Advanced multifunctional inorganic nanostructured oxides for controlled release and sensing

ADVANCED MULTIFUNCTIONAL INORGANIC NANOSTRUCTURED OXIDES FOR CONTROLLED RELEASE AND SENSING. We demonstrate here certain examples of multifunctional nanostructured oxidematerials for biotechnological and environmental applications.Various in-house synthesized homogeneous nanostructured viz.mesoporous and nanotubes silica and titania have been employed for controlled drug delivery and electrochemical biosensing applications. Confinement of macromolecules such as proteins studied via electrochemical, thermal and spectroscopic methods showed no detrimental effect on native protein structure and function, thus suggesting effective utility of oxide nanostructures as bio-encapsulators. Multi-functionalitywas demonstrated via employing similar nanostructures for sensing organic water pollutants e.g. textile dyes.

Photocatalytic degradation with combustion synthesized WO3 and WO3-TiO2 mixed oxides under UV and visible light

The photocatalytic activity of commercial titanium dioxide under UV and visible radiation was improved by composites of tungsten trioxide (WO3) with TiO2. WO3 was prepared by solution combustion synthesis and the mixed oxides/composites of WO3-TiO2 were prepared in different weight ratios (0, 0.10, 0.15, 0.20, 0.25, 0.50, 0.75, and 1) by physical mixing. These catalysts were characterized by XRD, DRS, BET, SEM, TEM, pH drift method, TGA and photoluminescence. The photocatalytic activity varies with the WO3 loading in the composites. The optimum loading of WO3 in the composites was found to be 15 wt% for both UV and visible radiation. This loading showed faster dye degradation rate than commercial TiO2 (TiO2-C) and WO3 (WO3-C). The effect of initial concentrations of methylene blue (MB) and orange G (OG) and the effect of the functional group on dye degradation was studied with both anionic and cationic dyes with 15 wt% WO3-TiO2. (C) 2012 Elsevier B.V. All rights reserved.

Nanostructured Pd modified Ni/CeO2 catalyst for water gas shift and catalytic hydrogen combustion reaction

Nanostructured Pd-modified Ni/CeO2 catalyst was synthesized in a single step by solution combustion method and characterized by XRD, TEM, XPS, TPR and BET surface analyzer techniques. The catalytic performance of this compound was investigated by performing the water gas shift (WGS) and catalytic hydrogen combustion (CHC) reaction. The present compound is highly active and selective (100%) toward H-2 production for the WGS reaction. A lack of CO methanation activity is an important finding of present study and this is attributed to the ionic substitution of Pd and Ni species in CeO2. The creation of oxide vacancies due to ionic substitution of aliovalent ions induces dissociation of H2O that is responsible for the improved catalytic activity for WGS reaction. The combined H-2-TPR and XPS results show a synergism exists among Pd, Ni and ceria support. The redox reaction mechanism was used to correlate experimental data for the WGS reaction and a mechanism involving the interaction of adsorbed H-2 and O-2 through the hydroxyl species was proposed for CHC reaction. The parity plot shows a good correspondence between the experimental and predicted reaction rates. (c) 2012 Elsevier B.V. All rights reserved.

Optical and structural properties of nanostructured oxide thin films by sol‐gel technique

TiO2 and Al2O3 are commonly used materials in optical thin films in the visible and near‐infrared wavelength region due to their high transparency and good stability. In this work, TiO2 and Al2O3 single, and nano composite thin films with different compositions were deposited on glass and silicon substrates at room temperature using a sol‐gel spin coater. The optical properties like reflectance, transmittance and refractive index have been studied using Spectrophotometer, and structural properties using X‐Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM).

