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.