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Abstract Elemental phosphorus in its various allotropes has received tremendous research attention recently due to its intriguing electronic and structural properties. Notably, the application of nanostructured materials to overcome the inherent flaws in bulk materials is promising. However, many challenges need to be addressed before its widespread implementation. Thus, a specific tenet to design novel and robust nanomaterials is a decisive factor in the desired outcome, and the most daunting task before realizing this is solving the Schrödinger equation. First principle density functional theory (DFT) calculations have emerged as an insightful and accurate design tool to investigate the structural, electronic, and possible synthesis scenarios of yet undiscovered materials at atomic levels. In this review, the basic principles and the importance of DFT are discussed, followed by a summary of recent advances in the first principle study of elemental phosphorus‐based nanomaterials. Elemental phosphorus‐based nanomaterials and their allotropes have attracted growing interest in the renewable energy community due to their modulable product selectivity. However, the understanding of the physical phenomena of allotropic modification is still lacking. Therefore, the aim is to motivate experimental researchers to conduct DFT studies and experiments to comprehend relevant engineered nanomaterials better. Finally, the challenges and potential future research directions for further theoretical and computational development of phosphorus‐based nanomaterials are outlined.

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.