Organophotocatalysis in nanostructured soft gel materials as tunable reaction vessels: comparison with homogeneous and micellar solutions

Riboflavin tetraacetate-catalyzed aerobic photooxidation of 1-(4-methoxyphenyl)ethanol was investigated as a model reaction under blue visible light in different soft gel materials, aiming to establish their potential as reaction vessels for photochemical transformations. Three strategies involving different degrees of organization of the catalyst within the gel network were explored, and the results compared to those obtained in homogeneous and micellar solutions. In general, physical entrapment of both the catalyst and the substrate under optimized concentrations into several hydrogel matrices (including low-molecular-weight and biopolymer-based gels) allowed the photooxidation with conversions between 55 and 100% within 120 min (TOF similar to 0.045-0.08 min(-1); k(obs) similar to 0.011-0.028 min(-1)), albeit with first-order rates ca. 1-3-fold lower than in solution under comparable non-stirred conditions. Remarkably, the organogel made of a cyclohexane-based bisamide gelator in CH3CN not only prevented the photodegradation of the catalyst but also afforded full conversion in less than 60 min (TOF similar to 0.167 min(-1); k(obs) similar to 0.073 min(-1)) without the need of additional proton transfer mediators (e. g., thiourea) as it occurs in CH3CN solutions. In general, the gelators could be recycled without detriment to their gelation ability and reaction rates. Moreover, kinetics could be fine-tuned according to the characteristics of the gel media. For instance, entangled fibrillar networks with relatively high mechanical strength were usually associated with lower reaction rates, whereas wrinkled laminated morphologies seemed to favor the reaction. In addition, the kinetics results showed in most cases a good correlation with the aeration efficiency of the gel media.

A Comparison of mechanical and tribological behavior of nanostructured and conventional WC-12Co detonation-sprayed coatings

In the present study, WC-12Co coatings were deposited by detonation-spraying technique using conventional and nanostructured WC-12Co feedstock at four different oxy/fuel ratios (OF ratio). The coatings exhibited the presence of phases like W2C and W due to the decarburization of the WC phase, and the proportions of these phases were higher in the nano WC-12Co coatings compared with conventional WC-12Co coatings. Coating hardness and fracture toughness were measured. The tribological performance of coatings was examined under dry sand rubber wheel abrasion wear, and solid particle erosion wear conditions. The mechanical and wear properties of coatings were influenced by degree of decarburization and more so in the case of nanostructured WC-Co coatings. The results indicate that the extent of decarburization has a substantial influence on the elastic modulus of the coating which in turn is related to the extent of intersplat cracking of the coating.

Synthesis, morphology, optical and photocatalytic performance of nanostructured beta-Ga2O3

Fine powders of beta-Ga2O3 nanostructures were prepared via low temperature reflux condensation method by varying the pH value without using any surfactant. The pH value of reaction mixture had great influence on the morphology of final products. High crystalline single phase beta-Ga2O3 nanostructures were obtained by thermal treatment at 900 degrees C which was confirmed by X-ray diffraction and Raman spectroscopy. The morphological analysis revealed rod like nanostructures at lower and higher pH values of 6 and 10, while spindle like structures were obtained at pH = 8. The phase purity and presence of vibrational bands were identified using Fourier transform infrared spectroscopy. The optical absorbance spectrum showed intense absorption features in the UV spectral region. A broad blue emission peak centered at 441 nm due to donor-acceptor gallium-oxygen vacancy pair recombination appeared. The photocatalytic activity toward Rhodamine B under visible light irradiation was higher for nanorods at pH 10.

Nanostructured GdxZn1-xO thin films by nebulizer spray pyrolysis technique: Role of doping concentration on the structural and optical properties

Nanostructured GdxZn1-xO thin films with different Gd concentration from 0% to 10% deposited at 400 degrees C using the NSF technique. The films were characterized by structural, surface and optical properties, respectively. X-ray diffraction analysis shows that the Gd doped ZnO films have lattice parameters a = 3.2497 angstrom and c = 5.2018 angstrom with hexagonal structure and preferential orientation along (002) plane. The estimated values compare well with the standard values. When film thickness increases from 222 to 240 nm a high visible region transmittance (>70%) is observed. The optical band gap energy, optical constants (n and k), complex dielectric constants (epsilon(r), and epsilon(i)) and optical conductivities (sigma(r), and sigma(i)) were calculated from optical transmittance data. The optical band gap energy is 3.2 eV for pure ZnO film and 3.6 eV for Gd0.1Zn0.9-O film. The PL studies confirm the presence of a strong UV emission peak at 399 nm. Besides, the UV emission of ZnO films decreases with the increase of Gd doping concentration correspondingly the ultra-violet emission is replaced by blue and green emissions.

