Influence of surface and acid properties of vanadia supported on ceria promoted with rice husk silica on cyclohexanol decomposition

Cyclohexanol decomposition activity of supported vanadia catalysts is ascribed to the high surface area, total acidity and interaction between supported vanadia and the amorphous support. Among the supported catalysts, the effect of vanadia over various wt% V2O5 (2–10) loading indicates that the catalyst comprising of 6 wt% V2O5 exhibits higher acidity and decomposition activity. Structural characterization of the catalysts has been done by techniques like energy dispersive X-ray analysis, X-ray diffraction and BET surface area. Acidity of the catalysts has been measured by temperature programmed desorption using ammonia as a probe molecule and the results have been correlated with the activity of catalysts.

Vanadia Supported on Rice Husk Silica Promoted Rare Earth Oxides

The selective oxidation of alkylaromatics is one of the main processes since the reaction products are important as intermediates in numerous industrial organic chemicals. Side-chain oxidation of alkyl aromatic compounds catalyzed by heterogeneous catalysts using cleaner peroxide oxidants is an especially attractive goal since classical synthetic laboratory procedures preferably use permanganate or acid dichromate as stoichiometric oxidants. In spite of many studies, there are very few which use hydrogen peroxide as a source of oxygen in the C-H activation of alkanes. Eflective utilization of ethylbenzene, available in the xylene stream of the petrochemical industry to more value added products is a promising one in chemical industry. The oxidation products of ethylbenzene are widely employed as intermediates in organic, steroid and resin synthesis.

Structural and catalytic investigation of vanadia supported on ceria promoted with high surface area rice husk silica

Rice husk silica was utilized as the promoter of ceria for preparing supported vanadia catalysts. Effect of vanadium content was investigated with 2–10 wt.% V2O5 loading over the support. Structural characterization of the catalysts was done by various techniques like energy dispersive X-ray (EDX), X-ray diffraction (XRD), BET surface area, thermal analysis (TGA/DTA), FT-infrared spectroscopy (FT-IR), UV–vis diffused reflectance spectroscopy (DR UV–vis), electron paramagnetic spectroscopy (EPR) and solid state magnetic resonance spectroscopies (29Si and 51V MASNMR). Catalytic activity was studied towards liquid-phase oxidation of benzene. Surface area of ceria enhanced upon rice husk silica promotion, thus makes dispersion of the active sites of vanadia easier. Highly dispersed vanadia was found for low V2O5 loading and formation of cerium orthovanadate (CeVO4) occurs as the loading increases. Spectroscopic investigation clearly confirms the formation of CeVO4 phase at higher loadings of V2O5. The oxidation activity increases with vanadia loading up to 8 wt.% V2O5, and further increase reduces the conversion rate. Selective formation of phenol can be attributed to the presence of highly dispersed active sites of vanadia over the support.

Investigations on Some Titania Supported Catalysts

Titania is a versatile metal oxide with multiple applications. Titania supported catalysts are reported to be much more active compared to conventional silica or alumina supported ones in some reactions. TiO2 (anatase) having high surface area, with better crystallinity and high onset temperature of rutilation can be prepared by thermal hydrolysis of titanyl sulfate solution under controlled conditions. Calcinations at 350oC for 6 hrs were necessary to crystallize anatase. Method of preparation and percentage of the loaded metal oxides have greater influence on surface area. Drastic decrease in surface area was observed upon rutilation. Rutilation started at different temperatures depending on the metal oxide and the method of preparation. TiO2 should be characterized with high surface area, phase purity and high onset temperature of rutilation.Which should be well above the optimum temperature of a designated reaction in which it is employed as a catalyst. Variation in physical properties, depending upon the method of preparation is greater in TiO2 supported catalysts. Methanation activity was found to be highly dependent on nickel concentration present on the surface of the pellets. The methanation activity is strongly influenced by support material. The rate and turn over frequency of methanation and toluene oxidation activity of these catalysts are also equally important from an industrial point of view.

Singlet Oxygen in Microporous Silica Xerogel:Quantum Yield and Oxidation at the Gas–Solid Interface

The quantum yields of singlet oxygen production and lifetimes at the gas–solid interface in silica gel material are determined. Different photosensitizers (PS) are encapsulated in parallelepipedic xerogel monoliths (PS-SG). PS were chosen according to their known photooxidation properties: 9,10-dicyanoanthracene (DCA), 9,10-anthraquinone (ANT), and a benzophenone derivative, 4-benzoyl benzoic acid (4BB). These experiments are mainly based on time-resolved 1O2 phosphorescence detection, and the obtained FD and tD values are compared with those of a reference sensitizer for production, 1H-phenalen-1- one (PN), included in the same xerogel. The trend between their ability to oxidize organic pollutants in the gas phase and their efficiency for production is investigated through photooxidation experiments of a test pollutant dimethylsulfide (DMS). The FD value is high for DCA-SG relative to the PN reference, whereas it is slightly lower for 4BB-SG and for ANT-SG. FD is related to the production of sulfoxide and sulfone as the main oxidation products for DMS photosensitized oxidation. Additional mechanisms, leading to C!S bond cleaveage, appear to mainly occur for the less efficient singlet oxygen sensitizers 4BB-SG and ANTSG.

Surface properties and catalytic activity of vanadia supported on rare earth oxides

An investigation on the physical and chemical characterisation of rare earth oxide supported vanadia is attempted in the present study. La2O3, Sm2O3 and DY2O3 serve the purpose of supports. Supported catalysts were prepared and characterised using various physico chemical techniques. A detailed investigation of acid base properties is also carried out. The nature of interaction of vanadia with lanthanide oxide is discussed and the effect of vanadia loading on the activity of the systems towards reactions of industrial importance is explored.

