The increased demand for outstanding and sustainable semiconductor heterojunctions highlighted bismuth oxyiodide (Bi4O5l2) as a promising photocatalyst due to its attractive light utilization, intrinsic electric field, and favorable layered structure. Our review introduces a deep description of the latest progress in synthesis, characterization, structure modifications, and photocatalytic activity of Bi4O5l2-based heterojunction. Particularly, it was focused on the morphology control and composite formation of Bi4O5l2-based nanomaterials via solvothermal, hydrothermal, and ultrasonic-assisted strategies, exhibiting well-integrated Bi4O5l2-based heterojunctions with upgraded charge dynamic and surface characteristics. The architecture and chemical states of the Bi4O5l2-based hybrid materials were clarified through a combination of density functional theory (DFT) calculations and several experimental characterization techniques, including XRD, FT-IR, Raman, and XPS. Together, these methods provided consistent evidence for the stability of the structure, the compatibility at the interfaces, and the electronic features of the composite materials. The morphological and optical investigations declared that defect modulation, surface modification, and metal or rare-earth doping narrow the band gap and expand the light consumption of Bi4O5l2-based hybrids. Besides, key heterojunction mechanisms, like Z-scheme, S-scheme, Type-I, Type-II, p-n, and Schottky systems, were extremely assessed to clarify the improved photocarrier transportation over the integration of Bi4O5l2. The role of Bi4O5l2-based hybrids in diverse organic degradation was discussed and optimized with catalyst dosage, pH, and coexisting ions, understanding the relationship between radical generation and surface chemistry. The organic degradation intermediates over Bi4O5l2-based hybrids were analyzed using QSAR, DFT, LC-MS, and fluorescence analyses. Finally, the ideal design of Bi4O5l2-based systems introduced exceptional perspective for sustainable water treatment and environmental restoration.
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