Variations in Magnetic Properties of Nanostructured Nickel

The magnetic properties of carbon nanotube encapsulated nickel nanowires (C. E. nanowires of diameter similar to 10 nm), and its comparison to other forms of Ni are carried out in this work. The saturation magnetization (M-s) and coercivity (H-c) for C. E. nanowires are 1.0 emu/g and 230 Oe. The temperature dependence of coercivity follows T-0.77 dependence indicating a superparamagnetic behavior. The field-cooled and zero-field-cooled plots indicate that the blocking temperature (T-B) similar to 300 K. These altered magnetic properties of C. E. nanowires are mainly due to the nanoscale confinement effect from carbon nanotube encapsulation. The shape and magnetic environment enhance the total magnetic anisotropy of C. E. nanowires by a factor of four.

Platinum surface additive based nanostructured CuO films for ethanol sensing

In the present work, Platinum (Pt)/Copper (II) oxide (CuO) thin film based ethanol sensors were fabricated by sputtering of Pt in varying concentrations over pre-sputtered nanostructured CuO films. The responses of these sensors as a function of Pt concentrations were studied using operating temperature modulation (200-450 °C) and ethanol concentration modulation (100-2500 ppm). During these modulations, it was found that the sensing response was maximum at operating temperature near 400 °C for all the samples irrespective of the Pt concentration dispersed over them. Moreover, the sensing behavior improves for lower Pt concentration (Pt/CuO-60s) and deteriorates for higher Pt concentration (Pt/CuO-120s). In comparison with bare CuO sample, the sensitivity of Pt/CuO-60s increased up to 22% in the linear range and 33% for maximum ethanol concentration. Hence, the well dispersed optimum Pt additive concentration improves the overall sensing behavior including sensitivity, linear working range and response as well as recovery time.

Nanostructured CexZn1-xO thin films: Influence of Ce doping on the structural, optical and electrical properties

Thin films of CexZn1-xO thin films were deposited on glass substrates at 400 degrees C by nebulizer spray pyrolysis technique. Ce doping concentration (x) was varied from 0 to 10%, in steps of 2.5%. X-ray diffraction reveals that all the films have polycrystalline nature with hexagonal crystal structure and high preferential orientation along (002) plane. Optical parameters such as; transmittance, band gap energy, refractive index (n), extinction coefficient (k), complex dielectric constants (epsilon(r), epsilon(i)) and optical conductivity (sigma(r), sigma(i)) have been determined and discussed with respect to Ce concentration. All the films exhibit transmittance above 80% in the wavelength range from 330 to 2500 nm. Optical transmission measurements indicate the decrease of direct band gap energy from 3.26 to 3.12 eV with the increase of Ce concentration. Photoluminescence spectra show strong near band edge emission centered similar to 398 nm and green emission centered similar to 528 nm with excitation wavelength similar to 350 nm. High resolution scanning electron micrographs indicate the formation of vertical nano-rod like structures on the film surface with average diameter similar to 41 nm. Electrical properties of the Ce doped ZnO film have been studied using ac impedance spectroscopy in the frequency range from 100 Hz-1 MHz at different temperatures. (C) 2013 Elsevier B.V. All rights reserved.

