Xavier, K O; Chacko, J; Mohammed Yusuff, K K(Elsevier, Applied Catalysis A :General, September 4, 2003)
[+]
[-]
Abstract:
Co(II), Ni(II) and Cu(II) complexes of dimethylglyoxime and N,N-ethylenebis(7-methylsalicylideneamine) have been synthesized in situ
in Y zeolite by the reaction of ion-exchanged metal ions with the flexible ligand molecules that had diffused into the cavities. The hybrid
materials obtained have been characterized by elemental analysis, SEM, XRD, surface area, pore volume, magnetic moment, FTIR, UV-Vis
and EPR techniques. Analysis of data indicates the formation of complexes in the pores without affecting the zeolite framework structure, the
absence of any extraneous species and the geometry of encapsulated complexes. The catalytic activities for hydrogen peroxide decomposition
and oxidation of benzyl alcohol and ethylbenzene of zeolite complexes are reported. Zeolite Cu(II) complexes were found to be more active
than the corresponding Co(II) and Ni(II) complexes for oxidation reactions. The catalytic properties of the complexes are influenced by their
geometry and by the steric environment of the active sites. Zeolite complexes are stable enough to be reused and are suitable to be utilized as
partial oxidation catalysts.
Manju, Kurian; Sugunan, S(Indian Journal of Chemistry, October , 2003)
[+]
[-]
Abstract:
Iron, aluminium and mixed iron aluminium pillared clays have been prepared by partial hydrolysis method and doped
with IO% Mo, V and Cr. The samples have been characterised by XRD, FTIR and surface area and pore Volume
measurements. The surface acid site distribution has been determined by temperature programmed desorption of ammonia.
Vanadia incorporated systems show maximum acidity. Benzylation of o-xylene has been done as probe reaction to test
catalytic activity. Benzyl chloride is a superior benzylating agent compared to benzyl alcohol in activity and selectivity.
Cent percent selectivity towards monobenzylated product is obtained in all the cases. Fe pillared systems exhibit maximum
activity. The catalytic activities of the systems can be correlated with the amount of strong add sites. The effects of various
reaction variables on the reaction have been studied. Presence of moisture has a diminishing effect on the reaction rate.
Sreekumar, K(Taylor and francis, October 20, 2003)
[+]
[-]
Abstract:
Polymer materials find application in optical storage technology,
namely in the development of high information density and fast access type
memories. A new polymer blend of methylene blue sensitized polyvinyl alcohol
(PVA) and polyacrylic acid (PAA) in methanol is prepared and characterized
and its comparison with methylene blue sensitized PVA in methanol and
complexed methylene blue sensitized polyvinyl chloride (CMBPVC) is presented.
The optical absorption spectra of the thin films of these polymers
showed a strong and broad absorption region at 670-650 nm, matching the
wavelength of the laser used. A very slow recovery of the dye on irradiation was
observed when a 7:3 blend of polyvinyl alcohol/polyacrylic acid at a pHof 3.8
and a sensitizer concentration of 4.67 10 5 g/ml were used. A diffraction
efficiency of up to 20% was observed for the MBPVA/alcohol system and an
energetic sensitivity of 2000 mJ/cm2 was obtained in the photosensitive films
with a spatial frequency of 588 lines/mm.
The 2,4,6-triphenylthiapyrylium ion has been obtained imprisoned inside the supercages of the tridirectional,
large pore zeolites Y and beta via ship-in-a-bottle synthesis from chalcone and acetophenone in the presence of
hydrogen sulfide. The resulting solids are efficient and robust photocatalysts that are able to degrade phenol and
aniline in water with a higher efficiency than the P-25 TiO2 standard. Preliminary tests have shown that these
encapsulated dye materials are also efficient photocatalysts for the oxidative degradation of malodorous sulfurcontaining
molecules.
Mohammed Yusuff, K K; Anas, K(Elsevier, Applied Catalysis A :General 264 (2004) 213–217, December 25, 2003)
[+]
[-]
Abstract:
CoMo/gama-Al2O3 catalysts for hydrodesulphurisation activity were prepared by making use of the molecular designed dispersion (MDD)
method. Molybdenum and cobalt pyrrolidine-N-carbodithioate (Pydtc) complexes were used for the incorporation of metals on the support.
The catalysts were characterized by elemental analysis, low temperature oxygen chemisorption, temperature programmed reduction (TPR)
and laser Raman spectroscopy. The hydrodesulphurisation activity of all the catalysts were carried out and results were compared with those
of the catalysts prepared through the conventional method. Higher molybdenum dispersion, smaller molybdenum clusters, lower reduction
temperature of catalyst and better hydrodesulphurisation activity were observed for the catalysts prepared through the MDD method
Transition metal-loaded (3%) nanocrystalline sulfated titania (ST) powders are prepared using the sol–gel technique. Anatase is found as the active phase in all the samples. Sulfate ion impregnation decreases the crystallite size and stabilizes the anatase phase of TiO2. Acidity of the samples is found to increase by the incorporation of sulfate ion and also by the modification by transition metal ions. All the prepared catalysts are found stable up to 700 °C.
