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

Surface modification of inorganic nanoparticles for development of organic–inorganic nanocomposites—A review

Characterizing the state of nanoparticles (such as size, surface charge, and degree of agglomeration) in aqueous suspensions and understanding the parameters that affect this state are imperative for toxicity investigations. In this study, the role of important factors such as solution ionic strength, pH, and particle surface chemistry that control nanoparticle dispersion was examined. The size and zeta potential of four TiO2 and three quantum dot samples dispersed in different solutions (including one physiological medium) were characterized. For 15 nm TiO2 dispersions, the increase of ionic strength from 0.001 M to 0.1 M led to a 50-fold increase in the hydrodynamic diameter, and the variation of pH resulted in significant change of particle surface charge and the hydrodynamic size. It was shown that both adsorbing multiply charged ions (e.g., pyrophosphate ions) onto the TiO2 nanoparticle surface and coating quantum dot nanocrystals with polymers (e.g., polyethylene glycol) suppressed agglomeration and stabilized the dispersions. DLVO theory was used to qualitatively understand nanoparticle dispersion stability. A methodology using different ultrasonication techniques (bath and probe) was developed to distinguish agglomerates from aggregates (strong bonds), and to estimate the extent of particle agglomeration. Probe ultrasonication performed better than bath ultrasonication in dispersing TiO2 agglomerates when the stabilizing agent sodium pyrophosphate was used. Commercially available Degussa P25 and in-house synthesized TiO2 nanoparticles were used to demonstrate identification of aggregated and agglomerated samples.

Characterization of size, surface charge, and agglomeration state of nanoparticle dispersions for toxicological studies

Silver nanoparticles (Ag-NPs) readily transform in the environment, which modifies their properties and alters their transport, fate, and toxicity. It is essential to consider such transformations when assessing the potential environmental impact of Ag-NPs. This review discusses the major transformation processes of Ag-NPs in various aqueous environments, particularly transformations of the metallic Ag cores caused by reactions with (in)organic ligands, and the effects of such transformations on physical and chemical stability and toxicity. Thermodynamic arguments are used to predict what forms of oxidized silver will predominate in various environmental scenarios. Silver binds strongly to sulfur (both organic and inorganic) in natural systems (fresh and sea waters) as well as in wastewater treatment plants, where most Ag-NPs are expected to be concentrated and then released. Sulfidation of Ag-NPs results in a significant decrease in their toxicity due to the lower solubility of silver sulfide, potentiall...

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Environmental transformations of silver nanoparticles: impact on stability and toxicity.

This review paper encompasses a detailed study of semiconductor metal oxide (SMO) gas sensors. It provides for a detailed comparison of SMO gas sensors with other gas sensors, especially for ammonia gas sensing. Different parameters which affect the performance (sensitivity, selectivity and stability) of SMO gas sensors are discussed here under. This paper also gives an insight about the dopant or impurity induced variations in the SMO materials used for gas sensing. It is concluded that dopants enhance the properties of SMOs for gas sensing applications by changing their microstructure and morphology, activation energy, electronic structure or band gap of the metal oxides. In some cases, dopants create defects in SMOs by generating oxygen vacancy or by forming solid solutions. These defects enhance the gas sensing properties. Different nanostructures (nanowires, nanotubes, heterojunctions), other than nanopowders have also been studied in this review. At the end, examples of SMOs are given to illustrate the potential use of different SMO materials for gas sensing.

Semiconductor metal oxide gas sensors: A review

Since the development of the first chemoresistive metal oxide based gas sensors, transducers with innovative properties have been prepared by a variety of wet- and dry-deposition methods. Among these, direct assembly of nanostructured films from the gas phase promises simple fabrication and control and with the appropriate synthesis and deposition methods nm to μm thick films, can be prepared. Dense structures are achieved by tuning chemical or vapor deposition methods whereas particulate films are obtained by deposition of airborne, mono- or polydisperse, aggregated or agglomerated nanoparticles. Innovative materials in non-equilibrium or sub-stoichiometric states are captured by rapid cooling during their synthesis. This Review presents some of the most common chemical and vapor-deposition methods for the synthesis of semiconductor metal oxide based detectors for chemical gas sensors. In addition, the synthesis of highly porous films by novel aerosol methods is discussed. A direct comparison of structural and chemical properties with sensing performance is given.