Structural Evolution and Phase Stability of Hume-Rothery Phase in a Mechanically Driven Nanostructured Ag-15 at. pct Sn Alloy

The paper reports phase evolution in mechanically driven Ag-15 at. pct Sn alloy powder starting with elemental powders in order to establish the feasibility of designing nanocomposites of a Ag-Sn solid solution. This alloy lies in the phase field of the hexagonal zeta-phase which is a well-known Hume-Rothery electron compound with an electron-to-atom ratio of about 1.45 and hexagonal crystal structure (a = 0.2966 nm, c = 0.4782 nm). Through a systematic use of X-ray diffraction and transmission electron microscopy, the results establish the formation of the zeta-phase which co-exists with the Ag solid solution during the initial phase of milling. Mechanical milling for long duration (55 hours) destabilizes the zeta-phase. A complete solid solution of Ag with a grain size of similar to 8 nm could be achieved after 60 hours of milling. Additional milling can induce decomposition of the solid solution that results in a reappearance of zeta-phase. We present a detailed thermodynamic calculation which indicates that complete Ag solid solution of the present alloy composition would be possible if the crystallites size can be reduced below a certain critical size. In particular, we show that both Ag and zeta-phase grain sizes need to be taken into account for determining the metastable equilibrium and the phase change that has been experimentally observed. Finally, we argue that recrystallization processes set a limit to the achievable size of the nanoparticles with metastable Ag solid solution.

Organic solar cell by using vertically aligned nanostructured ZnO nanorods

A low temperature solution approach was employed to grow zinc oxide (ZnO) nanorods with various aspect ratios. Various sizes (diameter-10-25nm) of the nanorods were grown by changing the concentrations of the growth solution. The length (50nm-500nm) of nanorods was controlled using growth times. These one-dimensional (1D) nanostructures with direct paths for a charge transport with high surface area for light harvesting, are promising candidates for organic photovoltaics (OPV). The structural and optical properties of the prepared ZnO nanorods have been studied using SEM, XRD and UV-Vis absorption spectroscopy. Using as-grown ZnO inverted OPV was fabricated. ZnO nanorods were subjected to various doses of UV-ozone irradiation which led to improvement in transmission and hence enhanced device performance.

Tailoring the Microstructural, Optical, and Electrical Properties of Nanocrystalline WO3 Thin Films Using Al Doping

We have studied the influence of Al doping on the microstructural, optical, and electrical properties of spray-deposited WO3 thin films. XRD analyses confirm that all the films are of polycrystalline WO3 in nature, possessing monoclinic structure. EDX profiles of the Al-doped films show aluminum peaks implying incorporation of Al ions into WO3 lattice. On Al doping, the average crystallite size decreases due to increase in the density of nucleation centers at the time of film growth. The observed variation in the lattice parameter values on Al doping is attributed to the incorporation of Al ions into WO3 lattice. Enhancement in the direct optical band gap compared to the undoped film has been observed on Al doping due to decrease in the width of allowed energy states near the conduction band edge. The refractive indices of the films follow the Cauchy relation of normal dispersion. Electrical resistivity compared to the undoped film has been found to increase on Al doping.

Nanostructured electrode materials for electrochemical energy storage and conversion

Manipulation of matter at the nanoscale is a way forward to move beyond our current choices in electrochemical energy storage and conversion technologies with promise of higher efficiency, environmental benignity, and cost-effectiveness. Electrochemical processes being basically surface phenomena, tailored multifunctional nanoarchitecturing can lead to improvements in terms of electronic and ionic conductivities, diffusion and mass transport, and electron transfer and electrocatalysis. The nanoscale is also a domain in which queer properties surface: those associated with conversion electrodes, ceramic particles enhancing the conductivity of polymer electrolytes, and transition metal oxide powders catalyzing fuel cell reactions, to cite a few. Although this review attempts to present a bird's eye view of the vast literature that has accumulated in this rather infant field, it also lists a few representative studies that establish the beneficial effects of going `nano'. Investigations on nanostructuring and use of nanoparticles and nanoarchitectures related to lithium-ion batteries (active materials and electrolytes), supercapacitors (electrical double-layer capacitors, supercapacitors based on pseudo-capacitance, and hybrid supercapacitors), and fuel cells (electrocatalysts, membranes and hydrogen storage materials) are highlighted. (C) 2012 John Wiley & Sons, Ltd.