Pt‐Activated Surface Nucleophilicity on High‐Entropy Oxides Enables Superior Biomass Upgrading

Abstract Strategic engineering of the surface electronic structure in high‐entropy oxides (HEOs) to enable efficient and selective electrocatalytic 5‐hydroxymethylfurfural oxidation reaction (HMFOR) presents significant challenges. Herein, a Pt‐decorated Zn(AlCrMnFeCo) 2 O 4 (Pt/HEO) catalyst is fabricated and harnessed the strong metal‐support interaction (SMSI) between Pt and HEO, alongside the intrinsic strong intermetallic synergies within the HEO lattice, to strategically engineer the surface electron configuration of HEO. Pt/HEO catalyst achieves a 2,5‐furandicarboxylic acid (FDCA) production rate of 80 mA cm −2 at 1.38 V versus RHE with a near‐unity Faradaic efficiency (≈99.8%) and selectivity (≈96.8%). These performances surpass majority of recently reported state‐of‐the‐art catalysts. The excellent performance originates from the anchored Pt‐induced charge redistribution within the HEO lattice, driven by the strong intermetallic synergies among multiple metal components. The resulting electronic effect strengthens nucleophilic interaction between HMF and metal‐oxyhydroperoxide (M─OOH) on metal‐oxygen (M─O) sites. This work establishes a viable strategy for strategic electronic modulation of HEOs, offering a paradigm for designing robust electrocatalysts to advance sustainable biomass valorization.