Engineering Nanoscale Homo–Heterojunction for Robust Z‐Scheme CO2 Conversion through Synchronous Amalgamation of Oxygen‐Defective Ultrathin BiVO4 and Red/Black Phosphorus

Sunlight‐driven CO2 conversion into value‐added fuels emerges as an avant‐garde strategy to mitigate the imminent energy scarcity and global warming. Nevertheless, sluggish charge kinetics and rapid carrier recombination are deemed as the foremost bottlenecks of efficient CO2 photoreduction. In this contribution, the aforementioned shortcomings are addressed by assembling a homo–hetero architecture comprising oxygen‐defective ultrathin BiVO4 (BiVO4–Ov) and red/black phosphorus (RP/BP) homojunction with a built‐in nanoscale dual Z‐scheme electronic configuration. The development of BiVO4–Ov@RP/BP confers two electron relaying channels, that is, one from the RP/BP homojunction and another from the BiVO4–Ov/RP heterojunction, which warrant the efficient separation of electron–hole pairs. Besides, the ultrathin 2D and oxygen vacant nature of BiVO4–Ov exposes more active sites and renders electron trapping for efficient utilization of photogenerated charges. Amalgamating the desirable properties, the meticulously developed dual Z‐scheme homo–heterojunction system on the basis of surface defect‐engineered ultrathin BiVO4–Ov nanosheets integrated with RP/BP offers a new avenue for the exploration, design, and fabrication of new generation photocatalysts with exceptional photocatalytic activities. In particular, the BiVO4–Ov@RP/BP system demonstrates a remarkably high CH4 yield of 14.52 μmol g−1 after 6 h of visible light illumination, which resembles a leading‐edge photocatalytic performance among the existing BiVO4‐ and P‐based semiconductors. This study focuses on the construction of oxygen‐defective bismuth vanadate nanosheets (BiVO4–Ov) and red/black phosphorus (RP/BP) with dual Z‐scheme configuration. The ultrathin two‐dimensional structure enhances the surface area of BiVO4–Ov, thus exposing more surface atoms, while the presence of oxygen vacancies facilitates electron trapping. The BiVO4–Ov@RP/BP exhibits an outstanding CH4 yield from CO2 reduction under visible‐light illumination.