Molybdenum defect complexes in bismuth vanadate

Monoclinic bismuth vanadate (BiVO4) is a promising n-type semiconductor for applications in sunlight-driven water splitting. Several studies have shown that its photocatalytic activity is greatly enhanced by high concentrations of Mo and W dopants. In the present work, we performed ab initio calculations to assess the most favorable relative position between pairs of Mo dopants in BiVO4. Surprisingly, we verify that the lowest energy configuration for MoV pairwise defects in BiVO4 occurs on nearest-neighbor sites, despite the higher electrostatic repulsion and larger strain on the crystal lattice. Similar results were observed for WV defect pairs in W-doped BiVO4. We show that the origin of this effect lies in a favorable hybridization between the atomic orbitals of the impurities that is only verified when they are closest to each other, resulting in an enthalpy gain that overcomes the repulsive components of the pair formation energy. As a consequence, Mo and/or W doped BiVO4 are likely to present donor-donor defect complexes, which is an outcome that can be applied in experimental approaches for improving the photocatalytic activity of these metal oxides.