Semiconductor Gas Sensors: Dry Synthesis and Application

Ferroelectric e-WO3 nanoparticles were synthesized and stabilized above room temperature for the first time. A sensor based on this material was found to be highly sensitive and selective to acetone gas which will serve as a good candidate for diabetes diagnosis based on human breath analysis.

Ferroelectric WO3 Nanoparticles for Acetone Selective Detection

Nanostructured anatase TiO2 was produced by flame spray pyrolysis (FSP) and tested for sensing of volatile organic compounds and CO at 500 °C. The as-prepared powders were characterized by transmission/scanning electron microscopy, X-ray diffraction and nitrogen adsorption. Titania films about 30 μm thick on alumina substrates interdigitated with gold electrodes were prepared by drop-coating a heptanol suspension of these powders. The films showed a high signal of n-type sensor to isoprene, acetone and ethanol at concentrations ranging from 1 to 75 ppm in dry N2/O2 at 500 °C. The response (within seconds) and recovery (within minutes) times were very fast. Heat-treatment at 900 °C caused a nearly complete anatase to rutile transformation and a transition to p-type sensing behavior. That resulted in a poor sensor signal to all hydrocarbons tested and considerably longer recovery times than that of the anatase sensor. That rutile sensor could detect CO that the original, anatase sensor could not. For ethanol the sensor response changed back to n-type.

/pdf/sensing-of-organic-vapors-by-flame-made-tio2-nanoparticles-u6159j0yqe.pdf

Sensing of Organic Vapors by Flame-Made TiO2 Nanoparticles

Hybrid plasmonic-magnetic nanoparticles possess properties that are attractive in bioimaging, targeted drug delivery, in vivo diagnosis and therapy. The stability and toxicity, however, of such nanoparticles challenge their safe use today. Here, biocompatible, SiO2-coated, Janus-like Ag/Fe2O3 nanoparticles are prepared by one-step, scalable flame aerosol technology. A nanothin SiO2 shell around these multifunctional nanoparticles leaves intact their morphology, magnetic and plasmonic properties but minimizes the release of toxic Ag+ ions from the nanosilver surface and its direct contact with live cells. Furthermore, this silica shell hinders flocculation and allows for easy dispersion of such nanoparticles in aqueous and biological buffer (PBS) solutions without any extra functionalization step. As a result, these hybrid particles exhibited no cytotoxicity during bioimaging and remained stable in suspension with no signs of agglomeration and sedimentation or settling. Their performance as biomarkers was explored by selectively binding them with live tagged Raji and HeLa cells enabling their detection under dark-filed illumination. Therefore, these SiO2-coated Ag/Fe2O3 nanoparticles do not exhibit the limiting physical properties of each individual component but retain their desired functionalities facilitating thus, the safe use of such hybrid nanoparticles in bio-applications.

/pdf/hybrid-silica-coated-janus-like-plasmonic-magnetic-2vai72bbt4.pdf

Hybrid, silica-coated, Janus-like plasmonic-magnetic nanoparticles.

Effective iron fortification of foods is difficult, because water-soluble compounds that are well absorbed, such as ferrous sulphate (FeSO(4)), often cause unacceptable changes in the colour or taste of foods. Poorly water-soluble compounds, on the other hand, cause fewer sensory changes, but are not well absorbed. Here, we show that poorly water-soluble nanosized Fe and Fe/Zn compounds (specific surface area approximately 190 m(2) g(-1)) made by scalable flame aerosol technology have in vivo iron bioavailability in rats comparable to FeSO(4) and cause less colour change in reactive food matrices than conventional iron fortificants. The addition of Zn to FePO(4) and Mg to Fe/Zn oxide increases Fe absorption from the compounds, and doping with Mg also improves their colour. After feeding rats with nanostructured iron-containing compounds, no stainable Fe was detected in their gut wall, gut-associated lymphatics or other tissues, suggesting no adverse effects. Nanosizing of poorly water-soluble Fe compounds sharply increases their absorption and nutritional value.

Alexandra Teleki

Papers

Semiconductor Gas Sensors: Dry Synthesis and Application

Ferroelectric WO3 Nanoparticles for Acetone Selective Detection

Sensing of Organic Vapors by Flame-Made TiO2 Nanoparticles

Hybrid, silica-coated, Janus-like plasmonic-magnetic nanoparticles.

Iron from nanocompounds containing iron and zinc is highly bioavailable in rats without tissue accumulation