Mo doped TiO2: Impact on oxygen vacancies, anatase phase stability and photocatalytic activity

Vignesh Kumaravel*, Stephen Rhatigan, Snehamol Mathew, Marie Clara Michel, John Bartlett, Michael Nolan*, Steven J. Hinder, Antonio Gascó, César Ruiz-Palomar, Daphne Hermosilla, Suresh C. Pillai*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

70 Citations (Scopus)


This work outlines an experimental and theoretical investigation of the effect of molybdenum (Mo) doping on the oxygen vacancy formation and photocatalytic activity of TiO2. Analytical techniques such as x-ray diffraction (XRD), Raman, x-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to probe the anatase to rutile transition (ART), surface features and optical characteristics of Mo doped TiO2 (Mo–TiO2). XRD results showed that the ART was effectively impeded by 2 mol% Mo doping up to 750 °C, producing 67% anatase and 33% rutile. Moreover, the crystal growth of TiO2 was affected by Mo doping via its interaction with oxygen vacancies and the Ti–O bond. The formation of Ti–O–Mo and Mo–Ti–O bonds were confirmed by XPS results. Phonon confinement, lattice strain and non-stoichiometric defects were validated through the Raman analysis. DFT results showed that, after substitutional doping of Mo at a Ti site in anatase, the Mo oxidation state is Mo6+ and empty Mo-s states emerge at the titania conduction band minimum. The empty Mo-d states overlap the anatase conduction band in the DOS plot. A large energy cost, comparable to that computed for pristine anatase, is required to reduce Mo–TiO2 through oxygen vacancy formation. Mo5+ and Ti3+ are present after the oxygen vacancy formation and occupied states due to these reduced cations emerge in the energy gap of the titania host. PL studies revealed that the electron–hole recombination process in Mo–TiO2 was exceptionally lower than that of TiO2 anatase and rutile. This was ascribed to introduction of 5s gap states below the CB of TiO2 by the Mo dopant. Moreover, the photo-generated charge carriers could easily be trapped and localised on the TiO2 surface by Mo6+ and Mo5+ ions to improve the photocatalytic activity.

Original languageEnglish
Article number025008
JournalJPhys Materials
Issue number2
Publication statusPublished - Apr 2020
Externally publishedYes


  • Nanomaterials
  • Photocatalysis
  • TiO

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • General Materials Science


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