Surface Reconstruction-Engineered Transition Metals Composite Nanosheets for Green and High-Efficiency Electrocatalytic Conversion of Biomass-Derived HMF to FDCA

Abstract

The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a sustainable alternative to petroleum-derived polymers, is limited by high energy demands and precious-metal reliance. This work presents a cost-effective Ni-Co PTA nanosheet electrocatalyst fabricated via electrodeposition, solvothermal treatment, and in situ activation. Unlike conventional Au/Pd-based catalysts or transition metal hydroxides, the activated catalyst features ultrathin hexagonal nanosheets with enriched Ni³⁺/Co³⁺ species, achieving 99.9% conversion and high FDCA yield at 0.35 V(vs. HgO/Hg), outperforming non-precious benchmarks and approaching noble metals. Mechanistic analysis reveals that alkaline cycling drives evolution from dense hydroxide precursors into nanosheets., enlarging the electrochemical surface area and reducing charge-transfer resistance. XPS and in situ Raman spectroscopy confirm Ni²⁺→Ni³⁺/Co²⁺→Co³⁺ transitions, enabling NiOOH formation at lower potentials. Notably, the catalyst exhibits versatile oxidation activity toward glycerol, urea, and methanol, while maintaining high yield under practical concentrations. This work provides a scalable and sustainable strategy for biomass valorization, bridging the gap between non-precious catalyst design and industrial feasibility for green chemical synthesis.