One-pot acetalizations of cyclohexanone. acetophenone and benzophenone were carried out using methanol over H-montmorillonite clay
(a mesoporous material). silica, alumina, and different zeolites such as HFAU-Y.HBeta, H-ZSM-5, and H-mordenite. In all the cases a single
product-the corresponding dimethylacetal-was obtained in high yields. Hemiacetal formation was not observed with any catalyst. A
comparison of catalytic activity indicated that montmorillonite K-10 is the most active catalyst for the reaction. As evidenced by the reaction
time studies, the catalyst decay is greater over the zeolite catalyst than over the clay.
Nishamol, K; Rahna, K S; Sugunan, S(Elsevier, 2004)
[+]
[-]
Abstract:
Various compositions of chromium manganese ferrospinels were tested as catalysts for the vapour phase alkylation of aniline with methanol. The samples were prepared by room temperature co-precipitation technique and characterized by various physico-chemical methods. The acidity–basicity determination revealed that the samples possess greater amount of basic sites than acidic sites. All the ferrite samples proved to be selective and active for N-monoalkylation of aniline leading to N-methyl aniline; Cr0.6Mn0.4Fe2O4, Cr0.8Mn0.2Fe2O4 and CrFe2O4 exhibited cent percent selectivity for N-methyl aniline. Neither C-alkylated products nor any other side products were detected for all catalyst samples. The catalytic activity of the samples studied in this reaction is related to their acid–base properties and also on the cation distribution. Under the optimized reaction conditions all the systems showed constant activity for a long duration.
The effect of residual cations in rare earth metal modified faujasite–Y zeolite has been monitored using magic angle spinning NMR spectral analysis and catalytic activity studies. The second metal ions being used are Na+, K+ and Mg+. From a comparison of the spectra of different samples, it is concluded that potassium and magnesium exchange causes a greater downfield shift in the 29Si NMR peaks. Also, lanthanum exchanged samples show migration behavior from large cages to small cages, which causes the redistribution of second counter cations. It is also observed that Mg2+ causes the most effective migration of lanthanum ions due to its greater charge. The prepared systems were effectively employed for the alkylation of benzene with 1-octene in the vapor phase. From the deactivation studies it is observed that the as-exchanged zeolites possess better stability towards reaction condition over the pure HFAU zeolite.
Sreekumar, K(Optical society of America, June 20, 2004)
[+]
[-]
Abstract:
A methylene-blue-sensitized polymer blend of polyvinyl alcohol and polyacrylic acid is fabricated and
tested for holographic recording. It was found to have good characteristics such as high sensitivity,
storage stability, ease of fabrication, and environmental stability. Optimization of the ratio of polyvinyl
alcohol polyacrylic acid, the sensitizer concentration, pH, energy, diffraction efficiency measurements,
etc., have been done. pH is found to have a great influence on the recovery of the dye in this matrix.
The results of experimental investigations into the properties of this new material are reported.
Sunajadevi, K R; Sugunan, S(Elsevier, October , 2004)
[+]
[-]
Abstract:
Chromia loaded sulfated titania has been synthesized via sol–gel route with different chromia loadings. These catalysts are characterized using conventional techniques such as XRD analysis, FTIR analysis, surface area and pore volume measurements, EDX, SEM and UV–Vis diffuse reflectance spectral analysis. Acidity is measured using spectrophotometric monitoring of adsorption of perylene, thermogravimetric desorption of 2,6-dimethylpyridine and temperature programmed desorption of ammonia. Activity studies are done in the liquid phase. It has been concluded that Lewis acid sites are responsible for the benzylation of arenes with benzyl chloride.
A series of rare-earth neodymia supported vanadium oxide catalysts with various V205 loadings ranging from 3 to 15 wt.% were prepared
by the wet impregnation method using ammonium metavanadate as the vanadium precursor. The nature of vanadia species formed on the
support surface is characterized hy a series of different physicochemical techniques like X-ray diffraction (XRD). Fourier transform infrared
spectroscopy (FTIR). BET surface area, diffuse reflectance UV-vis spectroscopy (DR UV-vis), thermal analysis (TG-DTG/DTA) and SEM.
The acidity of the prepared systems were verified by the stepwise temperature programmed desorprion of ammonia (NH3-TPD) and found that
the total acidity gets increased with the percentage of vanadia loading. XRD and FT1R results shows the presence of surface dispersed vanadyl
species at lower loadings and the formation of higher vanadate species as the percentage composition of vanadia is increased above 9 wt.%.
