Synthesis and catalytic properties of cobalt- and molybdenum-containing mesoporous MCM-41 molecular sieves

Mesoporous MCM-41 type silicas containing molybdenum and cobalt have been prepared with pore sizes in the range 30-38 Angstrom and 54-59 Angstrom. Catalytic properties of these materials have been examined with respect to the oxidation of cyclooctene and aniline.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Dispersed ZrO2 nanoparticles in MCM-48 with high adsorption activity

A new two-step synthesis of ZrO2-MCM nanocomposites using the gel combustion technique was accomplished; the resulting material had a high-surface area and showed very high adsorption activity. The deposition of 25 nm ZrO2 particles over MCM was achieved using gel combustion technique with glycine as a fuel, and the formation of nanocomposites was confirmed using transmission electron microscopy. The composites were also characterized by XRD, SEM, FTIR and N2 adsorption-desorption analysis. The nanocomposites were tested for the adsorption of cationic dyes. High rates of adsorption and large dye uptake were observed over the nanocomposites. The rate of adsorption over the nanocomposites was higher than that observed for physical ZrO2-MCM mixtures and commercial activated carbon. The nanocomposite with 10 wt % ZrO2 showed the highest rate of adsorption owing to the synergistic effects of ZrO2 surface groups, smaller particle size, fine dispersion and high-surface area of the composite. (c) 2012 American Institute of Chemical Engineers AIChE J, 58: 29872996, 2012

Structure of the noncubic phase in the ferroelectric state of Pr-substituted SrTiO3

Sr1−xPrxTiO3 has recently been shown to exhibit ferroelectricity at room temperature. In this paper powder x-ray and neutron-diffraction patterns of this system at room temperature have been analyzed to show that the system exhibits cubic (Pm-3m) structure for x<=0.05 and tetragonal (I4/mcm) for x>0.05. The redundancy of the noncentrosymmetric structural model (I4cm) in the ferroelectric state suggests the absence of long-range ordered ferroelectric domains and supports the relaxor ferroelectric model for this system.

A new genotype of Neurospora crassa that selectively produces abundant microconidia in submerged shake culture

A new microcycle microconidiating strain (mcm) ofNeurospora crassa was derived by successive backcrosses of a soil isolate to a laboratory wild-type strain. Surface grown cultures show normal wild-type vegetative morphology. However, under continuous agitation in liquid cultures at 22°C, macroconidial germlings bypass the usual mycelial phase and produce abundant numbers of uninucleate microconidia within 24 h. Temperature and culture media affect the production of microconidia.

Inhibition of a Protein Tyrosine Phosphatase Using Mesoporous Oxides

The feasibility of utilizing mesoporous matrices of alumina and silica for the inhibition of enzymatic activity is presented here. These studies were performed on a protein tyrosine phosphatase by the name chick retinal tyrosine phosphotase-2 (CRYP-2), a protein that is identical in sequence to the human glomerular epithelial protein-1 and involved in hepatic carcinoma. The inhibition of CRYP-2 is of tremendous therapeutic importance. Inhibition of catalytic activity was examined using the Sustained delivery of p-nitrocatechol sulfate (pNCS) from bare and amine functionalized mesoporous silica (MCM-48) and mesoporous alumina (Al2O3). Among the various mesoporous matrices employed, amine functionalized MCM-48 exhibited the best release of pNCS and also inhibition of CRYP-2. The maximum speed of reaction nu(max) (= 160 +/- 10 mu mol/mnt/mg) and inhibition constant K-i (=85.0 +/- 5.0 mu mol) estimated using a competitive inhibition model were Found to be very similar to inhibition activities of protein tyrosine phosphatases using other methods.

