Pt2+ Dispersed in Ce0.83Ti0.15O2-delta: Significant Improvement in PROX Activity by Ti Substitution in CeO2 in Hydrogen Rich Stream

Pt2+ ion dispersed in CeO2, Ce1-xTixO2-delta and TiO2 have been tested for preferential oxidation of carbon monoxide (PROX) in hydrogen rich stream. It is found that Pt2+ substituted CeO2 and Ce(1-x)TixO(2-delta) in the form of solid solution Ce0.98Pt0.02O2-delta and Ce0.83Ti0.15Pt0.02O2-delta are highly CO selective low temperature PROX catalysts in hydrogen rich stream. Just 15% of Ti substitution in CeO2 improves the overall PROX activity.

Sonochemical synthesis of Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta nanocrystallites: oxygen storage material, CO oxidation and water gas shift catalyst

Nanocrystalline Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta of similar to 4 nm sizes were synthesized by a sonochemical method using diethyletriamine (DETA) as a complexing agent. Compounds were characterized by powder X-ray diffraction (XRD), X-ray photo-electron spectroscopy (XPS) and transmission electron microscopy (TEM). Ce1-xFexO2-delta (0 <= x <= 0.45) and Ce0.65Fe0.33Pd0.02O2-delta crystallize in fluorite structure where Fe is in +3, Ce is in +4 and Pd is in +2 oxidation state. Due to substitution of smaller Fe3+ ion in CeO2, lattice oxygen is activated and 33% Fe substituted CeO2 i.e. Ce0.67Fe0.33O1.835 reversibly releases 0.31O] up to 600 degrees C which is higher or comparable to the oxygen storage capacity of CeO2-ZrO2 based solid solutions (Catal. Today 2002, 74, 225-234). Due to interaction of redox potentials of Pd2+/0(0.89 V) and Fe3+/2+ (0.77 V) with Ce4+/3+ (1.61 V), Pd ion accelerates the electron transfer from Fe2+ to Ce4+ in Ce0.65Fe0.33Pd0.02O1.815, making it a high oxygen storage material as well as a highly active catalyst for CO oxidation and water gas shift reaction. The activation energy for CO oxidation with Ce0.65Fe0.33Pd0.02O1.815 is found to be as low as 38 kJ mol(-1). Ce0.67Fe0.33O1.835 and Ce0.65Fe0.33Pd0.02O1.815 have also shown high activity for the water gas shift reaction. CO conversion to CO2 is 100% H-2 specific with these catalysts and conversion rate was found to be as high 27.2 mu moles g(-1) s(-1) and the activation energy was found to be 46.4 kJ mol(-1) for Ce0.65Fe0.33Pd0.02O1.815.

CO oxidation by CeO(2)-Al(2)O(3)-CeAlO(3) hybrid oxides

A modified solution combustion technique was successfully used to synthesize sub-10 nm crystallites of hybrid CeO(2)-Al(2)O(3)-CeAlO(3). The fuel in the solution combustion was tuned to obtain mixed oxides and solid solutions of the compound. The compounds were characterized by X-ray diffraction, transmission electron microscopy and X-ray photoelectron spectroscopy. XRD and TEM analysis showed the substitution of Al(3+) ions in the CeO(2) matrix when a combination of glycine, urea, hexamine and oxalyl dihydrazide was used as fuel for the synthesis. The compounds showed high activity for CO oxidation and the activity of the compounds was dependent upon the composition of the oxide.

Activation of Lattice Oxygen of TiO2 by Pd2+ Ion: Correlation of Low-Temperature CO and Hydrocarbon Oxidation with Structure of Ti1-xPdxO2-x (x=0.01-0.03)

