High-Value Conversion of Biomass-Derived Chemicals by In Situ Construction of Ni(OH)/CeVO@NF Catalysts Enriched with Oxygen Vacancies.

2,5-Furandicarboxylic acid (FDCA), synthesized via selective oxidation of 5-hydroxymethylfurfural (HMF), is a structural analog to petroleum-derived terephthalic acid (PTA) and a key precursor for renewable polyesters like polyethylene furanoate (PEF). Recent advances in electrocatalytic HMF oxidation (HMFOR) enable efficient synthesis under mild conditions, aligning with renewable energy integration. In this work, catalysts with oxygen-rich vacancies by growing Ce, V bimetallic-dopsynthesizeded Ni(OH) nanosheets in situ on nickel foam for electrocatalytic HMF oxidation to FDCA are prepared. The experimental results show that the electronic coupling of Ce and V modulated the d-band center of Ni, optimized the electronic structure of Ni(OH), and also enhanced the adsorption and activation ability of the catalyst toward HMF molecules. In addition, the catalytic system provided electrons to HMF via Ni/Ni redox pairs and exhibits excellent catalytic performance for complete HMF conversion (100%), FDCA yield (97.8%), and high Faraday Efficiency (97.6%). DFT calculations show that the oxidation step from FFCA to FDCA is considered to be the decisive acceleration step for the whole conversion process. This study not only provides a novel strategy for designing efficient non-precious Ni-based electrocatalysts, but also opens up new avenues for the value-added conversion of biomass-derived platform molecules.