Interfacial Bond Fabricated From High Entropy MOFs Facilitates Electric Field Modulation for Boosted Photoelectrochemical DHA Formation on BiVO 4

BiVO 4 (BVO) photoanodes are promising for photoelectrochemical glycerol oxidation (PEC GOR), but their performance is limited by sluggish hole extraction, V 5+ dissolution, and poor control over selective C 3 oxidation. Herein, we develop an in situ surface‐confined topological transformation strategy to construct an amorphous FeCoNiCuMn high‐entropy MOF interfacial layer on BVO (BVO‐H MOF). The high‐entropy layer acts as a catalytically coupled interface rather than a passive coating: it induces a Ni–V–O X activation layer to suppress V 5+ leaching and establishes an interfacial electric field that promotes directional hole extraction. In situ XPS, Raman, ATR‐SEIRAS, and DFT calculations indicate that electron‐deficient Ni sites favor adsorption through the secondary hydroxyl group of glycerol and promote the DHA‐forming pathway. As a result, BVO‐H MOF achieves a DHA formation rate of 361.5 mmol m −2 h – 1 and a selectivity of 69.8% at 1.0 V (vs. RHE), outperforming previously reported catalysts. More importantly, the Ni–V–O X activation layer generated by in situ conversion enabled stable operation for 120 h in an unbiased integrated PEC system. This work establishes high‐entropy MOF‐derived interfacial activation as a promising strategy for coupling solar‐driven biomass valorization with pollutant conversion.