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Molybdenum defect complexes in bismuth vanadate.

Enesio Marinho1, Cedric Rocha Leão1

  • 1Federal University of ABC (UFABC), 09210-580 Santo André, São Paulo, Brazil. cedric.rocha@ufabc.edu.br.

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|July 11, 2020
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Summary
This summary is machine-generated.

Monoclinic bismuth vanadate (BiVO4) doped with Mo or W shows enhanced photocatalytic activity. Unexpectedly, dopant pairs form most stably on nearest-neighbor sites due to favorable orbital hybridization, improving solar water splitting.

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Area of Science:

  • Materials Science
  • Solid State Chemistry
  • Photocatalysis

Background:

  • Monoclinic bismuth vanadate (BiVO4) is an n-type semiconductor with potential for solar-driven water splitting.
  • Doping BiVO4 with molybdenum (Mo) and tungsten (W) significantly enhances its photocatalytic performance.

Purpose of the Study:

  • To investigate the most energetically favorable configurations for Mo and W dopant pairs in BiVO4.
  • To understand the underlying mechanisms driving dopant pair formation and their impact on material properties.

Main Methods:

  • Ab initio calculations were employed to simulate and analyze defect configurations in BiVO4.
  • The study focused on pairwise Mo (MoV) and W (WV) defects within the BiVO4 crystal lattice.

Main Results:

  • The lowest energy configuration for MoV and WV defect pairs in BiVO4 was found to be on nearest-neighbor sites.
  • This nearest-neighbor configuration is attributed to favorable hybridization between impurity atomic orbitals, leading to enthalpy gain.
  • This gain overcomes electrostatic repulsion and lattice strain, which are typically disfavored at such proximity.

Conclusions:

  • Mo and/or W doped BiVO4 are predicted to form donor-donor defect complexes.
  • This finding provides a crucial insight for experimental strategies aimed at optimizing the photocatalytic activity of these metal oxides for water splitting.