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

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)₂O₄ (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.