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

Abstract

This work outlines an experimental and theoretical investigation of the effect of molybdenum (Mo) doping on the oxygen vacancy formation and photocatalytic activity of TiO 2 . 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 TiO 2 (Mo-TiO 2 ). 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 TiO 2 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 Mo 6+ 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-TiO 2 through oxygen vacancy formation. Mo 5+ and Ti 3+ 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-TiO 2 was exceptionally lower than that of TiO 2 anatase and rutile. This was ascribed to introduction of 5s gap states below the CB of TiO 2 by the Mo dopant. Moreover, the photo-generated charge carriers could easily be trapped and localised on the TiO 2 surface by Mo 6+ and Mo 5+ ions to improve the photocatalytic activity. coatings [8,9]. The most commonly existing crystalline polymorphs of TiO 2 are anatase, rutile and brookite [10][11][12]. Anatase is accepted to be the more active phase of TiO 2 and is preferred by the ceramic industries to fabricate light active antimicrobial indoor building materials such as ceramics, glass, tiles and sanitary surfaces [13,14]. This requires thermal stability of the anatase phase under typical ceramic processing conditions. TiO 2 anatase is mainly fabricated at low calcination temperatures (∼500°C) to prevent the anatase to rutile phase transition (ART) [15][16][17], which produces the less photo-active rutile phase. The photo-activity of anatase arises from its appropriate band edge positions, electron affinity, ionisation potential, and the long lifetime of charge carriers [10,12,18]. Moreover, transient photo-conductance analysis has revealed that the electron-hole recombination phenomena in anatase (101) phase is much slower compared to rutile (110), which is credited in part to the indirect band gap of anatase [11,19].The unit cells of anatase and rutile phases are composed of TiO 6 octahedra with titanium atoms at the centre and oxygen atoms at the vertices [20]. Both anatase and rutile have a t...

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