h −1 ) 18.5% higher than that of UIO‐NHC‐CF 3 ‐Pd and the lowest activation energy ( E a = 25.15 kJ·mol −1 ). These findings propose an effective ligand‐driven electronic modulation strategy for optimizing 5‐HydroxyMethylFurfural (HMF) oxidation catalysts, providing a blueprint for sustainable chemical synthesis.