Solar H 2 O 2 generated from O 2 and H 2 O is an economical and green protocol. However, most photocatalysts only perform well in the presence of sacrificial donors or the photocatalysts are composed by organic materials, thus hindering their applicability. Herein, an inorganic matrix, i.e. ZnIn 2 S 4 @BiVO 4 (ZIS@BVO), is constructed as a model catalyst for photocatalytic H 2 O 2 production in non-sacrificial systems. Excellent performance (1.8 mmol g −1 h −1 ) under visible-light is realized, and an apparent quantum yield of 5.18% is realized at 420 nm. Thorough investigation helps us to rationalize its exceptional performance and structural characteristics. Of note, the electron spin resonance spectroscopy results, in combination with scavenger capture experiments, reveal the discovery of an overlooked pathway. Specifically, except for the well-known two-electron oxygen reduction reaction (ORR), the involvement of 1 O 2 intermediate is verified during the H 2 O 2 generation. Beyond presenting high performance of the inorganic composites, this finding also discloses a different reaction path for H 2 O 2 production.
How to achieve high-speed directional migration and separation of photogenerated carriers at heterointerfaces is still an important factor restricting efficient photocatalytic reactions. Herein, hierarchical columnar ZnIn 2 S 4 /BiVO 4 (ZIS/BVO) Z-scheme composite with photogenerated carriers highway in heterogeneous interface are designed by an in situ technique. Ultrathin ZIS nanosheets are uniformly grown upright on the surface of mulberry-like BVO pillars. The confined built-in electric field and Z-scheme heterojunction in ZIS/BVO are verified in detailed by synchronous illumination X-ray photoelectron spectroscopy, theoretical calculation, electron spin resonance spectroscopy, and high-resolution TEM. The photogenerated electrons in the conduction band (CB) of BVO migrate to the valence band (VB) of ZIS through heterojunction, whereas holes in the VB of BVO and electrons in the CB of ZIS maintain the original high redox capability. These holes and electrons with high redox capability react with H 2 O and O 2 to generate more OH and O 2 − , respectively, achieving enhanced photocatalytic mineralization antibiotic properties. The mineralization rate of antibiotics in the optimized ZIS/BVO material are 4.4 and 1.8 times higher than that of pure BVO and ZIS, respectively.
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