Platinum Ion-Doped TiO2: High Catalytic Activity of Pt2+ with Oxide Ion Vacancy in Ti1-x4+Ptx2+O2-x Compared to Pt4+ without Oxide Ion Vacancy in Ti1-x4+Ptx4+O2

Ti0.97Pt0.032+O1.97 and Ti0.97Pt0.034+O2 have been synthesized by a solution combustion method using alanine and glycine as the fuels, respectively. Both crystallize in anatase TiO2 structure with 15 nm average crystallite size. X-ray photoelectron spectroscopy (XPS) confirmed Pt ions are in the 2+ state in Ti0.97Pt0.03O1.97 (alanine) and 4+ state in Ti0.97Pt0.03O2 (glycine). The rate of CO oxidation occurring over Ti0.97Pt0.032+O1.97 (0.76 mu mol.g(-1).s(-1)) is similar to 10, times more than that over Ti0.97Pt0.034+O2 at 60 degrees C (0.08 mu mol.g(-1).s(-1)). A large shift in 100% hydrocarbons conversion to lower temperature was observed for Pt2+ ion-substituted TiO2 relative 10 that for Pt4+ ion-substituted TiO2. After reoxidation of the reduced compound by H-2 as well as CO, Pt ions are stabilized in mixed valences, 2+ and 4+ states. The role of oxide ion vacancy has been demonstrated by CO oxidation and H-2 + O-2 recombination reactions in the presence and absence of O-2. We analyze the activated lattice oxygens upon substitution of Pt2+ and Pt4+ ions in TiO2, using first-principles density functional theory (DFT) calculations with supercells of Ti31Pt1O63, Ti30Pt2O62, and Ti29Pt3O61 for Pt2+ ion substitution and Ti31Pt1O64, Ti30Pt2O62, and Ti29Pt3O61 for Pt4+ ion substitution in TiO2. We find that the local structure of Pt2+ ion has a distorted square planar geometry and that of Pt4+ ion has an octahedral geometry similar to that of Ti4+ ion in pure TiO2. The change in coordination of Pt2+ ion gives rise to weakly bonded oxygens, and these oxygens are involved in high rates of catalytic reaction. Thus, the high catalytic activity results from synergistic roles of Pt2+ ion and oxide ion vacancy and weakly bonded lattice oxygen.

Effect of Net-Fluence on waveguide formation in ultrafast laser inscribed chalcogenide glass

Waveguides were fabricated on GeGaSEr chalcogenide glass using ultrafast laser inscription method. The thermal diffusion model is discussed for understanding the light matter interaction and shown the effect of net-fluence in waveguide formation on chalcogenide glass. (C) 2012 Optical Society of America

Laser receptive polyelectrolyte thin films doped with biosynthesized silver nanoparticles for antibacterial coatings and drug delivery applications

We report a simple method to fabricate multifunctional polyelectrolyte thin films to load and deliver the therapeutic drugs. The multilayer thin films were assembled by the electrostatic adsorption of poly (allylamine hydrochloride) (PAH) and dextran sulfate (DS). The silver nanoparticles (Ag NPs) biosynthesized from novel Hybanthus enneaspermus leaf extract as the reducing agent were successfully incorporated into the film. The biosynthesized Ag NPs showed excellent antimicrobial activity against the range of enteropathogens, which could be significantly enhanced when used with commercial antibiotics. The assembled silver nano composite multilayer films showed rupture and deformation when they are exposed to laser. The Ag NPs act as an energy absorption center, locally heat up the film and rupture it under laser treatment. The antibacterial drug, moxifloxacin hydrochloride (MH) was successfully loaded into the multilayer films. The total amount of MH release observed was about 63% which increased to 85% when subjected to laser light exposure. Thus, the polyelectrolyte thin film reported in our study has significant potential in the field of remote activated drug delivery, antibacterial coatings and wound dressings. (C) 2013 Elsevier B.V. All rights reserved.

Dielectric Function of Undoped and Doped Poly2-methoxy-5-(3 `,7 `-dimethyloctyloxy)-1,4-phenylene-vinylene] by Ellipsometry in a Wide Spectral Range

Ellipsometric measurements in a wide spectral range (from 0.05 to 6.5 eV) have been carried out on the organic semiconducting polymer, poly2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylene-vinylene] (MDMO-PPV), in both undoped and doped states. The real and imaginary parts of the dielectric function and the refractive index are determined accurately, provided that the layer thickness is measured independently. After doping, the optical properties show the presence of new peaks, which could be well-resolved by spectroscopic ellipsometry. Also for the doped material, the complex refractive index, with respect to the dielectric function, has been determined. The broadening of the optical transitions is due to the delocalization of polarons at higher doping level. The detailed information about the dielectric function as well as refractive index function obtained by spectroscopic ellipsometry allows not only qualitative but also quantitative description of the optical properties of the undoped/doped polymer. For the direct characterization of the optical properties of MDMO-PPV, ellipsometry turns out to be advantageous compared to conventional reflection and transmission measurements.

