Titanium dioxide, TiO2, is an important photocatalytic material that exists as two main polymorphs, anatase and rutile. The presence of either or both of these phases impacts on the photocatalytic performance of the material. The present work reviews the anatase to rutile phase transformation. The synthesis and properties of anatase and rutile are examined, followed by a discussion of the thermodynamics of the phase transformation and the factors affecting its observation. A comprehensive analysis of the reported effects of dopants on the anatase to rutile phase transformation and the mechanisms by which these effects are brought about is presented in this review, yielding a plot of the cationic radius versus the valence characterised by a distinct boundary between inhibitors and promoters of the phase transformation. Further, the likely effects of dopant elements, including those for which experimental data are unavailable, on the phase transformation are deduced and presented on the basis of this analysis.

https://link.springer.com/content/pdf/10.1007%2Fs10853-010-5113-0.pdf

Review of the anatase to rutile phase transformation

UV-Visible ار راد ن .د TiO2 ( تیفرظ راون مان هب نورتکلا یاراد یژرنا زارت لماش VB و ) رگید زارت ی یژرنا اب ( ییاناسر راون مان هب نورتکلا زا یلاخ و رتلااب VB یم ) .دشاب ت ود نیا نیب یژرنا توافت یژرنا فاکش زار ، پگ دناب هدیمان یم .دوش هک ینامز زا نورتکلا لاقتنا VB هب VB یم ماجنا دریگ ، TiO2 اب ودح یژرنا بذج د ev 2 / 3 ، نورتکلا تفج کی دیلوت یم هرفح .دیامن و نورتکلا هرفح ی نا اب هدش دیلوت یم کرتشم حطس هب لاقت ثعاب دناوت شنکاو ماجنا اه یی ددرگ . TiO2 دربراک ،دراد یدایز یاه هلمج زا یم ناوت اوه یگدولآ هیفصت یارب (CO2) و بآ و ... نآ زا هدافتسا درک .

Advanced Nanoarchitectures for Solar Photocatalytic Applications

Hybrid nanostructures composed of semiconductor and plasmonic metal components are receiving extensive attention. They display extraordinary optical characteristics that are derived from the simultaneous existence and close conjunction of localized surface plasmon resonance and semiconduction, as well as the synergistic interactions between the two components. They have been widely studied for photocatalysis, plasmon-enhanced spectroscopy, biotechnology, and solar cells. In this review, the developments in the field of (plasmonic metal)/semiconductor hybrid nanostructures are comprehensively described. The preparation of the hybrid nanostructures is first presented according to the semiconductor type, as well as the nanostructure morphology. The plasmonic properties and the enabled applications of the hybrid nanostructures are then elucidated. Lastly, possible future research in this burgeoning field is discussed.

Metal/Semiconductor Hybrid Nanostructures for Plasmon-Enhanced Applications

Owing to the unique mechanism of photoelectron storage and release, long persistent phosphorescence, also called long persistent luminescence or long lasting afterglow/phosphorescence, plays a pivotal role in the areas of spectroscopy, photochemistry, photonics and materials science. In recent years, more research has focused on the manipulation of the morphology, operational wavebands and persistent duration of long persistent phosphors (LPPs). These desired achievements stimulated the growing interest in designing bio-labels, photocatalysts, optical sensors, detectors and photonic devices. In this review, we present multidisciplinary research on synthetic methods, afterglow mechanisms, characterization techniques, materials system, and applications of LPPs. First, we introduce the recent developments in LPPs for the synthesis of nanoparticles from the aspects of particle sizes, monodispersity and homogeneity based on the urgent application of bio-imaging. In the later sections, we present the possible mechanisms, which involve the variation of trap distribution during the trapping and de-trapping process, complicated photo-ionization reaction of trap site levels and impurity centers together with their corresponding migration kinetics of carriers. Meanwhile, we emphasize the characterization techniques of defects, used to qualitatively or quantitatively describe the types, concentrations and depths of the traps. This review article also highlights the recent advances in suggested LPPs materials with a focus on the LPPs' hosts and optically active centers as well as their control, tuning and intrinsic links. We further discuss the classification of LPPs based on the different emission and excitation wavebands from the ultraviolet to the near-infrared region along with an overview of the activation mode of afterglow. Afterwards, we provide an exhibition of new products towards diverse application fields, including solar energy utilization, bio-imaging, diagnosis, and photocatalysts. Finally, we summarize the current achievements, discuss the problems and provide suggestions for potential future directions in the aforementioned parts.