Microcycle conidiation and its genetic basis in Neurospora crassa

Some wild isolates of Neurospora show microcycle conidiation in liquid culture under continuous agitation. Macroconidia from agar-grown mycelial cultures germinated in liquid and the germlings spontaneously produced conidia with no intervening mycelial phase. Three types of microcycle conidiation were seen among progeny of N. crassa Vickramam A x N. crassa a wild-type: (1) multinucleate blastoconidia produced by apical budding and septation, (2) multinucleate arthroconidia produced by holothallic septation and disarticulation of cells, and (3) uninucleate microconidia produced directly from conidiogenous cells of the germlings. Two genes were identified which control specific patterns of microcycle conidiogenesis. A single gene mcb in linkage group VR near al-3 (3.2% recombination) controls blastoconidiation. This gene is epistatic to gene mcm located in linkage group IIL, very near ro-7 (1.4%). mcm controls both microconidiation and arthroconidiation depending on temperature. Strains of genotype mcm produce microconidia almost exclusively at 18-22 degrees C, but arthroconidia with few or no microconidia at 30 degrees C. Because they result in rapid and synchronized conidiation in liquid culture, the two genes should be useful for studies of developmental gene regulation. mcm makes it possible to obtain large quantities of pure microconidia rapidly for experimentation.

Potentiometric determination of the gibbs energies of formation of SrZrO3 and BaZrO3

The Gibbs free energies of formation of strontium and barium zirconates have been determined in the temperature range 960 to 1210 K using electrochemical cells incorporating the respective alkaline-earth fluoride single crystals as solid electrolytes. Pure strontium and barium monoxides were used in the reference electrodes. During measurements on barium zirconate, the oxygen partial pressure in the gas phase over the electrodes was maintained at a low value of 18.7 Pa to minimize the solubility of barium peroxide in the monoxide phase. Strontium zirconate was found to undergo a phase transition from orthorhombic perovskite to) with space group Cmcm; D-2h(17) to tetragonal perovskite (t) having the space group 14/mcm; D-4h(18) at 1123 (+/- 10) K. Barium zirconate does not appear to undergo a phase transition in the temperature range of measurement. It has the cubic perovskite (c) structure. The standard free energies of formation of the zirconates from their component binary oxides AO (A = Sr, Ba) with rock salt (rs) and ZrO2 with monoclinic (m) structures can be expressed by the following relations:SrO (rs) + ZrO2 (m) --> SrZrO3 (o) Delta G degrees = -74,880 - 14.2T (+/-200) J mol(-1) SrO (rs) + ZrO2 (m) --> SrZrO3 (t) Delta G degrees = -73,645 - 15.3T (+/-200) J mol(-1) BaO (rs) + ZrO2 (m) --> BaZrO4 (c) Delta G degrees = -127,760 - 1.79T (+/-250) J mol(-1) The results of this study are in reasonable agreement with calorimetric measurements reported in the literature. Systematic trends in the stability of alkaline-earth zirconates having the stoichiometry AZrO(3) are discussed.

Esterification of stearic acid with p-cresol over modified Indian bentonite clay catalysts

The esterification of stearic acid with p-cresol using modified Indian bentonite clay catalysts has been reported. The reaction was studied over exchanged clays, acid activated clays, exchanged acid activated clays, aluminium pillared clay, aluminium pillared acid activated clay, molecular sieve Al-MCM-41, zeolite H beta, ZrO2, S-ZrO2, p-TSA, montmorillonite K10, and montmorillonite KSF in o-xylene for 6 h. The catalysts were characterized by X-ray diffraction and surface area measurements. The acidity was determined by n-butylamine back-titration method and DRIFTS after pyridine adsorption. Acid activated Indian bentonite (AAIB) was found to be a better catalyst compared to other catalysts in the esterification of stearic acid with p-cresol.

High Temperature Phase Transition Studies and Dielectric Properties of Sr2SbMnO6

Sr2SbMnO6 (SSMO) ceramics were, fabricated using the nanocrystalline powders obtained via molten salt synthesis (MSS) method. High temperature X-ray diffraction studies confirmed the structural phase transition (room temperature tetragonal (I4/mcm) to the cubic phase (Pm-3m)) temperature to be around 736K. The discontinuity in the phase transition indicated its first order nature reflecting the presence of ferroelectric-like distortions in SSMO prepared from MSS which seemed to be unique as it was not observed so far in the case of SSMO prepared using solid-state reaction method. The dielectric behavior of SSMO was studied in the 300-950 K temperature range at high frequencies (MHz range) in order to suppress the of space charge and related effects that dominate at such higher temperatures and mask the real phase transition.

