Synthesis and photocatalytic performance of quasi-fibrous ZnO

The combustion of oxidizer zinc nitrate and fuel oxalic acid results in quasi-fibrous zinc oxide. The processing parameters including oxidizer to fuel ratio, time and temperature were optimized for the resultant crystal structure and morphology. Pure hexagonal phase formation does not depend on the fuel ratio, but a stoichiometric ratio of oxidizer to fuel at 450 degrees C and 30 min results in highly crystalline ZnO with 3 mu m length and 0.5 mu m width. This quasi-fiber originates from partial fusion of near spherical, similar to 60 nm particles during the rapid rate of reaction in the combustion process. Transmission electron microscopic analysis confirms the anisotropic primary particle orientation and pore distribution within the developed quasi-fibrous particles. The degradation of methyl orange was assessed by degrading the dye in the presence of the synthesized ZnO (2.95 eV) under both UV and visible light. Quasi-fibrous zinc oxide exhibits effective photocatalytic efficiency under visible light irradiation.

Enhancing the photocatalytic efficiency of sprayed ZnO thin films through double doping (Sn plus F) and annealing under different ambiences

Doubly (Sn + F) doped zinc oxide (ZnO:Sn:F) thin films were deposited onto glass substrates using a simplified spray pyrolysis technique. The deposited films were annealed at 400 degrees C under two different ambiences (air and vacuum) for 2 h. The photocatalytic activity of these films was assessed through photocatalytic decolorization kinetics of Methylene Blue (MB) dye and the decolorization efficiency of the annealed films was compared with that of their as-deposited counterpart. The photocatalytic studies reveal that the ZnO:Sn:F films annealed under vacuum environment exhibits better photocatalytic efficiency when compared with both air annealed and as-deposited films. The SEM and TEM images depict that the surface of each of the films has an overlayer comprising of nanobars formed on a bottom layer, having spherical grains. The studies show that the diameter of the nanobars plays crucial role in enhancing the photocatalytic activity of the ZnO:Sn:F films. The structural, optical and electrical studies substantiate the discussions on the photocatalytic ability of the deposited films. (C) 2014 Elsevier B.V. All rights reserved.

Studying Microstructure in Molecular Crystals With Nanoindentation: Intergrowth Polymorphism in Felodipine

Intergrowth polymorphism refers to the existence of distinct structural domains within a single crystal of a compound. The phenomenon is exhibited by form II of the active pharmaceutical ingredient felodipine, and the associated microstructure is a significant feature of the compound's structural identity. Employing the technique of nanoindentation on form II reveals a bimodal mechanical response on specific single-crystal faces, demonstrating distinct properties for two polymorphic forms within the same crystal.

Herringbone to cofacial solid state packing via H-bonding in diketopyrrolopyrrole (DPP) based molecular crystals: influence on charge transport

Themono-alkylation of DPP derivatives leads to cofacial pi-pi stacking via H-bonding unlike their di-alkylated counterparts, which exhibit a classical herringbone packing pattern. Single crystal organic field-effect transistor (OFET) measurements reveal a significant enhancement of charge carrier mobility for mono-hexyl DPP derivatives.

ZnO/ITO core/shell nanostructure electrodes for future prototype solar cell devices

The impact of indium tin oxide (ITO) layers over vertically aligned zinc oxide nanorods (ZnO NRs) has been investigated to consider ITO nanolayers as transparent conducting oxide electrodes (TCOE) for hierarchical heteronanostructure solar cell devices that have ZnO nanostructures as branches. ZnO/ITO core/shell nanostructures were prepared in two- steps using vapor-liquid-solid and evaporation processes, and further the structures were annealed at various temperatures. Transmission electron microscopic studies show that the as-grown ZnO/ITO structures consist of an amorphous ITO shell on single crystalline ZnO cores, whereas the structures annealed above 300 degrees C consist of a single crystalline ITO shell. ITO layer deposited ZnO NRs exhibit a small red-shift in ZnO near-band-edge emission as well as optical band gap. The electrical measurements carried out on single ZnO/ITO core/shell NR under dark and UV light showed excellent thermionic transport properties. From these investigations it is emphasized that ITO nanolayers could be used as TCO electrodes for prototype ZnO based hierarchical solar cell devices.

