Surface contamination by microbes is a major public health concern. A damp environment is one of potential sources for microbe proliferation. Smart photocatalytic coatings on building surfaces using semiconductors like titania (TiO2) can effectively curb this growing threat. Metal-doped titania in anatase phase has been proven as a promising candidate for energy and environmental applications. In this present work, the antimicrobial efficacy of copper (Cu)-doped TiO2 (Cu-TiO2) was evaluated against Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) under visible light irradiation. Doping of a minute fraction of Cu (0.5 mol %) in TiO2 was carried out via sol-gel technique. Cu-TiO2 further calcined at various temperatures (in the range of 500–700 °C) to evaluate the thermal stability of TiO2 anatase phase. The physico-chemical properties of the samples were characterized through X-ray diffraction (XRD), Raman spectroscopy, X-ray photo-electron spectroscopy (XPS) and UV–visible spectroscopy techniques. XRD results revealed that the anatase phase of TiO2 was maintained well, up to 650 °C, by the Cu dopant. UV–vis results suggested that the visible light absorption property of Cu-TiO2 was enhanced and the band gap is reduced to 2.8 eV. Density functional theory (DFT) studies emphasize the introduction of Cu+ and Cu2+ ions by replacing Ti4+ ions in the TiO2 lattice, creating oxygen vacancies. These further promoted the photocatalytic efficiency. A significantly high bacterial inactivation (99.9999%) was attained in 30 min of visible light irradiation by Cu-TiO2.

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The thermal stability of anatase titanium dioxide (TiO2) is a prerequisite to fabricate photocatalyst coated indoor building materials for use in antimicrobial and self-cleaning applications under normal room light illumination. Metal doping of TiO2 is an appropriate way to control the anatase to rutile phase transition (ART) at high processing temperature. In this present work, ART of indium (In) doped TiO2 (In-TiO2) was investigated in detail in the range of 500 °C -900 °C. In-TiO2 (In mol % = 0 to 16) was synthesized via a modified solgel approach. These nanoparticles were further characterized by means of powder X-ray diffraction (XRD), Raman, photoluminescence (PL), transient photocurrent response, and Xray photoelectron spectroscopy (XPS) techniques. XRD results showed that the anatase phase was maintained up to 64 % by 16-mol % of In doping at 800 °C of calcination temperature.XPS results revealed that the binding energies of Ti 4+ (Ti 2p1/2 and Ti 2p3/2) were red-shifted by In doping. The influence of In doping on the electronic structure and oxygen vacancy formation of anatase TiO2 was studied using density functional theory corrected for on-site Coulomb interactions (DFT+U). First principles results showed that the charge compensating oxygen vacancies form spontaneously at sites adjacent to the In dopant. DFT+U calculations revealed the formation of In -5s states in the band gap of the anatase host. The formation of In2O3 at the anatase surface was also examined using a slab model of the anatase (101)

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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Ceria nanocluster modification of TiO2 rutile (110): Ce3+ formation, reduced energy gap, and enhanced CO2 and water activation.

Water splitting to produce hydrogen gas, using renewably produced electricity (electrocatalysis) or by direct conversion of solar energy (photocatalysis), is a strategy that addresses key environmental and energy challenges. The overall water splitting reaction proceeds as two half reactions, namely the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), each of which require catalysts specifically tailored to maximize efficiency. The benchmark catalysts for the HER are noble metals. However, their expense and rarity makes them economically unfeasible for large-scale H2 production from water. Consequently, there are considerable efforts to find cheap, abundant materials that can efficiently catalyze the HER. Over the last decade, metal chalcogenides and phosphides have emerged as promising candidates for HER. In this review article, we discuss a selection of the multitude of studies and materials in these two classes of catalyst to give a flavor of the relevant developments and properties of these materials. In addition to the selection of catalyst materials, preparation and structuring are playing a strong role in enhancing HER and overcoming fundamental challenges. The role of modeling in the performance of HER catalysts is also discussed and we end with a short perspective on the key attributes of a good HER catalyst.

Surface modification of titania surfaces with dispersed metal oxide nanoclusters has the potential to enhance photocatalytic activity. These modifications can induce visible light absorption and suppress charge carrier recombination which are vital in improving the efficiency. We have studied heterostructures of Mn 4 O 6 nanoclusters modifying the TiO 2 rutile (110) and anatase (101) surfaces using density functional theory (DFT) corrected for on-site Coulomb interactions (DFT + U). Such studies typically focus on the pristine surface, free of the point defects and surface hydroxyls present in real surfaces. In our study we have considered partial hydroxylation of the rutile and anatase surfaces and the role of cation reduction, via oxygen vacancy formation, and how this impacts on a variety of properties governing the photocatalytic performance such as nanocluster adsorption, light absorption, charge separation, and reducibility. Our results indicate that the modifiers adsorb strongly at the surface and that modification extends light absorption into the visible range. MnO x -modified titania can show an off-stoichiometric ground state, through oxygen vacancy formation and cation reduction spontaneously, and both modified rutile and anatase are highly reducible with moderate energy costs. Manganese ions are therefore present in a mixture of oxidation states. Photoexcited electrons and holes localize at cluster metal and oxygen sites, respectively. The interaction of water at the modified surfaces depends on the stoichiometry and spontaneous dissociation to surface bound hydroxyls is favored in the presence of oxygen vacancies and reduced metal cations. Comparisons with bare TiO 2 and other TiO 2 -based photocatalyst materials are presented throughout.