Physical and magnetic properties of (Co, Ag) doped ZnO nanoparticles

Undoped and (Co, Ag) co-doped ZnO nanostructure powders are synthesized by chemical precipitation method without using any capping agent and annealed in air ambient at 500 A degrees C for 1 h. Here, the Ag concentration is fixed at 5 mol% and Co concentration is increased from 0 to 5 mol%. The X-ray diffraction studies reveal that undoped and doped ZnO powders consist of pure hexagonal structure and nano-sized crystallites. The novel Raman peak at 530 cm(-1) has corroborated with the Co doped ZnO nanoparticles. Moreover, the PL studies reveal that as the Co doping concentration increases and it enters into ZnO lattice as substitutional dopant, it leads to the increase of oxygen vacancies (Vo) and zinc interstitials (Zn-i). From the magnetization measurements, it is noticed that the co-doped ZnO nanostructures exhibit considerably robust ferromagnetism i.e. 4.29 emu g(-1) even at room temperature. These (Co, Ag) co-doped ZnO nanopowders can be used in the fabrication of spintronic and optoelectronic device applications.

Electric field activated nonlinear anisotropic charge transport in doped polypyrrole

Electric field activated nonlinear transport is investigated in polypyrrole thin film in both in-plane and out-of-plane geometries down to 5 K and strong anisotropy is observed. A morphological model is suggested to explain the anisotropy through inter-chain and intra-chain transport. The deviation from the variable range hopping at low temperature is accounted by fluctuation assisted transport. From Zabrodaskii plots, it is found that electric field can tune the transport from insulating to metallic regime. Glazman-Matveev model is used to describe the nonlinear conduction. Field scaling analysis shows that conductance data at different temperature falls on to a single curve. Nonlinearity exponent, m(T) and characteristic length, L-E are estimated to characterize the transport in both the geometries. (C) 2013 AIP Publishing LLC.

Mechanical and electronic properties of pristine and Ni-doped Si, Ge, and Sn sheets

Silicene, a graphene analogue of silicon, has been generating immense interest due to its potential for applications in miniaturized devices. Unlike planar graphene, silicene prefers a buckled structure. Here we explore the possibility of stabilizing the planar form of silicene by Ni doping using first principles density functional theory based calculations. It is found that planar as well as buckled structure is stable for Ni-doped silicene, but the buckled sheet has slightly lower total energy. The planar silicene sheet has unstable phonon modes. A comparative study of the mechanical properties reveals that the in-plane stiffness of both the pristine and the doped planar silicene is higher compared to that of the buckled silicene. This suggests that planar silicene is mechanically more robust. Electronic structure calculations of the planar and buckled Ni-doped silicene show that the energy bands at the Dirac point transform from linear behavior to parabolic dispersion. Furthermore, we extend our study to Ge and Sn sheets that are also stable and the trends of comparable mechanical stability of the planar and buckled phases remain the same.

Origin of enhanced thermoelectric properties of doped CrSi2

Using first principles density functional theory, we report for CrSi2, a linear relationship between thermodynamic charge state transition levels of defects and maxima of thermopower T-m, thus proposing a unique way of tuning thermoelectric properties. We show for doped CrSi2 that the peak of thermopower occurs at the temperature which corresponds to the position of the defect transition level. Therefore, by modifying the defect transition level, a thermoelectric material with a given operational temperature can be designed.

Supercapacitors based on nitrogen-doped reduced graphene oxide and borocarbonitrides

Nitrogen-doped reduced giaphene oxide (RGO) samples with different nitrogen content, prepared by two different methods, as well as nitrogen-doped few-layer graphene have been investigated as supercapacitor electrodes. Two electrode measurements have been carried out both in aqueous (6 M KOH) and in ionic liquid media. Nitrogen-doped reduced graphene oxides exhibit satisfactory specific capacitance, the values reaching 126 F/g at a scan rate of 10 mV/s in aqueous medium. Besides providing supercapacitor characteristics, the study has shown the nitrogen content and surface area to be important factors. High surface-area borocarbonitrides, BxCyNz, prepared by the urea route appear to be excellent supercapacitor electrode materials. Thus, BC4.5N exhibits a specific capacitance of 169 F/g at a scan rate of 10 mV/s in aqueous medium. In an ionic liquid medium, nitrogen-doped RGO and BC4.5N exhibit specific capacitance values of 258 F/g and 240 F/g at a scan rate of 5 mV/s. The ionic liquid enables a larger operating voltage range of 0.0-2.5 V compared to 0.0-1 V in aqueous medium. (C) 2013 Elsevier Ltd. All rights reserved.