Lattice oxygen of TiO2 is activated by the substitution of Pd ion in its lattice. Ti1-xPdxO2-x (x = 0.01-0.03) have been synthesized by solution combustion method crystallizing in anatase TiO2 structure. Pd is in +2 oxidation state and Ti is in +4 oxidation state in the catalyst. Pd is more ionic in TiO2 lattice compared to Pd in PdO. Oxygen storage capacity defined by ``amount of oxygen that is used reversibly to oxidize CO'' is as high as 5100 mu mol/g of Ti0.97Pd0.03O1.97. Oxygen is extracted by CO to CO2 in absence of feed oxygen even at room temperature which is more than 20 times compared to pure TiO2. Rate of CO oxidation is 2.75 mu mol g(-1) s(-1) at 60 degrees C over Ti0.97Pd0.03O1.97 and C2H2 gets oxidized to CO2 and H2O at room temperature. Catalyst is not poisoned on long time operation of the reactor. Such high catalytic activity is due to activated lattice oxygen created by the substitution of Pd ion as seen from first-principles density functional theory (DFT) calculations with 96 atom supercells of Ti32O64, Ti31Pd1O63, Ti30Pd2O62, and Ti29Pd3O61. The compounds crystallize in anatase TiO2 structure with Pd2+ ion in nearly square planar geometry and TiO6 octahedra are distorted by the creation of weakly bound oxygens. Structural analysis of Ti31Pd1O63 which is close to 3% Pd ion substituted TiO2 shows that oxygens associated with both Ti and Pd ions in the lattice show bond valence sum of 1.87, a low value characteristic of weak oxygen in the lattice compared to oxygens with valence 2 and above in the same lattice. Exact positions of activated oxygens have been identified in the lattice from DFT calculations.

Investigations on structural and optical properties of co-doped (Ag, Co) ZnO nanoparticles

Undoped and co-doped (Ag, Co) ZnO powders were synthesized by chemical co-precipitation method without using any capping agent. The X-ray diffraction results indicate that the undoped and co-doped ZnO powders have pure hexagonal structure and are consisting of nanosized single-crystalline particles. The size of the nanoparticles increases with increasing Ag concentration from 1 to 5 mol% as compared to that of undoped ZnO. The presence of substitution dopants of Ag and Co in the ZnO host material was confirmed by the Energy dispersive analysis of X-rays (EDAX). Optical absorption measurements indicate blue shift and red-shift in the absorption band edge upon doping concentration of Ag and blue emission was observed by photoluminescence (PL) studies.

Synthesis and characterization of Fe- and Co-based ferrite nanoparticles and study of the T-1 and T-2 relaxivity of chitosan-coated particles

In pursuit of newer and more effective contrast agents for magnetic resonance imaging, we report in this article the use of biocompatible chitosan-coated ferrite nanoparticles of different kinds with a view to determine their potential applications as the contrast agents in the field of nuclear magnetic resonance. The single-phase ferrite particles were synthesized by chemical co-precipitation (CoFe2O4 and Fe3O4) and by applying ultrasonic vibration (CoFe2O4 and Co0.8Zn0.2Fe2O4). Although magnetic anisotropy of CoFe2O4 nanoparticle leads to finite coercivity even for nanoensembles, it has been reduced significantly to a minimum level by applying ultrasonic vibration. Fe3O4 synthesized by chemical co-precipitation yielded particles which already possess negligible coercivity and remanence. Substitution of Co by Zn in CoFe2O4 increases the magnetization significantly with a small increase in coercivity and remanence. Particles synthesized by the application of ultrasonic vibration leads to the higher values of T-2 relaxivities than by chemical coprecipitation. We report that the T-2 relaxivities of these particles are of two orders of magnitude higher than corresponding T-1 relaxivities. Thus, these particles are evidently suitable as contrast agent for T-2 weighted MR images.

Synthesis, microstructure and thermal expansion studies on Ca0 center dot 5+x/2Sr0 center dot 5+x/2Zr4P6-2x Si-2x O-24 system prepared by co-precipitation method

