Herein, we designed an interface-engineered heterojunction between bismuth oxyiodide (BiOI) and a Keggin-type polyoxometalate (H3PW12O40, PW, POM) to accelerate interfacial charge transfer for dual photocatalytic functions: pollutant degradation and green H2 evolution. The BiOI/PW composites were prepared by a hydrothermal route, and comprehensively characterized (XRD, SEM/EDS, XPS, BET, UV–vis DRS, PL, EIS, and Mott–Schottky). Morphological changes and elemental analysis from SEM/EDS together with XPS shifts and BET results, verified the integration of PW and robust its interfacial bonding with BiOI. The coupling of PW preserved the BiOI crystal phase while modulating its optoelectronic properties. EIS analysis revealed a reduced interfacial resistance consistent with faster carrier transport. Mott–Schottky analysis confirmed n-type behavior and the calculated band positions proposed direct Z-scheme charge migration across the interface. In the photocatalytic remediation tests, the optimized BiOI/PW (1: 4) achieved 84.7% degradation of crystal violet (CV) under visible light (vs 55.1% for BiOI) with a 2.72-fold higher apparent rate constant (0.00942 min−1). Beyond CV, the composite exhibited notable versatility against structurally diverse dyes (e.g., 86.5% for allura red, 79.5% for sunset yellow) and pharmaceutical contaminants, such as doxycycline (82.8% vs 72.3% for BiOI), ciprofloxacin (58.1% vs 29.0%), and tetracycline (74.7% vs 70.0%), demonstrating broad-spectrum pollutant removal capability. Moreover, acute Daphnia magna bioassays revealed that the photocatalytic treatment markedly reduced ecotoxicity, with immobilization decreasing to below 50%Finally, the photocatalytic hydrogen evolution reached 6101 μmol g−1 h−1 for BiOI/PW (1, 4), 1.3-times greater than that of BiOI, underscoring the merit of POM-assisted interfacial design for multifunctional photocatalysis.
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