N,W-Cooperative Modulation of Ni3S2 for Efficient Electrocatalytic Oxidation of 5-Hydroxymethylfurfural to 2,5-Furandicarboxylic Acid

en 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. 摘要 zh Ni 3 S 2 凭借其独特的物理化学性质,已成为一种极具前景的催化剂,可用于将生物质衍生的5-羟甲基糠醛(HMF)电化学氧化为2,5-呋喃二甲酸(FDCA)。然而,其实际催化效率因大量电化学惰性表面位点和较差的电子导电性而受到严重阻碍。为解决这些问题,本研究设计了一种具有工程化晶态-非晶态异质结构的Ni 3 S 2 催化剂的氮、钨协同调控体系(N,W-Ni 3 S 2 ),并以5,10,15,20-四苯基卟啉(TPP)作为氮源。这种创新结构整合了钨掺杂的晶态Ni 3 S 2 与氮掺杂的非晶碳,二者协同增强电荷传输并诱导界面电荷极化,显著提升了催化活性。优化后的N,W-Ni 3 S 2 在HMF氧化生成FDCA的反应中表现出优异的电催化性能:HMF转化率达100%,FDCA产率达97%,法拉第效率达97%; 在10次连续循环中,FDCA产率和法拉第效率均保持在95%以上。理论计算与实验结果表明,在重构Ni 3 S 2 的电子结构方面,氮掺杂比钨掺杂的影响更为显著,可在异质界面处引发不对称的电子重新分布。这种独特的电子扰动会降低Ni活性位点周围的电子密度,形成缺电子状态,从而显著促进真正活性物种NiOOH的原位生成。此外,这种定制化的电子环境大幅降低了氧化路径中决速步的能垒,进而实现了高效且接近定量的FDCA生成。