An alkaline direct borohydride fuel cell with hydrogen peroxide as oxidant

A novel alkaline direct borohydride fuel cell (ADBFC) using varying concentrations of hydrogen peroxide as oxidant and sodium borohydride with sodium hydroxide, each of differing concentration, as fuel is reported. A peak power density of ca. 150 in W cm(-2) at a cell voltage of 540 mV can be achieved from the optimized ADBFC operating at 70 degrees C. (c) 2004 Elsevier B.V. All rights reserved.

Effect of fuel on the formation structure, transport and magnetic properties of LaMnO3+nanopowders

Single-step low-temperature solution combustion (LCS) synthesis was adopted for the preparation of LaMnO3+ (LM) nanopowders. The powders were well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS),surface area and Fourier transform infrared spectroscopy (FTIR). The PXRD of as-formed LM showed a cubic phase but, upon calcination (900degrees C, 6 h), it transformed into a rhombohedral phase. The effect of fuel on the formation of LM was examined, and its structure and magnetoresistance properties were investigated. Magnetoresistance (MR) measurements on LM were carried out at 0, 1, 4 and 7 T between 300 and 10 K. LM (fuel-to-oxidizer ratio; = 1) showed an MR of 17% at 1 T, whereas, for 4 and 7 T, it exhibited an MR of 45 and 55%, respectively, near the TM-I. Metallic resistivity data below TM-I showed that the double exchange interaction played a major role in this compound. It was interesting to observe that the sample calcined at 1200 degrees C for 3 h exhibited insulator behavior.

The influence of Zr/Ti content on the morphotropic phase boundary in the PZT-PZN system

A quantitative structural investigation was carried out on (1-y)PbZrxTi1-xO3-yPbZn(1/3)Nb(2/3)O(3) where y=0.1 and 0.2 ((1-y)PZT-yPZN). High resolution XRD data have been used for quantitative phase analysis. The nominal compositions were prepared by a two-step low temperature calcining solid-state method. The sintered samples show an average grain size of 1-2 mu m. It is demonstrated that the increase in the concentration of PZN leads to the shift of the morphotropic phase boundary (MPB) of PZT towards the PbZrO3 end member. In the present work, an effort has been made to quantitatively determine the MPB phase contents and to regain the coexistence of tetragonal and monoclinic phases by varying the value of x(i.e. Zr/Ti ratio). The width of the MPB becomes considerably larger for y=0.10 and 0.20 as compared to pure PZT. This is attributed to the considerably lower grain size of our samples resulting from the adopted preparation method. (C) 2010 Elsevier B.V. All rights reserved.

Pd and Pt ions as highly active sites for the water-gas shift reaction over combustion synthesized zirconia and zirconia-modified ceria

Noble metal substituted ionic catalysts were synthesized by solution combustion technique. The compounds were characterized by X-ray diffraction, FT-Raman spectroscopy, and X-ray photoelectron spectroscopy. Zirconia supported compounds crystallized in tetragonal phase. The solid solutions of ceria with zirconia crystallized in fluorite structure. The noble metals were substituted in ionic form.The water-gas shift reaction was carried out over the catalysts.Negligible conversions were observed with unsubstituted compounds. The substitution of a noble metal ion was found to enhance the reaction rate. Equilibrium conversion was obtained below 250 degrees C in the presence of Pt ion substituted compounds. The formation of Bronsted acid-Bronsted base pairs was proposed to explain the activity of zirconia catalysts. The effect of oxide ion vacancies on the reactions over substituted ceria-zirconia solid solutions was established. (c)2010 Elsevier B.V. All rights reserved.

Synthesis, Structure, and Magnetic Properties of Amine-Templated Transition-Metal Phosphites

Transition-metal phosphites of cobalt and vanadium, [C4N2H12][Co(HPO3)(2)] (I), [C4N2H14][Co(HPO3)(2)] (II), [Co[C4H8N12)(H2PO3)(2)] (III),[C4N2H14][(VF)-F-III(HPO3)(2)]center dot H2O (IV), and[C3N2H5](2)[V-4(III)(H2O)(3)(HPO3)(4)(HPO4)(3)] (V), have been synthesized and characterized. Organophosphorus esters were employed to stabilize cobalt in tetrahedral coordination and also to prepare the low-dimensional structures, which are otherwise difficult to synthesize. The structures have one- (I, II, IV), two- (III) and three-dimensionally (V) extended networks built up by the linking of metal polyhedra and phosphite units. Another vanadyl phosphite, [C2N2H10][((VO)-O-IV)(3)(H2O) (HPO3)(4)]center dot H2O,([15]) was also prepared and investigated extensively by ESR, magnetic susceptibility, and other studies. All the compounds in the present study exhibit antiferromagnetic interactions. Well-established magnetic models have been used to fit the experimental data. The compounds havealso been characterized in detail by using UV/Vis spectroscopic studies.

Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in ``Soggy Sand''Electrolytes

The role of oxide surface chemical composition and solvent on ion solvation and ion transport of ``soggy sand'' electrolytes are discussed here. A ``soggy sand'' electrolyte system comprising dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate methoxy polyethylene glycol solution was employed for the study. Static and dynamic rheology measurements show formation of an attractive particle network in the case of the composite with unmodified aerosil silica (i.e., with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e., for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. No enhancement in ionic conductivity compared to the liquid electrolyte was observed in the case of the unmodified silica. This was attributed to the existence of a very strong particle network, which led to the ``expulsion'' of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity dependent on the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol, and no percolation in ionic conductivity was observed.

Structure of Ce1-xSnxO2 and its relation to oxygen storage property from first-principles analysis

CeO2-SnO2 solid solution has been reported to possess high oxygen storage/release property which possibly originates from local structural distortion. We have performed first-principles based density functional calculations of Ce1-xSnxO2 structure (x=0, 0.25, 0.5, 1) to understand its structural stability in fluorite in comparison to rutile structure of the other end-member SnO2, and studied the local structural distortion induced by the dopant Sn ion. Analysis of relative energies of fluorite and rutile phases of CeO2, SnO2, and Ce1-xSnxO2 indicates that fluorite structure is the most stable for Ce1-xSnxO2 solid solution. An analysis of local structural distortions reflected in phonon dispersion show that SnO2 in fluorite structure is highly unstable while CeO2 in rutile structure is only weakly unstable. Thus, Sn in Ce1-xSnxO2-fluorite structure is associated with high local structural distortion whereas Ce in Ce1-xSnxO2-rutile structure, if formed, will show only marginal local distortion. Determination of M-O (M=Ce or Sn) bond lengths and analysis of Born effective charges for the optimized structure of Ce1-xSnxO2 show that local coordination of these cations changes from ideal eightfold coordination expected of fluorite lattice to 4+4 coordination, leading to generation of long and short Ce-O and Sn-O bonds in the doped structure. Bond valence analyses for all ions show the presence of oxygen with bond valence similar to 1.84. These weakly bonded oxygen ions are relevant for enhanced oxygen storage/release properties observed in Ce1-xSnxO2 solid solution. (C) 2010 American Institute of Physics.

Role of entropy in the stability of cobalt titanates

The standard molar Gibbs free energy of formation of Co2TiO4, CoTiO3,and CoTi2O5 as a function of temperature over an extended range (900 to 1675) K was measured using solid-state electrochemical cells incorporating yttria-stabilized zirconia as the electrolyte, with CoO as reference electrode and appropriate working electrodes. For the formation of the three compounds from their component oxides CoO with rock-salt and TiO2 with rutile structure, the Gibbs free energy changes are given by:Delta(f)G degrees((ox))(Co2TiO4) +/- 104/(J . mol(-1)) = -18865 - 4.108 (T/K)Delta(f)G degrees((ox))(CoTiO3) +/- 56/(J . mol(-1)) = -19627 + 2.542 (T/K) Delta(f)G degrees((ox))(CoTi2O5) +/- 52/(J . mol(-1)) = -6223 - 6.933 (T/K) Accurate values for enthalpy and entropy of formation were derived. The compounds Co2TiO4 with spinel structure and CoTi2O5 with pseudo-brookite structure were found to be entropy stabilized. The relatively high entropy of these compounds arises from the mixing of cations on specific crystallographic sites. The stoichiometry of CoTiO3 was confirmed by inert gas fusion analysis for oxygen. Because of partial oxidation of cobalt in air, the composition corresponding to the compound Co2TiO4 falls inside a two-phase field containing the spinet solid solution Co2TiO4-Co3O4 and CoTiO3. The spinel solid solution becomes progressively enriched in Co3O4 with decreasing temperature. (c) 2010 Elsevier Ltd. All rights reserved.

Crystal structure of an intermolecular 2:1 complex between adenine and thymine.Evidence for both Hoogsteen and `quasi-Watson-Crick' interactions

The titled complex, obtained by co-crystallization (EtOH/25 degrees C),is apparently the only known complex of the free bases. Its crystal structure, as determined by X-ray diffraction at both 90 K and 313 K, showed that one A-T pair involves a Hoogsteen interaction, and the other a Watson-Crick interaction but only with respect to the adenine unit. The absence of a clear-cut Watson-Crick base pair raises intriguing questions about the basis of the DNA double helix. (C) 2010 Elsevier Ltd. All rights reserved.

1,3,6-Trimethylpyrano[4,3-b]pyrrol-4(1H)-one

All the non-H atoms of the title compound, C10H11NO2, are almost coplanar [maximum deviation = 0.040 (3) angstrom]. The crystal structure is stabilized by C-H center dot center dot center dot O hydrogen bonds.