Long persistent phosphors—from fundamentals to applications

Hydrothermal technology for nanotechnology

High purity, spherical anatase nanocrystals were prepared by a modified sol−gel method. Mixing of anhydrous TiCl4 with ethanol at about 0 °C yielded a yellowish sol that was transformed into phase-pure anatase of 7.7 nm in size after baking at 87 °C for 3 days. This synthesis route eliminates the presence of fine seeds of the nanoscale brookite phase that frequently occurs in low-temperature formation reactions and also significantly retards the phase transformation to rutile at high temperatures. Heating the as-is 7.7 nm anatase for 2 h at temperatures up to 600 °C leads to an increase in grain size of the anatase nanoparticles to 32 nm. By varying the calcination time from 2 to 48 h at 300 °C, the particle size could be controlled between 12 and 15.3 nm. The grain growth kinetics of anatase nanoparticles was found to follow the equation, D2 − D02 = k0tme(-Ea/RT) with a time exponent m = 0.286(±9) and an activation energy of Ea = 32 ± 2 kJ·mol-1. Thermogravimetric analysis in combination with infrared an...

High Purity Anatase TiO2 Nanocrystals: Near Room-Temperature Synthesis, Grain Growth Kinetics, and Surface Hydration Chemistry

Scheelite nanostructures Ca1−2x(Eu,Na)2xWO4 (0 < x ≤ 0.135) were prepared from 5 nm Ca0.968(Eu,Na)0.032WO4 by hydrothermal treatment. The preparation of 5 nm Ca0.968(Eu,Na)0.032WO4 at room temperature and subsequent hydrothermal treatment allow control over chemical compositions and particle size of CaWO4-based red phosphors that has not yet possible when using traditional preparation methods. By careful structural and electronic characterization, it is shown that simultaneous substitutions of Eu3+ and Na+ at Ca2+ sites were possible using this methodology, which allows one to vary the local symmetry surrounding Eu3+ and moreover the energy transfer from O2− to Eu3+ and tungstate groups to Eu3+ for optimum luminescence. As a consequence, the obtained CaWO4-based nanocrystals displayed excellent luminescence properties as demonstrated by luminescence lifetimes of milliseconds, abnormally narrowed emissions, and maximum quantum efficiencies of 92%. The results reported in this work show that it is possible ...

Synthesis and Optimum Luminescence of CaWO4-Based Red Phosphors with Codoping of Eu3+ and Na+

The nature of room-temperature ferromagnetism in diluted magnetic semiconductors, ZnO:M (M is Ni, Co, Fe, etc.), remains in debate, most likely because previous theoretical and experimental studies have excluded the magnetic contribution from secondary phases of transition metal oxide nanocrystals including NiO and CoO. In this work, the authors initiated a study on NiO nanocrystals that demonstrated room-temperature ferromagnetic behavior with relatively large coercive forces, in apparent contradiction to the previous conjectures in the literature. With size reduction, NiO nanocrystals showed an abnormal magnetic crossover, which is closely related to weakened superexchange interactions in their multisublattices.

Magnetic crossover of NiO nanocrystals at room temperature

Specific heats (15−350 K) have been measured on 7 nm TiO2 anatase and rutile nanoparticles containing significant amounts of surface-adsorbed water. By successively reducing the water content without changing particle size, we observed two types of water behavior. The specific heat of bare 7 nm particles was estimated using the water specific heats. Contrary to previous literature reports, the bare small particle specific heats are the same as those of the bulk, within experimental error.

Surface water and the origin of the positive excess specific heat for 7 nm rutile and anatase nanoparticles

Highly crystalline Zn1−xCoxO nanorods were prepared using a hydrothermal method. With increasing Co2+ dopant concentration, the lattice volume enlarged considerably, which is associated with the enhanced repulsive interactions of defect dipole moments on the wall surfaces. This lattice modification produced a significant decrease in band gap energies with its magnitude that followed the relationship, ΔEg=ΔE0∙(e−xB−1), where x and B are Co2+ dopant concentration and a constant, respectively. The abnormal band gap energies were indicated to originate from the sp-d exchange interactions that are proportional to the square of lattice volume.

Liping Li

Papers

High Purity Anatase TiO2 Nanocrystals: Near Room-Temperature Synthesis, Grain Growth Kinetics, and Surface Hydration Chemistry

Synthesis and Optimum Luminescence of CaWO4-Based Red Phosphors with Codoping of Eu3+ and Na+

Magnetic crossover of NiO nanocrystals at room temperature

Surface water and the origin of the positive excess specific heat for 7 nm rutile and anatase nanoparticles

Nature of the abnormal band gap narrowing in highly crystalline Zn1-xCoxO nanorods