We report on the synthesis, microstructure and thermal expansion studies on Ca0 center dot 5 + x/2Sr0 center dot 5 + x/2Zr4P6 -aEuro parts per thousand 2x Si-2x O-24 (x = 0 center dot 00 to 1 center dot 00) system which belongs to NZP family of low thermal expansion ceramics. The ceramics synthesized by co-precipitation method at lower calcination and the sintering temperatures were in pure NZP phase up to x = 0 center dot 37. For x a parts per thousand yen 0 center dot 5, in addition to NZP phase, ZrSiO4 and Ca2P2O7 form as secondary phases after sintering. The bulk thermal expansion behaviour of the members of this system was studied from 30 to 850 A degrees C. The thermal expansion coefficient increases from a negative value to a positive value with the silicon substitution in place of phosphorous and a near zero thermal expansion was observed at x = 0 center dot 75. The amount of hysteresis between heating and cooling curves increases progressively from x = 0 center dot 00 to 0 center dot 37 and then decreases for x > 0 center dot 37. The results were analysed on the basis of formation of the silicon based glassy phase and increase in thermal expansion anisotropy with silicon substitution.

A naturally occurring amino acid substitution in the voltage-dependent sodium channel selectivity filter affects channel gating

The pore of sodium channels contains a selectivity filter made of 4 amino acids, D/E/K/A. In voltage sensitive sodium channel (Nav) channels from jellyfish to human the fourth amino acid is Ala. This Ala, when mutated to Asp, promotes slow inactivation. In some Nav channels of pufferfishes, the Ala is replaced with Gly. We studied the biophysical properties of an Ala-to-Gly substitution (A1529G) in rat Nav1.4 channel expressed in Xenopus oocytes alone or with a beta 1 subunit. The Ala-to-Gly substitution does not affect monovalent cation selectivity and positively shifts the voltage-dependent inactivation curve, although co-expression with a beta 1 subunit eliminates the difference between A1529G and WT. There is almost no difference in channel fast inactivation, but the beta 1 subunit accelerates WT current inactivation significantly more than it does the A1529G channels. The Ala-to-Gly substitution mainly influences the rate of recovery from slow inactivation. Again, the beta 1 subunit is less effective on speeding recovery of A1529G than the WT. We searched Nav channels in numerous databases and noted at least four other independent Ala-to-Gly substitutions in Nav channels in teleost fishes. Thus, the Ala-to-Gly substitution occurs more frequently than previously realized, possibly under selection for alterations of channel gating.

Thermoelectric properties of Fe(0.2)Co(3.8)Sbi(12-x)Te(x) skutterudites

Skutterudites Fe(0.)2Co(3.8)Sb(12),Te-x (x = 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.6) were synthesized by induction melting at 1273 K, followed by annealing at 923 K for 144 h. X-ray powder diffraction and electron microprobe analysis confirmed the presence of the skutterudite phase as the main phase. The temperature-dependent transport properties were measured for all the samples from 300 to 818 K. A positive Seebeck coefficient (holes are majority carriers) was obtained in Fe0.2Co3.8Sb 12 in the whole temperature range. Thermally excited carriers changed from n-type to p-type in Fe(0.)2Co(3.8)Sb(12),Te-x 19Te0.1 at 570 K, while in all the other samples, Fe(0.)2Co(3.8)Sb(12),Te-x (x = 0.2, 0.3, 0.4, 0.5, 0.6) exhibited negative Seebeck coefficients in the entire temperature range measured. Whereas for the alloys up to x = 0.2 (Fe(0.)2Co(3.8)Sb(12),Te-x ) the electrical resistivity decreased by charge compensation, it increased for x> 0.2 with an increase in Te content as a result of an increase in the electron concentration. The thermal conductivity decreased with Te substitution owing to carrier phonon scattering and point defect scattering. The maximum dimensionless thermoelectric figure of merit, ZT = 1.04 at 818 K, was obtained with an optimized Te content for Fe0.2Co3.8Sb1 1.5Te0.5 and a carrier concentration of,,J1/ =- 3.0 x 1020 CM-3 at room temperature. Thermal expansion (a = 8.8 x 10-6 K-1), as measured for Fe(0.)2Co(3.8)Sb(12),Te-x , compared well with that of undoped Co4Sb12. A further increase in the thermoelectric figure of merit up to ZT = 1.3 at 820 K was achieved for Fe(0.)2Co(3.8)Sb(12),Te-x , applying severe plastic deformation in terms of a high-pressure torsion process. (C) 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of zinc substitution on the nanocobalt ferrite powders for nanoelectronic devices

