N,W‐Cooperative Modulation of Ni ₃ S ₂ for Efficient Electrocatalytic Oxidation of 5‐Hydroxymethylfurfural to 2,5‐Furandicarboxylic Acid

ABSTRACT Ni 3 S 2 has emerged as a promising catalyst for the electrochemical oxidation of biomass‐derived 5‐hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA), driven by its distinctive physicochemical properties. However, its practical catalytic efficiency is severely hindered by abundant electrochemically inactive surface sites and poor electronic conductivity. To overcome these challenges, an N,W‐cooperative modulation of Ni 3 S 2 catalyst (N,W‐Ni 3 S 2 ), featuring an engineered crystalline‐amorphous heterostructure, is designed, utilizing 5,10,15,20‐tetraphenylporphine (TPP) as the N source. This innovative architecture integrates W‐doped crystalline Ni 3 S 2 and N‐doped amorphous carbon, which synergistically enhances charge transport and induces interfacial charge polarization, substantially boosting catalytic activity. The optimized N,W‐Ni 3 S 2 demonstrates unprecedented electrocatalytic performance for the oxidation of HMF to FDCA, achieving 100% HMF conversion, 97% FDCA yield, and 97% Faradaic efficiency, with over 95% retention in both FDCA yield and Faradaic efficiency across 10 consecutive cycles. Theoretical calculations and experimental results unveil that N incorporation exerts a more profound influence than W in reshaping the electronic landscape of Ni 3 S 2 , triggering an asymmetric electron redistribution at the heterogeneous interface. This unique electronic perturbation depletes the electron density around Ni active sites, creating an electron‐deficient state that dramatically promotes the in situ generation of NiOOH as the true active species. Furthermore, the tailored electronic environment significantly lowers the energy barrier for the rate‐determining step in the oxidation pathway, thereby enabling near‐quantitative FDCA production with high efficiency.