Titania is one of the most widely used benchmark standard photocatalysts in the field of environmental applications. However, the large band gap of titania and massive recombination of photogenerated charge carriers limit its overall photocatalytic efficiency. The former can be overcome by modifying the electronic band structure of titania including various strategies like coupling with a narrow band gap semiconductor, metal ion/nonmetal ion doping, codoping with two or more foreign ions, surface sensitization by organic dyes or metal complexes, and noble metal deposition. The latter can be corrected by changing the surface properties of titania by fluorination or sulfation or by the addition of suitable electron acceptors besides molecular oxygen in the reaction medium. This review encompasses several advancements made in these aspects, and also some of the new physical insights related to the charge transfer events like charge carrier generation, trapping, detrapping, and their transfer to surface are discussed for each strategy of the modified titania to support the conclusions derived. The synergistic effects in the mixed polymorphs of titania and also the theories proposed for their enhanced activity are reported. A recent venture on the synthesis and applications of anatase titania with a large percentage of reactive {001} facets and their band gap extension to the visible region via nonmetal ion doping which is a current hot topic is briefly outlined.

Surface-bulk modification of zinc oxide for efficient photocatalysis.

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Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The non-aqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

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Mn 2+ ion was doped into the sol-gel anatase TiO 2 in the concentration range of 0.02-0.1%. Powder X-ray diffraction results revealed that the phase transformation from anatase to rutile proceeds at a slower rate up to an intermediate dopant concentration of 0.06% and accelerates for a higher dopant concentration of 0.1%. In comparison with the previous studies, the phase transition temperature was reduced by 100 °C for the intermediate dopant concentration. The photocatalytic activity of Mn 2+ (0.06%)-TiO 2 for the degradation of an oxo-fused polycyclic aromatic dye, Indanthrane BR Violet, was almost equal to that of Degussa P-25 under UV light, but under solar light its efficiency was nearly 4 times higher. This enhanced activity can be attributed to the (i) synergistic effect in the bicrystalline framework of anatase and rutile, (ii) small crystallite size, and (iii) high intimate contact between both the phases. The correlation of the crystallite size with the synergistic effect on the photocatalytic activity is studied in detail.

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