Support-Dependent Activity of Noble Metal Substituted Oxide Catalysts for the Water Gas Shift Reaction

The water gas shift reaction was carried out over noble metal ion substituted nanocrystalline oxide catalysts with different supports. Spectroscopic studies of the catalysts before and after the reaction showed different surface phenomena occurring over the catalysts. Reaction mechanisms were proposed based upon the surface processes and intermediates formed. The dual site mechanism utilizing the oxide ion vacancies for water dissociation and metal ions for CO adsorption was proposed to describe the kinetics of the reaction over the reducible oxides like CeO2. A mechanism based on the interaction of adsorbed CO and the hydroxyl group was proposed for the reaction over ZrO2. A hybrid mechanism based on oxide ion vacancies and surface hydroxyl groups was proposed for the reaction over TiO2. The deactivation of the catalysts was also found to be support dependent. Kinetic models for both activation and deactivation were proposed. (C) 2010 American Institute of Chemical Engineers AIChE J, 56: 2662-2676, 2010

Graphene analogue BCN: Femtosecond nonlinear optical susceptibility and hot carrier dynamics

Third-order nonlinear absorption and refraction coefficients of a few-layer boron carbon nitride (BCN) and reduced graphene oxide (RGO) suspensions have been measured at 3.2 eV in the femtosecond regime. Optical limiting behavior is exhibited by BCN as compared to saturable absorption in RGO. Nondegenerate time-resolved differential transmissions from BCN and RGO show different relaxation times. These differences in the optical nonlinearity and carrier dynamics are discussed in the light of semiconducting electronic band structure of BCN vis-a-vis the Dirac linear band structure of graphene. (C) 2010 Elsevier B.V. All rights reserved.

Impact of energy quantisation in single electron transistor island on hybrid complementary metal oxide semiconductor-single electron transistor integrated circuits

For the first time, the impact of energy quantisation in single electron transistor (SET) island on the performance of hybrid complementary metal oxide semiconductor (CMOS)-SET transistor circuits has been studied. It has been shown through simple analytical models that energy quantisation primarily increases the Coulomb Blockade area and Coulomb Blockade oscillation periodicity of the SET device and thus influences the performance of hybrid CMOS-SET circuits. A novel computer aided design (CAD) framework has been developed for hybrid CMOS-SET co-simulation, which uses Monte Carlo (MC) simulator for SET devices along with conventional SPICE for metal oxide semiconductor devices. Using this co-simulation framework, the effects of energy quantisation have been studied for some hybrid circuits, namely, SETMOS, multiband voltage filter and multiple valued logic circuits. Although energy quantisation immensely deteriorates the performance of the hybrid circuits, it has been shown that the performance degradation because of energy quantisation can be compensated by properly tuning the bias current of the current-biased SET devices within the hybrid CMOS-SET circuits. Although this study is primarily done by exhaustive MC simulation, effort has also been put to develop first-order compact model for SET that includes energy quantisation effects. Finally, it has been demonstrated that one can predict the SET behaviour under energy quantisation with reasonable accuracy by slightly modifying the existing SET compact models that are valid for metallic devices having continuous energy states.

Activity–Composition Relations in the Nickel Oxide–Magnesium Oxide System at 1300 K by the Solid-State Galvanic Cell Technique

The activity of NiO in NiO-MgO rock salt solid solution has been measured at 1300 K by employing a solid-state galvanic cell: Pt,Ni+ NiO||(CaO)ZrO2||Ni + (Nix,Mgl-x)O, Pt. A high-density tube of Zr02-15 mol% CaO has been used as the solid electrolyte for the emf measurements. The activities of the component oxides in the rock salt solid solution exhibit negative deviation from ideality at the temperature of investigation. The solid solution obeys regular solution behavior at 1300 K. The value of the regular solution parameter is found to be -12000 ((l000) J mol-1. The composition dependence of ΔGEx obtained in this study agrees reasonably well with the calorimetric data reported in the literature for NiO-MgO solid solution.

Structural, optical and electrical characteristics of transparent bismuth vanadate films deposited on indium tin oxide coated glass substrates

Bismuth vanadate (BVO) thin films were fabricated on indium tin oxide (ITO) coated glass substrates using pulsed laser ablation technique and investigated their structural, optical and electrical properties. The use of the indium tin oxide coated glass substrate resulted in reducing the leakage current characteristics of crystalline BVO thin films. The X-ray diffraction (XRD) studies confirmed the monophasic nature of the post annealed (500 A degrees C/1 h) films. The atomic force microscopy indicated the homogeneous distribution of crystallites in the as-deposited films. The as-deposited and the post annealed films were almost 90% transparent (380-900 nm) as confirmed by optical transmission studies. Dielectric constant of around 52 was attained accompanied by the low dielectric loss of 0.002 at 10 kHz for post annealed films. The leakage current of the post annealed BVO films on ITO coated glass substrates measured at room temperature was 8.1 x 10(-8) A at an applied electric field of 33 kV/cm, which was lower than that of the films with platinum and SrRuO3 as the bottom electrodes.