The low surface area of the support. calcination temperature and the percentage of vanadia loading are found to influence the formation of
higher vanadia species. The catalytic activity of the V205-Nd203 catalysts was probed in the liquid phase hydroxylation of phenol and the
result show that the present catalysts are active at lower vanadia concentrations.
Iron and mixed iron aluminium pillared montmorillonites prepared by partial hydrolysis method was subjected to room temperature exchange with transition metals of the first series. The materials exhibit good structural as well as thermal stability. Exchanged metals were found to be present inside the porous network, in the environs of the pillars. Mixed pillaring resulted in the intercalation of Al 13 like polymers in which Al is partially substituted by Fe. The acidic structure was followed by temperature programmed desorption of ammonia and cumene cracking test reaction. Weak and medium sites overshadow the strong sites in all systems. However, exchange with metals increases the number of strong sites. The prepared materials are efficient catalysts for gas phase MTBE synthesis. The catalytic activity can be well correlated with the total amount of weak and medium acid sites.
Rare earth metal ion exchanged (La3+, Ce3+, RE3+) KFAU-Y zeolites were prepared by simple ion-exchange methods and have
been characterized using different physico-chemical techniques. In this paper a novel application of solid acid catalysts in the dehydration/
Beckmann rearrangement of aldoximes; benzaldoxime and 4-methoxybenzaldoxime is reported. Dehydration/Beckmann
rearrangement reactions of benzaldoxime and 4-methoxybenzaldoxime is carried out in a continuous down flow reactor at
473K. 4-Methoxybenzaldoxime gave both Beckmann rearrangement product (4-methoxyphenylformamide) and dehydration product
(4-methoxybenzonitrile) in high overall yields. The difference in behavior of the aldoximes is explained in terms of electronic
effects. The production of benzonitrile was near quantitative under heterogeneous reaction conditions. The optimal protocol allows
nitriles to be synthesized in good yields through the dehydration of aldoximes. Time on stream studies show a fast decline in the
activity of the catalyst due to neutralization of acid sites by the basic reactant and product molecules.
Iron and mixed iron aluminium pillared montrnorillonites prepared by partial hydrolysis method were subjected to room temperature
exchange with transition metals of the first series. The resulting materials were characterised by different spectroscopic techniques
and surface area measurements. About 1-3% transition metals were incorporated into the porous network. The structural
stability of the porous network was not affected by exchange. XRD and AI NMR spectroscopy evidenced the presence of iron
substituted Al13 like polymers in FeAl pillared systems. Acidity and basicity benefited much as a result of metal exchange. Acidity
and basicity were quantified by model reactions, viz., cumene cracking and cyclohexanol decomposition respectively. The presence
of basic sites in otherwise acidic pillared clays, though diminutive in amount can be of much importance in acid base catalysed
reactions.
Invertase was immobilised on microporous montmorillonite K-10 via adsorption and covalent binding. The immobilised enzymes were tested for sucrose hydrolysis activity in a batch reactor. Km for immobilised systems was greater than free enzyme. The immobilised forms could be reused for 15 continuous cycles without any loss in activity. After 25 cycles, 85% initial activity was retained. A study on leaching of enzymes showed that 100% enzyme was retained even after 15 cycles of reuse. Leaching increased with reaction temperature. Covalent binding resisted leaching even at temperatures of 70 °C.
A new photopolymerizable recording media is introduced based on poly
(vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed
that this MBPVA/VAc system can be reused a number of times without
significant decrease in diffraction . The PVA-VAc ratio was optimized
at 2:1. Diffraction efficiency of 6.3% was obtained without any fixing at a dye
concentration of 9.3 10 4 mol/l at an exposure of 750 mJ/cm2. The material is
attractive on account of its reusability.
A new photopolymerizable recording media is introduced based on poly
(vinyl alcohol) and vinyl acetate sensitized with methylene blue. It is observed
that this MBPVA/VAc system can be reused a number of times without
significant decrease in diffraction efficiency. The PVA-VAc ratio was optimized
at 2:1. Diffraction efcienc4y of 6.3% was obtained without any fixing at a dye
concentration of 9.3 x 10- mol/l at an exposure of 750mJ/cm2. The material is
attractive on account of its reusability.
Girish Kumar,K; Muthuselvi,R(Department of Applied Chemistry, March 30, 2005)
[+]
[-]
Abstract:
A spectrophotometric method employing 2-hydroxybenzaldiminoglycine (HBIG) is proposed for
the determination of chromium(III). The results of the determinations are compared with the standard diphenyl
carbazide method. The presently developed method is direct, simple, rapid, selective, sensitive and precise.