An insight to the low temperature conduction mechanism of c-axis grown Al-doped ZnO, a widely used transparent conducting oxide

Al-doped ZnO thin films were synthesized from oxygen reactive co-sputtering of Al and Zn targets. Explicit doping of Al in the highly c-axis oriented crystalline films of ZnO was manifested in terms of structural optical and electrical properties. Electrical conduction with different extent of Al doping into the crystal lattice of ZnO (AZnO) were characterized by frequency dependent (40 Hz-50 MHz) resistance. From the frequency dependent resistance, the ac conduction of them, and correlations of localized charge particles in the crystalline films were studied. The dc conduction at the low frequency region was found to increase from 8.623 mu A to 1.14 mA for the samples AZnO1 (1 wt% Al) and AZnO2 (2 wt% Al), respectively. For the sample AZnO10 (10 wt% Al) low frequency dc conduction was not found due to the electrode polarization effect. The measure of the correlation length by inverse of threshold frequency (omega(0)) showed that on application of a dc electric field such length decreases and the decrease in correlation parameter(s) indicates that the correlation between potentials wells of charge particles decreases for the unidirectional nature of dc bias. The comparison between the correlation length and the extent of correlation in the doped ZnO could not be made due to the observation of several threshold frequencies at the extent of higher doping. Such threshold frequencies were explained by the population possibility of correlated charge carriers that responded at different frequencies. For AZnO2 (2% Al), the temperature dependent (from 4.5 to 288 K) resistance study showed that the variable range hopping mechanism was the most dominating conduction mechanism at higher temperature whereas at low temperature region it was influenced by the small polaronic hopping conduction mechanism. There was no significant influence found in these mechanisms on applications of 1, 2 and 3 V as biases.

Simple chemical aqueous synthesis of dahlia nanoflower consisting of finger-like ZnO nanorods and observation of stable ultraviolet photoluminescence emission

In this work, we have reported the synthesis of dahlia flower-like ZnO nanostructures consisting of human finger-like nanorods by the hydrothermal method at 120 degrees C and without using any capping agent. Optical properties of the samples, including UV-vis absorption and photoluminescence (PL) emission characteristics are determined by dispersing the samples in water as well as in ethanol media. The quenching of PL emission intensity along-with the red shifting of the PL emission peak are observed when the samples are dispersed in water in comparison to those obtained after dispersing the samples in ethanol. It has been found that PL emission characteristic, particularly the spectral nature of PL emission, of the samples remains almost unaltered (except some improvement in UV PL emission) even after thermally annealing it for 2 h at the temperature of 300 degrees C. Also the synthesized powder samples, kept in a plastic container, showed a very stable PL emission even after 15 months of synthesis. Therefore, the synthesized samples might be useful for their applications in future optoelectronics devices. (C) 2014 Elsevier Ltd. All rights reserved.

Enhanced photocatalytic efficiency of AuPd nanoalloy decorated ZnO-reduced graphene oxide nanocomposites

Inhibition of electron-hole pair recombination is the most desirable solution for stimulating photocatalytic activity in semiconductor nanostructures. To implement this, herein we study the photocatalytic efficiency of elemental Au, Pd and bimetallic AuPd nanoalloy decorated pristine and reduced graphene oxide (RGO) hybridized ZnO nanorods for degrading rhodamine 6G (R6G) dye. Fabrication of Au, Pd and AuPd nanoalloy on pristine and RGO modified ZnO nanorods is simple and more importantly surfactant or polymer free. AuPd nanoalloyed ZnO-RGO nanocomposites exhibit higher photocatalytic activity for degrading dye than both Au and Pd hybridized ones, indicating the promising potential of bimetallic nanoalloys over elemental components. A non-monotonic dependence on the composite composition was found by analyzing photodegradation efficiency of a series of ZnO-RGO-AuPd hybrid nanostructures with different weight percentages of RGO. The hybrid nanostructure ZnO-RGO (5 wt%)-AuPd (1 wt%) exhibits highest photodegradation efficiency (similar to 100% degradation in 20 min) with an improvement in rate constant (k) by a factor of 10 compared to that of the ZnO-RGO nanocomposite. The enhancement of the photocatalytic activity is attributed to the better separation of photogenerated charge carriers in photocatalysts thereby suggesting possible usefulness in a broad range of applications, such as sensing, photocatalysis and solar energy conversion.

Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Highly efficient WO3-ZnO mixed oxides for photocatalysis

Monoclinic nanocuboid WO3 enhanced the photocatalyst efficiency of quasi nanobelt zinc oxide for dye degradation in the presence of visible light radiation. Combustion synthesized ZnO resulted in a belt-like morphology through in situ cluster formation of near spherical particles but homogenously disperses and strongly adheres to nanocuboid WO3 during physical mixing. Cationic methylene blue (MB) and anionic orange G (OG) undergo degradation through a charge transfer mechanism in the presence of WO3-ZnO (1 : 9 weight percentage ratio) mixture. The photocatalytic reaction was enhanced due to the reduction in the recombination of photogenerated electron-holes. The high degree of 90% degradation of both dyes is due to the activity of the mixed oxides, which is much higher than that obtained either with WO3 or ZnO individually.