Transition metal oxide perovskites by photoelectron and x-ray absorption spectroscopy

X-ray and ultraviolet photoelectron spectroscopy as well as x-ray absorption spectroscopy have been employed to investigate transition metal oxide perovskites of the general formula ABOs (A=La or rare-earth ion, B=trivalent transition metalion). Systematics in the core levels and in the valence bands in the series of LaBOa compounds have been discussed. Lanthanum chemical shifts in the x-ray absorption spectra in this series show interesting trends. Photoelectron spectra of the solid solutions, LaNil_x Coxes, LaNix_x FexO8 and LaFel_x Coxes show that the rigid band model is applicable to these systems. It is shown that x-ray photoelectron spectroscopy can be employed to identify multiple oxidation states of transition metal ions in oxide perovskites.

Synthesis of graphene oxide-intercalated alpha-hydroxides by metathesis and their decomposition to graphene/metal oxide composites

Graphene oxide-intercalated alpha-metal hydroxides were prepared using layers from the delaminated colloidal dispersions of cetyltrimethylammonium-intercalated graphene oxide and dodecylsulfate-intercalated alpha-hydroxide of nickel/cobalt as precursors. The reaction of the two dispersions leads to de-intercalation of the interlayer ions from both the layered solids and the intercalation of the negatively charged graphene oxide sheets between the positively charged layers of the alpha-hydroxide. Thermal decomposition of the intercalated solids yields graphene/nanocrystalline metal oxide composites. Electron microscopy analysis of the composites indicates that the nanoparticles are intercalated between graphene layers. (C) 2010 Elsevier Ltd. All rights reserved.

Reactivity with hydrogen of pure iron oxide and of iron oxides doped with oxides of Mn, Co, Ni and Cu

Using dynamic TG in H2, X-ray powder diffraction and Mössbauer Spectroscopy the reactivities fot hydrogen reduction of Fe2O3 prepared at different temperatures, Fe2O3 doped with oxides of Mn, Co, Ni and Cu prepared at 300DaggerC from nitrate precursors and intermediate spinels derived from above samples during reduction have been explored. The reactivity is higher for finely divided Fe2O3 prepared at 250DaggerC. The reduction is retarded by Mn, marginally affected by Co and accelerated by Ni and Cu, especially at higher (5 at.%) dopant concentration. These reactivities confirmed also by isothermal experiments, are ascribed to the nature of disorder in the metastable intermediate spinels and to hydrogen rsquospill overrsquo effects.

Synthesis and spectral studies of polyamide-phosphate esters from phosphine-oxide-containing diols with aryl phosphorodichloridates and their thermal and flammability behaviour

Polyamide-phosphate esters were synthesized by interfacial polycondensation of aryl phosphorodichloridates with the diols of phenoxaphosphine and phosphine oxide in the presence of a phase-transfer catalyst. The polymers were characterized by infra-red and 1H, 13C and 31P nuclear magnetic resonance (n.m.r.) spectroscopy. The molecular weights were determined by end-group analysis using 31P n.m.r. spectral data. The phenoxaphosphine-containing polymers showed superior thermostability and flame retardancy over the phosphine-oxide-containing polymers.

Terminal solid solubilities at 900–1000°C in the magnesium oxide-zinc oxide system measured using a magnesium fluoride solid-electrolyte galvanic cell

The terminal solid solubilities of the periclase (MgO-rich) and zincite (ZnO-rich) solid solutions in the MgO---ZnO system have been determined by measuring the activity of MgO using a solid-state galvanic cell of the type 02(g), Pt/MgO, MgF2//MgF2//{χMgO+(1-χ)ZnO}(s, sln), MgF2/Pt, O2(g) in the temperature range 900–1050°C. The ZnO activity was calculated by graphical Gibbs-Duhem integration. The activity-composition plots of both components exhibit a strong positive deviation from ideality and are characterised by a miscibility gap. The terminal solid solubilities of the periclase and zincite solid solutions obtained from the activity-composition plots are found to be in reasonable agreement with those reported in the literature.

Nuclear-quadrupole resonance in coordination chemistry- identification of bridiging and therminal chlorines in the mercuric chloride-4-picoline n-oxide complex

The temperature dependence of the chlorine-35 n.q.r. in the mercuric chloride-4-picoline N-oxide complex has been studied from 77 K to room temperature, and the results are used to assign the observed frequencies to terminal and bridging chlorines.