Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Vertical growth and resonator properties of hexagonally shaped zinc oxide nanonails

We synthesized vertically aligned nail-shaped ZnO nanocrystal arrays on silicon substrates via a combination of a carbothermal reduction method and textured ZnO seeding layers that were precoated on silicon substrates by thermally decomposing zinc acetate, and studied their optical properties using cathodoluminescence (CL) and photoluminescence techniques. The ZnO nanonails show a sharp band-gap edge UV emission and a defect-related broad green emission. Monochromatic CL images of an individual ZnO nanonail show variations in spatial distributions of respective CL bands that had different origins. We attribute the spatial variation of CL images to an uneven distribution of luminescent defects and/or a structure-related light out-coupling from hexagonal ZnO nanostructures. The most distinct CL feature from the hexagonal head of an individual ZnO nanonail was the occurrence of a series of distinct resonant peaks within the visible wavelength range. It appeared that the head of a nanonail played the role of a hexagonal cavity so that polarizationdependent whispering gallery modes were stimulated by electron beam excitation.

Facet-controlled Self-assembly of ZnO Nanocrystals by Non-Hydrolytic Aminolysis and their Photodegradation Activities

We report a method for controlling the exposed facets and hence the dimensionality and shape of ZnO nanocrystals using a non-hydrolytic aminolysis synthesis route. The effects of changes to reaction conditions on ZnO formation were investigated and possible self-assembly mechanisms proposed. The crystal facet growth and hence morphologies of the ZnO nanocrystals were controlled by varying reaction temperature and the reactant ratio. Four distinct ZnO nanocrystal types were produced (nanocones, nanobullets, nanorods and nanoplates). The relative photocatalytic activities of the exposed facets of these ZnO nanostructures were also examined, which showed the activities obviously depended on the reactivity of exposed crystal facets in the order: {1011}>>{0001}, {1010}.

Efficient catalysts of zeolite nanocrystals grown with a preferred orientation on nanofibers

An innovative structure — nanozeolites (as shell) grown with preferred orientation on ceramic nanofibers (as core) was proposed. The Y-zeolite nanocrystals on TiO2 nanofibers exhibited superior ability to catalyze acetalization and carboxylation reaction, achieving high conversions to desired products with selectivity of 100% under moderate conditions.

Non-square-well potential profile and suppression of blinking in compositionally graded Cd1−xZnxSe/CdxZn1−xSe nanocrystals

Random blinking is a major problem on the way to successful applications of semiconducting nanocrystals in optoelectronics and photonics, which until recently had neither a practical solution nor a theoretical interpretation. An experimental breakthrough has recently been made by fabricating non-blinking Cd1-xZnxSe/ZnSe graded nanocrystals [Wang et al., Nature, 2009, 459, 686]. Here, we (1) report an unequivocal and detailed theoretical investigation to understand the properties (e.g., profile) of the potential-well and the distribution of Zn content with respect to the nanocrystal radius and (2) develop a strategy to find the relationship between the photoluminescence (PL) energy peaks and the potential-well due to Zn distribution in nanocrystals. It is demonstrated that the non-square-well potential can be varied in such a way that one can indeed control the PL intensity and the energy-level difference (PL energy peaks) accurately. This implies that one can either suppress the blinking altogether, or alternatively, manipulate the PL energy peaks and intensities systematically to achieve a controlled non-random intermittent luminescence. The approach developed here is based on the ionization energy approximation and as such is generic and can be applied to any non-free-electron nanocrystals.

Plasma-controlled nanocrystallinity and phase composition of TiO2 : a smart way to enhance biomimetic response

This contribution sheds light on the role of crystal size and phase composition in inducing biomimetic apatite growth on the surface of nanostructured titania films synthesized by reactive magnetron sputtering of Ti targets in Ar+O2 plasmas. Unlike most existing techniques, this method enables one to deposit highly crystalline titania films with a wide range of phase composition and nanocrystal size, without any substrate heating or postannealing. Moreover, by using this dry plasma-based method one can avoid surface hydroxylation at the deposition stage, almost inevitable in wet chemical processes. Results of this work show that high phase purity and optimum crystal size appear to be the essential requirement for efficient apatite formation on magnetron plasma-fabricated bioactive titania coatings. © 2006 Wiley Periodicals, Inc.