Zinc substituted cobalt ferrite powders {Co(1-x)ZnxFe2O4} (0.0 <= x <= 0.5) were prepared by the solution combustion method. The structural, morphological, magnetic and electrical properties of as synthesized samples were studied. Powder X-ray diffraction patterns reveals single phase, cubic spinel structure with space group No. Fd (3) over barm (227). As zinc concentration increases, the lattice constant increases and the crystallite size decreases. The minimum crystallite size of similar to 12 nm was observed for x = 0.5 composition. The synthesized ferrite compounds show ferrimagnetic behavior, with coercivity value of 10779 Oe (Hard ferrite) at 20 K and 1298 Oe (soft ferrite) at room temperature (RT). The maximum saturation magnetization recorded for the Co0.5Zn0.5Fe2O4 composition was 99.78 emu g(-1) and 63.83 emu g(-1) at 20 K and RT respectively. The dielectric parameters such as dielectric constant, loss tangent and AC conductivity were determined as a function of frequency at RT. The magnetic and dielectric properties of the samples illustrates that the materials were quite useful for the fabrication of nanoelectronic devices. (C) 2013 Elsevier B.V. All rights reserved.

An oxygen evolution Co-Ac catalyst - the synergistic effect of phosphate ions

Formation of an amorphous cobalt based oxygen evolution catalyst called Co-Pi has been recently reported from a neutral phosphate buffer solution containing Co2+. But the concentration of Co2+ is as low as 0.5 mM due to poor solubility of a cobalt salt in phosphate medium. In the present study, a cobalt acetate based oxygen evolution catalyst (Co-Ac) is prepared from a neutral acetate buffer solution, where the solubility of Co2+ is very high (>100 times in comparison with phosphate buffer solution). The Co-Ac possesses better catalytic activity than the Co-Pi with an additional advantage of easy bulk scale preparation. The comparative studies on the oxygen evolution reaction (OER) activity of Co-Ac and Co-Pi in phosphate and acetate buffer electrolytes reveal that the Co-Ac exhibits enhanced synergistic catalytic activity in phosphate solution, probably due to partial substitution of acetate in the catalyst layer by phosphate, resulting in the formation of a Co-Ac-Pi catalyst.

Thermoelectric properties of Co substituted synthetic tetrahedrite

Transition metal atom (Co) substituted synthetic tetrahedrite compounds Cu12-xCoxSb4S13 (x = 0, 0.5, 1.0, 1.5, 2.0) were prepared by solid state synthesis. X-Ray Diffraction (XRD) patterns revealed tetrahedrite as the main phase, whereas for the compounds with x = 0, 0.5 a trace of impurity phase Cu3SbS4 was observed. The surface morphology showed a large grain size with low porosity, which indicated appropriate compaction for the hot pressed samples. The phase purity, as monitored by Electron Probe Micro Analysis (EPMA) is in good agreement with the XRD data. The elemental composition for all the compounds almost matched with the nominal composition. The X-ray Photoelectron Spectroscopy (XPS) data showed that Cu existed in both +1 and +2 states, while Sb exhibited +3 oxidation states. Elastic modulus and hardness showed a systematic variation with increasing Co content. The electrical resistivity and Seebeck coefficient increased with increase in the doping content due to the decrease in the number of carriers caused by the substitution of Co2+ on the Cu1+ site. The positive Seebeck coefficient for all samples indicates that the dominant carriers are holes. A combined effect of resistivity and Seebeck coefficient leads to the maximum power factor of 1.76 mW m(-1) K-2 at 673 K for Cu11.5Co0.5Sb4S13. This could be due to the optimization in the carrier concentration by the partial substitution of Co2+ on both the Cu1+ as well as Cu2+ site at the same doping levels, which is also supported by the XPS data. The total thermal conductivity systematically decreased with increase of doping content as it is mainly influenced by the decrease of carrier thermal conductivity. The maximum thermoelectric figure of merit zT = 0.98 was obtained at 673 K for Cu11.5Co0.5Sb4S13. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Nickel substitution induced effects on gas sensing properties of cobalt ferrite nanoparticles