Morphology controlled synthesis of Al doped ZnO nanosheets on Al alloy substrate by low-temperature solution growth method

We report the morphology-controlled synthesis of aluminium (Al) doped zinc oxide (ZnO) nanosheets on Al alloy (AA-6061) substrate by a low-temperature solution growth method without using any external seed layer and doping process. Doped ZnO nanosheets were obtained at low temperatures of 60-90 degrees C for the growth time of 4 hours. In addition to the synthesis, the effect of growth temperature on the morphological changes of ZnO nanosheets is also reported. As-synthesized nanosheets are characterized by FE-SEM, XRD TEM and XPS for their morphology, crystallinity, microstructure and compositional analysis respectively. The doping of Al in ZnO nanosheets is confirmed with EDXS and XPS. Furthermore, the effect of growth temperature on the morphological changes was studied in the range of 50 to 95 degrees C. It was found that the thickness and height of the nanosheets varied with respect to the growth temperature. The study has given an important insight into the structural morphology with respect to the growth temperature, which in turn enabled us to determine the growth temperature window for the ZnO nanosheets. These Al doped ZnO nanosheets have potential application possibilities in gas sensors, solar cells and energy harvesting devices like nanogenerators.

Nanorod to quantum dot conversion in ZnO dispersions with co-surfactants

A chemically-induced nanorod to quantum dot transition is reported in ZnO. This transition is achieved using co-surfactants in a marginally polar solvent in chimie douce (soft chemical) conditions. This is different from the physical instability driven transitions reported so far in metal nanowires and polymers. We propose a suitable mechanism for the observed phenomenon.

Synthesis, luminescence properties and EPR investigation of hydrothermally derived uniform ZnO hexagonal rods

One-dimensional (1D) zinc oxide (ZnO) hexagonal rods have been successfully synthesized by surfactant free hydrothermal process at different temperatures. It can be found that the reaction temperature play a crucial role in the formation of ZnO uniform hexagonal rods. The possible formation processes of 1-D ZnO hexagonal rods were investigated. The zinc hydroxide acts as the morphology-formative intermediate for the formation of ZnO nanorods. Upon excitation at 325 nm, the sample prepared at 180 degrees C show several emission bands at 400 nm (similar to 3.10 eV), 420 nm (similar to 2.95 eV), 482 nm (similar to 2.57 eV) and 524 nm (similar to 2.36 eV) corresponding to different kind of defects. TL studies were carried out by pre-irradiating samples with gamma-rays ranging from 1 to 7 kGy at room temperature. A well resolved glow peak at similar to 354 degrees C was recorded which can be ascribed to deep traps. Furthermore, the defects associated with surface states in ZnO nano-structures are characterized by electron paramagnetic resonance. (C) 2014 Elsevier B.V. All rights reserved.

Tuning Mechanical Properties of Pharmaceutical Crystals with Multicomponent Crystals: Voriconazole as a Case Study

Crystals of voriconazole, an antifungal drug, are soft in nature, and this is disadvantageous during compaction studies where pressure is applied on the solid. Crystal engineering is used to make cocrystals and salts with modified mechanical properties (e.g., hardness). Cocrystals with biologically safe coformers such as fumaric acid, 4-hydroxybenzoic acid, and 4-aminobenzoic acid and salts with hydrochloric acid and oxalic acid are prepared through solvent assisted grinding. The presence (salt) or absence (cocrystal) of proton transfer in these multicomponent crystals is unambiguously confirmed with single crystal X-ray diffraction. All the cocrystals have 1:1 stoichiometry, whereas salts exhibit variable stoichiometries such as HCl salt (1:2) and oxalate salts (1:1.5 and 1:1). The nanoindentation technique was applied on single crystals of the salts and cocrystals. The salts exhibit better hardness than the drug and cocrystals in the order salts drug cocrystals. The molecular origin of this mechanical modulation is explained on the basis of slip planes in the crystal structure and relative orientations of the molecules with respect to the nanoindentation direction. The hydrochloride salt is the hardest solid in this family. This may be useful for tableting of the drug during formulation and in drug development.

Designing Elastic Organic Crystals: Highly Flexible Polyhalogenated N-Benzylideneanilines

The intermolecular interactions and structural features in crystals of seven halogenated N-benzylideneanilines (Schiff bases), all of which exhibit remarkable flexibility, were examined to identify the common packing features that are the raison d'etre for the observed elasticity. The following two features, in part related, were identified as essential to obtain elastic organic crystals: 1)A multitude of weak and dispersive interactions, including halogen bonds, which may act as structural buffers for deformation through easy rupture and reformation during bending; and 2)corrugated packing patterns that would get interlocked and, in the process, prevent long-range sliding of molecular planes.