Combustion synthesis approach for spectral tuning of Eu doped CaAl2O4 phosphors

Despite being a particularly good emitter, use of divalent Eu has been seriously limited. This is because severe reducing environments or special hosts are needed during synthesis of divalent Eu containing phosphors. In this work we stabilize Eu in its 2+ state (in CaAl2O4) using an open-air solution combustion reaction. The impact of fuel (F) to oxidizer (O) molar ratios (F/O = 0.5-2.0) on luminescence properties is explored. Chromaticity of Eu:CaAl2O4 depends sensitively on the F/O ratio. In general, higher F/O inhibits Eu3+ and promotes Eu2+ formation, which in turn improves the quality of the blue phosphor. EPR spectra show inhomogeneous broadening effects with the increase in F/O ratio, which suggests that disorder creation is promoted when F/O is increase. This is also confirmed by an increase in emission line width in PL spectra, when F/O is increased. (C) 2013 Elsevier B.V. All rights reserved.

Controlled synthesis of TiO2 nanoparticles and nanospheres using a microwave assisted approach for their application in dye-sensitized solar cells

Rapid and facile synthesis of similar to 7 nm and similar to 100-400 nm nano-structures of anatase titania is achieved by exploiting the chemical nature of solvents through a microwave based approach. After using these nanostructures as a photoanode in dye-sensitized solar cells, a modest yet appreciable efficiency of 6.5% was achieved under the illumination of AM 1.5 G one sun (100 mW cm(-2)).

Correlations between mechanical and photoluminescence properties in Eu doped sodium bismuth titanate

Nanoindentation technique is utilized to examine mechanical property variation in Eu doped Na0.5Bi0.5 TiO3 (NBT). Doping levels of Eu in NBT is systematically varied. Dilute doping results in a linear reduction in both modulus and hardness. At higher concentrations, a recovery of the mechanical properties (to undoped NBT values) is observed. These experimental trends mirror variations in the optical emission intensities with Eu concentration. Observed trends are rationalized on the basis of a model, which hypothesizes phase segregation beyond a critical Eu doping level. Such segregation leads to the formation of pure NBT, nano-Eu saturated NBT, and nano-mixed Eu oxides in the microstructure. Pure NBT is optically inactive, while saturated Eu:NBT is a much better emitter when compared to europium oxide. Hence beyond the critical concentration, luminescence signal comes primarily from the saturated Eu:NBT phase. The model presented is supported by nanoindentation, and spectroscopic results. (C) 2013 Elsevier Ltd. All rights reserved.

Dielectric and electrical studies of Pr3+ doped nano CaSiO3 perovskite ceramics

CaSiO3 nano-ceramic powder doped with Pr3+ has been prepared by solution combustion method. The powder Ca0.5Pr0.05SiO3 is investigated for its dielectric and electrical properties at room temperature to study the effect of doping. The sample is characterized by X-ray diffraction and infrared spectroscopy. The size of either of volume elements of CaSiO3:Pr3+ estimated from transmission electron microscopy is about 180-200 nm. The sample shows colossal dielectric response at room temperature. This colossal dielectric behaviour follows Debye-type relaxation and can be explained by Maxwell-Wagner (MW) polarization. However, analysis of impedance and electric modulus data using Cole-Cole plot shows that it deviates from ideal Debye behaviour resulting from the distribution of relaxation times. The distribution in the relaxation times may be attributed to existence of electrically heterogeneous grains, insulating grain boundary, and electrode contact regions. Doping, thus, results in substantial modifications in the dielectric and electrical properties of the nano-ceramic CaSiO3. (C) 2013 Elsevier Ltd. All rights reserved.

On the mechanism of room temperature superconductivity in substitutionally doped graphene

A combined mechanism involving phononic and electronic processes is suggested for superconductivity in substitutionally doped graphene. The electronic mechanism is similar to the one used for doped fullerene system, MxC60 (M K, Rb, etc.) and triggered by bond polarization due to doped impurities such as B or Al. It is found that on increasing the doping, the superconducting critical temperature can be raised to room temperature. The details of the combined model are given along with the predicted values of T-c. (C) 2013 Elsevier Ltd. All rights reserved,

Origin of noise in two dimensionally doped Silicon and Germanium

We present the study of low-frequency noise, or 1/f noise, in degenerately doped Si: P and Ge: P delta-layers at low temperatures. For the Si: P d-layers we find that the noise is several orders of magnitude lower than that of bulk Si: P systems in the metallic regime and is one of the lowest values reported for doped semiconductors. Ge: P d-layers as a function of perpendicular magnetic field, shows a factor of two reduction in noise magnitude at the scale of B-phi, where B-phi is phase breaking field. We show that this is a characteristic feature of universal conductance fluctuations.