Abstract Monoclinic clinobisvanite BiVO4 is one of the most promising photocatalyst due to its stability, low cost, narrow band gap, and suitable valence band maximum (VBM) position. The valence band maximum of about −7.10 eV at vacuum level was observed, which is well below the redox potential of water. However, the conduction band minimum, CBM of about −4.86 eV at vacuum level, which was responsible for its low efficiency. The presence of metal (Bi or V) vacancy changed the charge density and VBM of pristine BiVO4. Our calculated results revealed that 0.04% of the intrinsic Bi or V defects enhanced p-type conductivity and hence improved photocatalytic activity than O-interstitial in pristine BiVO4. The optical properties of both pristine and intrinsically defective BiVO4 were calculated and analyzed with perspective of their photocatalytic properties. Conclusively, the role of Bi or V (metal) vacancies in pristine BiVO4 was found to be significant than O interstitials in enhancing the photocatalytic properties regarding the solar water splitting.

中文翻译：

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固有缺陷的未掺杂钒酸铋 (BiVO4) 光催化剂的光催化性能：DFT 研究

摘要 单斜斜斜二钒石BiVO4由于其稳定性好、成本低、带隙窄、价带最大值（VBM）位置合适等优点，是最有前景的光催化剂之一。在真空水平观察到约 -7.10 eV 的价带最大值，远低于水的氧化还原电位。然而，导带最小值 CBM 在真空级约为 -4.86 eV，这是其低效率的原因。金属（Bi 或 V）空位的存在改变了原始 BiVO4 的电荷密度和 VBM。我们的计算结果表明，在原始 BiVO4 中，0.04% 的固有 Bi 或 V 缺陷增强了 p 型电导率，因此比 O 间隙提高了光催化活性。从光催化性能的角度计算和分析了原始和固有缺陷 BiVO4 的光学性能。最后，发现原始 BiVO4 中 Bi 或 V（金属）空位的作用比 O 间隙在增强太阳能水分解的光催化性能方面更显着。