Organic Ligand‐Enhanced Covalent Fe Coordination in NiFe LDH for Efficient Biomass Upgrading

Abstract Electrocatalytic conversion of biomass‐derived 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) presents a promising route for the bio‐renewable polymer industry. However, the development of efficient catalysts remains a key challenge. Herein, a NiFe layered double hydroxide (LDH) catalyst modified with an organic carboxylate ligand, trimellitic acid (TA) (denoted as NiFe LDH‐TA) is designed. This catalyst exhibits impressive performance in HMF oxidation, achieving an impressive FDCA yield of 97.5% while maintaining stable operation for 200 h. X‐ray absorption spectroscopy and theoretical analysis reveal that the introduction of TA enhances the interaction between NiFe LDH and HMF, effectively facilitating efficient proton‐coupled electron transfer and boosting catalytic activity. Furthermore, the covalent coordination between Fe and O in NiFe LDH‐TA is strengthened as the number of carboxylate ligands increases. This reinforcement, attributed to the formation of robust Fe─O─C bonds, prevents its excessive oxidation and dissolution. This dual enhancement strategy, which simultaneously optimizes activity and durability, offers a promising avenue for efficient biomass upgrading.