Ni2+ ion induced unusual conductivity reversal and an enhancement in the gas sensing properties of ferrites based gas sensors, is reported. The Co1-xNixFe2O4 (for x = 0, 0.5 and 1) nanoparticles were synthesized by wet chemical co-precipitation method and gas sensing properties were studied as a function of composition and temperature. The structural, morphological and microstructural characterization revealed crystallite size of in the range 10-20 nm with porous morphology consisting of nano-sized grains. The Energy Dispersive X-ray (EDX) mapping confirms homogeneous distribution of Co, Ni, Fe and O elements in the ferrites. The non-stoichiometry of the inverse spinel type ferrites and the relative concentration of Ni3+/Co3+ defects were studied using X-ray photoelectron spectroscopy. It is found that the addition of Ni2+ ions into cobalt ferrite shows preferred selectivity towards CO gas at high temperature (325 degrees C) and ethanol gas at low temperature (250 degrees C), unlike undoped cobalt ferrite or undoped nickel ferrite, which show similar response for both these gases. Moreover, an unusual conductivity reversal is observed, except cobalt ferrite due to the difference in reactivity of the gases as well as characteristic non-stoichiometry of ferrites. This behavior is highly gas ambient dependent and hence can be well-exploited for selective detection of gases. (C) 2015 Elsevier B.V. All rights reserved.

Effect of bismuth oxide introduction on spectroscopic properties of Er3+/Yb3+ co-doped aluminophosphate glasses

The absorption spectra, emission spectra and infrared spectra of Er3+/Yb3+ co-doped xBi(2)O(3)-(65 - x)P2O5-4Yb(2)O(3)-11Al(2)O(3)-5BaO-15Na(2)O were measured and investigated. Spontaneous emission probability, radiative lifetime and branching ratios of Er3+ were calculated according to the Judd-Ofelt theory. The role of substitution of Bi2O3 for P2O5 on luminescence of Er3+/Yb3+ co-doped aluminophosphate glasses has been investigated. The calculated radiative lifetimes (tau(rad)) for I-4(13/2) and I-4(11/2) were decreasing with Bi2O3 content increases, whereas the measured total lifetime (tau(meas)) for I-4(13/2) showed linearly increasing trends. The effect of Bi2O3 introduction on OH- groups was also discussed according to the IR transmittance spectra of glasses. It was found that FWHM of glasses were not affected with the substitution of Bi2O3 for P2O5. The emission spectra intensity increased with Bi2O3 content due to the decreases of phonon energy and OH- content in glasses. (C) 2007 Elsevier B.V. All rights reserved.

Synthesis and properties of novel fluorinated poly(phenylene-co-imide)s

A new class of high-performance materials, fluorinated poly(phenylene-co-imide)s, were prepared by Ni(0)-catalytic coupling of 2,5-dichlorobenzophenone with fluorinated dichlorophthalimide. The synthesized copolymers have high molecular weights ((M) over bar (W)= 5.74 x 10(4)-17.3 x 10(4) g center dot mol(-1)), and a combination of desirable properties such as high solubility in common organic solvent, film-forming ability, and excellent mechanical properties. The glass transition temperature (T(g)s) of the copolymers was readily tuned to be between 219 and 354 degrees C via systematic variation of the ratio of the two comonomers. The tough polymer films, obtained by casting from solution, had tensile strength, elongation at break, and tensile modulus values in the range of 66.7-266 MPa, 2.7-13.5%, and 3.13-4.09 GPa, respectively. The oxygen permeability coefficients (P-O2) and permeability selectivity of oxygen to nitrogen (P-O2/P-N2) of these copolymer membranes were in the range of 0.78-3.01 barrer [1 barrer = 10(-10) cm(3) (STP) cm/(cm(2) center dot s center dot cmHg)] and 5.09-6.2 5, respectively. Consequently, these materials have shown promise as engineering plastics and gas-separation membrane materials.