Investigation of activated transport in hole doped rare earth manganites in the high temperature paramagnetic regime

Electronic transport in the high temperature paramagnetic regime of the colossal magnetoresistive oxides, La(1-x)A(x)MnO(3), A=Ca, Sr, Ba, x similar or equal to 0.1-0.3, has been investigated using resistivity measurements. The main motivation for this work is to relook into the actual magnitude of the activation energy for transport in a number of manganites and study its variation as a function of hole doping (x), average A-site cation radius (< r(A)>), cationic disorder (sigma(2)) and strain (epsilon(zz)). We show that contrary to current practice, the description of a single activation energy in this phase is not entirely accurate. Our results clearly reveal a strong dependence of the activation energy on the hole doping as well as disorder. Comparing the results across different substituent species with different < r(A)> reveals the importance of sigma(2) as a metric to qualify any analysis based on (r(A)). (c) 2006 Elsevier Ltd. All rights reserved.

A Comparative Study of Aromaticity in Substituted Tetracyclic and Hexacyclic Thiophenes

We have studied the nature of aromaticity in expanded porphyrinic analogues of thiophenes formed by four and six thiophenes. Using density functional theory (DFT) we have analyzed the aromaticity of both the macrocycle and individual molecular fragments. We find paramagnetic annulenic ring currents in the case of tetracyclic molecules and diamagnetic annulenic ring currents for hexacyclic molecules. We have also studied the effect of substitution of benzene rings within the macrocycle. We find that as the number of benzene rings is increased the aromaticity increases for tetracyclic systems and decreases for hexacyclic systems. All the results have been analyzed with various microscopic parameters, including geometry, excitation gap, and NMR criteria.

A Durable PEFC with Carbon-Supported Pt-TiO2 Cathode: A Cause and Effect Study

Durability is central to the commercialization of polymer electrolyte fuel cells (PEFCs). The incorporation of TiO2 with platinum (Pt) ameliorates both the stability and catalytic activity of cathodes in relation to pristine Pt cathodes currently being used in PEFCs. PEFC cathodes comprising carbon-supported Pt-TiO2 (Pt-TiO2/C) exhibit higher durability in relation to Pt/C cathodes as evidenced by cell polarization, impedance, and cyclic voltammetry data. The degradation in performance of the Pt-TiO2/C cathodes is 10% after 5000 test cycles as against 28% for Pt/C cathodes. These data are in conformity with the electrochemical surface area and impedance values. Pt-TiO2/C cathodes can withstand even 10,000 test cycles with nominal effect on their performance. X-ray diffraction, transmission electron microscope, and cross-sectional field-emission-scanning electron microscope studies on the catalytic electrodes reflect that incorporating TiO2 with Pt helps in mitigating the aggregation of Pt particles and protects the Nafion membrane against peroxide radicals formed during the cathodic reduction of oxygen. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3421970] All rights reserved.

Influence of finite size effect on magnetic and magnetotransport properties of La0.5Sr0.5CoO3 thin films

We present a comprehensive study of the thickness dependent structural, magnetic and magnetotransport properties of oriented La0.5Sr0.5CoO3 thin films grown on LaAlO3 by Pulsed Laser Deposition. We observe that these films undergo a reduction in Curie temperature (T-c) with a decrease in film thickness, and it is found to be primarily caused by the finite size effect since the finite scaling law [T-c(infinity) T-c(t)/T-c(infinity) = (c/t)lambda holds good over the studied thickness range. We rule out the contribution from the strain induced suppression of Curie temperature with decreasing film thickness since all the films exhibit a constant out of plane tensile strain (0.5%) irrespective of their varying thickness. However, we observe that the coercivity of the films is an order of magnitude higher than that of the bulk due to the tensile strain. In addition, we also observe an increase in the magneto resistance peak and a decrease in coercivity and electrical resistivity with an increase in film thickness. (C) 2010 Elsevier Ltd. All rights reserved.

Dielectric properties of some MM′O4 and MTiM′O6 (M=Cr, Fe, Ga; M′=Nb, Ta, Sb) rutile-type oxides

We describe an investigation of the structure and dielectric properties of MM'O-4 and MTiM'O-6 rutile-type oxides for M = Cr, Fe, Ga and M' = Nb. Ta and Sb. All the oxides adopt a disordered rutile structure (P4(2)/mnm) at ambient temperature. A partial ordered trirutile-type structure is confirmed for FeTaO4 from the low temperature (17 K) neutron diffraction studies While both the MM'O-4 oxides (CrTaO4 and FeTaO4) investigated show a normal dielectric property MTiM'O-6 oxides for M = Fe, Cr and M' = Nb/Ta/Sb display a distinct relaxor/relaxor-like response. Significantly the corresponding gallium analogs, GaTiNbO6 and GaTiTaO6, do not show a relaxor response at T<500K (C) 2010 Elsevier Inc All rights reserved