Monoclinic BiVO₄ is being used as a photocatalyst due to its stability, cost-effectiveness, ease of synthesis, and narrow band gap. Although, the valence band maximum, VBM (∼−6.80 eV vs vacuum) of BiVO₄ is well below the redox potential of water but having less positive conduction band minimum, CBM (−4.56 eV vs vacuum), responsible for its low efficiency. We have carried out a comprehensive periodic density functional theory (DFT) simulations for the pristine, Oxygen defective (O_v) and Se doped BiVO₄, to engineer not only its CB edge position but the overall photocatalytic and charge carrier properties. Our theoretical method has nicely reproduced the experimental data of pristine BiVO₄, which encouraged us to elaborate further its O_v and Se-doped characteristics. It is found that both the O_v (1% Oxygen vacancy) and Se-doped BiVO₄ (1–2% Se) have ideal band edges, band gaps, and small effective masses of electrons and holes, responsible for high photocatalytic activities. Moreover, Se-doped BiVO₄ behave as p-type semiconductor. Finally, the photocatalytic water-splitting behaviour of the selected surfaces were counterchecked with water interaction, where the strong water adsorption energy of about ∼−38 to −50 kcal/mol, confirms and predicts their higher efficiencies compared to that of parent BiVO₄.

单斜晶BiVO ₄由于其稳定性，成本效益，易于合成和窄带隙而被用作光催化剂。尽管BiVO _4的最大价带VBM（相对于真空约为-6.80 eV）远低于水的氧化还原电位，但正导带最小值CBM（相对于真空为-4.56 eV）较低，这是其低效率的原因。我们对原始的，氧缺陷的（O _v）和Se掺杂的BiVO ₄进行了全面的周期性密度泛函理论（DFT）模拟，以不仅对其CB边缘位置进行工程设计，而且对整个光催化和电荷载体性质进行工程设计。我们的理论方法很好地再现了原始BiVO ₄的实验数据，这鼓励我们进一步阐述其_Ov和Se掺杂的特性。发现O _v（1％的氧空位）和Se掺杂的BiVO ₄（1-2％的Se）都具有理想的能带边缘，能带隙以及较小的电子和空穴有效质量，它们具有较高的光催化活性。此外，掺Se的BiVO ₄表现为p型半导体。最后，通过水的相互作用对所选表面的光催化水分解行为进行了反检查，其中约〜-38至-50 kcal / mol的强水吸附能证实并预测了其与母体BiVO ₄相比更高的效率。