Multi‐Heteroatom‐Doped Carbon Framework From Yeast Biomass Enabling Embedded Nickel Phosphide Nanoparticles With Selective Electrochemical Upgrading of 5‐Hydroxymethylfurfural

ABSTRACT The interfacial electrochemical transformation of organic molecules is often influenced by the competitive oxygen evolution reaction initiated by the preferential adsorption of OH − ions. Here, we introduce an interfacial OH − regulation strategy enabled by integrating a multi‐heteroatom‐doped carbon framework (NPSC) onto Ni 12 P 5 nanomaterials, produced via Ni 2+ adsorption on yeast and subsequent carbonization. This catalytic system attains a peak faradaic efficiency of 90.1%, with an impressive 94.2% selectivity in synthesizing the bioplastic monomer 2,5‐furandicarboxylic acid through electrocatalytic conversion of 98.1% of 5‐hydroxymethylfurfural (HMF) at 1.45 V RHE . This exceptional performance is driven by the intimate interfacial coupling between the Ni 12 P 5 phase and NPSC, modulating the local catalytic environment. In situ characterizations reveal the dynamic generation and redox cycle of active NiOOH species from Ni 12 P 5 , corroborating the HMF oxidation pathway via the 5‐hydroxymethyl‐2‐furancarboxylic acid intermediate. Density functional theory calculations substantiate that NPSC‐supported Ni 12 P 5 effectively regulates interfacial OH * adsorption and elevates the energy barrier of oxygen intermediate conversion (OH * to O * ), inhibiting the oxygen evolution reaction while enhancing the kinetics of HMF oxidation. This work not only establishes a renewed and biomass‐derived protocol for fabricating electrocatalysts to facilitate biomass conversion efficiency but also offers new opportunities for leveraging biomass‐derived carbon materials in renewable energy systems.