First-principles perspectives on BiVO4 photocatalysis: electronic structure, facet anisotropy, and interface engineering

This review provides a systematic examination of recent advances in bismuth vanadate (BiVO4) photocatalyst research based on First-principles calculations. A particular focus is placed on elucidating the microscopic mechanisms underlying key aspects including crystal structure, facet effects, elemental doping, and heterojunction design. The role of Bi 6s2 lone pair electrons in monoclinic BiVO4 is clarified through density functional theory calculations, which show that these electrons induce a structural distortion and built-in electric field critical for visible-light absorption and charge separation. The review further reveals the anisotropic behavior of different exposed facets in carrier transport and surface reaction pathways. It elucidates, from an electronic structure perspective, how doping modulates band positions, defect states, and charge recombination dynamics. Additionally, the band alignment, charge transfer, and built-in field formation at heterojunction interfaces are analyzed, clarifying the theoretical foundations of enhanced photocatalytic performance in type-II, Z-scheme, and related heterostructures. This work establishes a coherent theoretical framework for the structure–property relationships in BiVO4 and demonstrates the predictive power of computational simulations in guiding the rational design of efficient photocatalysts.