Meso-Structured Silica-Nafion Hybrid Membranes for Direct Methanol Fuel Cells

A series of novel organic-inorganic hybrid membranes have been prepared employing Nafion and acid-functionalized meso-structured molecular sieves (MMS) with varying structures and surface area. Acid-functionalized silica nanopowder of surface area 60 m(2)/g, silica meso-structured cellular foam (MSU-F) of surface area 470 m(2)/g and silica meso-structured hexagonal frame network (MCM-41) of surface area 900 m(2)/g have been employed as potential filler materials to form hybrid membranes with Nafion framework. The structural behavior, water uptake, proton conductivity and methanol permeability of these hybrid membranes have been investigated. DMFCs employing Nafion-silica MSU-F and Nafion-silica MCM-41 hybrid membranes deliver peak-power densities of 127 mW/cm(2) and 100 mW/cm(2), respectively; while a peak-power density of only 48 mW/cm(2) is obtained with the DMFC employing pristine recast Nafion membrane under identical operating conditions. The aforesaid characteristics of the hybrid membranes could be exclusively attributed to the presence of pendant sulfonic acid groups in the filler, which provide fairly continuous proton-conducting pathways between filler and matrix in the hybrid membranes facilitating proton transport without any trade-off between its proton conductivity and methanol crossover. (C) 2012 The Electrochemical Society. DOI: 10.1149/2.036211jes] All rights reserved.

Evolution of structural phase coexistence in a half doped manganite Pr0.5Sr0.5MnO3: An evidence for magneto-structural coupling

Temperature dependent x-ray diffraction measurements have been performed to understand the implications of magnetic phase coexistence on crystallographic structure in a half-doped manganite Pr0.5Sr0.5MnO3. The compound shows a structural phase transition from high-temperature tetragonal-I4/mcm to low-temperature orthorhombic-Fmmm symmetry around the ferromagnetic to antiferro-magnetic transition. Rietveld analysis shows the coexistence of these two structures emerges at high temperature within the ferromagnetic state, and persists down to lowest temperature. Below around 40 K, however, this structural evolution stops, and a significant fraction (similar to 22%) of untransformed high-temperature phase remains. This agrees with earlier magnetization study, thus establishing its magneto-structural coupling. (C) 2012 Elsevier B.V. All rights reserved.

Mesostructured-aluminosilicate-Nafion hybrid membranes for direct methanol fuel cells

Organic-inorganic hybrid membranes are prepared from Nafion and acid functionalized aluminosilicate with varying structures and surface areas. Acid-functionalized mesostructured aluminosilicate with cellular foam framework (Al-MSU-F type) of surface area 463 m(2) g(-1), acid-functionalized aluminosilicate molecular sieves (Al-HMS type) of surface area 651 m(2) g(-1) and acid-functionalized mesostructured aluminosilicate with hexagonal network (Al-MCM-41 type) of surface area 799 m(2) g(-1) have been employed as potential filler materials to form hybrid membranes with Nafion. The structural behavior, water uptake, ion-exchange capacity, proton conductivity and methanol permeability of the hybrid membranes are extensively investigated. Direct methanol fuel cells (DMFCs) with Al-HMS-Nafion and Al-MCM-41-Nafion hybrid membranes deliver respective peak power-densities of 170 mW cm(-2) and 246 mW cm(-2), while a peak power-density of only 48 mW cm(-2) is obtained for the DMFC employing pristine recast-Nafion membrane under identical operating conditions. The unique properties associated with hybrid membranes could be exclusively attributed to the presence of pendant sulfonic-acid groups in the filler materials, which provide proton-conducting pathways between the filler and matrix in the hybrid membranes, and facilitate proton transport with adequate balance between proton conductivity and methanol permeability. (C) 2012 Elsevier Ltd. All rights reserved.