Oxidative dehydrogenation of ethylbenzene over La and Dy supported vanadia

A series of supported vanadia systems have been prepared by excess solvent technique using La203 and DY203 as supports. Physical characterization has been carried out using XRD, FTIR, TG studies, BET surface area measurement, pore volume analysis etc. Cyclohexanol decomposition has been used as a test reaction for evaluating the acid base properties of the supported system. The oxidative dehydrogenation of ethylbenzene has been employed as a chemical probe reaction to examine the catalytic activity. The active species correspond to amorphous and crystalline tetrahedral vanadyl units in the supported system.

Surface properties and catalytic activity of vanadia supported on samaria

Sm2O3 - vanadia catalysts have been prepared by wet impregnation method using NH4VO3 solution. The surface properties of the prepared catalysts have been studied using FTIR. XRD. surface area and pore volume data. The acid-base properties of the system have been investigated by titrimetric method using Hammett indicators. adsorption of electron acceptors as well as decomposition of cyclohexanol. Phenol alkylation reaction by methanol has been carried out to investigate the catalytic activity. It has been observed that the selectivity of the products depends upon the composition of the supported system

Acid activated montmorillonite: an efficient immobilization support for improving reusability, storage stability and operational stability of enzymes

Three enzymes, α-amylase, glucoamylase and invertase, were immobilized on acid activated montmorillonite K 10 via two independent techniques, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, N2 adsorption measurements and 27Al MAS-NMR spectroscopy. The XRD patterns showed that all enzymes were intercalated into the clay inter-layer space. The entire protein backbone was situated at the periphery of the clay matrix. Intercalation occurred through the side chains of the amino acid residues. A decrease in surface area and pore volume upon immobilization supported this observation. The extent of intercalation was greater for the covalently bound systems. NMR data showed that tetrahedral Al species were involved during enzyme adsorption whereas octahedral Al was involved during covalent binding. The immobilized enzymes demonstrated enhanced storage stability. While the free enzymes lost all activity within a period of 10 days, the immobilized forms retained appreciable activity even after 30 days of storage. Reusability also improved upon immobilization. Here again, covalently bound enzymes exhibited better characteristics than their adsorbed counterparts. The immobilized enzymes could be successfully used continuously in the packed bed reactor for about 96 hours without much loss in activity. Immobilized glucoamylase demonstrated the best results.

Vanadia supported on ceria: Characterization and activity in liquid-phase oxidation of ethylbenzene

Vanadia/ceria catalysts (2–10 wt% of V2O5) were prepared by wet impregnation of ammonium metavanadate in oxalic acid solution. Structural characterization was done with energy dispersive X-ray analysis (EDX), powder X-ray diffraction (XRD), BET surface area measurements, FT-IR spectroscopy and nuclear magnetic spectral analysis (51V MASNMR). XRD and 51V MASNMR results show highly dispersed vanadia species at lower loadings and the formation of CeVO4 phase at higher V2O5 loading. The catalytic activity of catalysts was conducted in liquid phase oxidation of ethylbenzene with H2O2 as oxidant. The oxidation activity is increased with loading up to 8 wt% V2O5 and then decreased with further increase in V2O5 content to 10 wt%. Different vanadia species evidenced by various techniques were found to be selective towards ethylbenzene oxidation. The CeVO4 formation associated with increased concentration of vanadia on ceria results the production of acetophenone along with 2-hydroxyacetophenone.

Propyl Gallate Synthesis Using Acidophilic Tannase and Simultaneous Production of Tannase and Gallic Acid by Marine Aspergillus awamori BTMFW032

Marine Aspergillus awamori BTMFW032, recently reported by us, produce acidophilic tannase as extracellular enzyme. Here, we report the application of this enzyme for synthesis of propyl gallate by direct transesterification of tannic acid and in tea cream solubilisation besides the simultaneous production of gallic acid along with tannase under submerged fermentation by this fungus. This acidophilic tannase enabled synthesis of propyl gallate by direct transesterification of tannic acid using propanol as organic reaction media under low water conditions. The identity of the product was confirmed with thin layer chromatography and Fourier transform infrared spectroscopy. It was noted that 699 U/ml of enzyme could give 60% solubilisation of tea cream within 1 h. Enzyme production medium was optimized adopting Box–Behnken design for simultaneous synthesis of tannase and gallic acid. Process variables including tannic acid, sodium chloride, ferrous sulphate, dipotassium hydrogen phosphate, incubation period and agitation were recognized as the critical factors that influenced tannase and gallic acid production. The model obtained predicted 4,824.61 U/ml of tannase and 136.206 μg/ml gallic acid after 48 h of incubation, whereas optimized medium supported 5,085 U/ml tannase and 372.6 μg/ml of gallic acid production after 36 and 84 h of incubation, respectively, with a 15-fold increase in both enzyme and gallic acid production. Results indicated scope for utilization of this acidophilic tannase for transesterification of tannic acid into propyl gallate, tea cream solubilisation and simultaneous production of gallic acid along with tannase

Sequential interactions of Silver-silica nanocomposite (Ag-SiO2NC) with cell wall, metabolism and genetic stability of Psedomonas aeruginosa, a multiple antibiotic resistant bacterium

The study was carried out to understand the effect of silver-silica nanocomposite (Ag-SiO2NC) on the cell wall integrity, metabolism and genetic stability of Pseudomonas aeruginosa, a multiple drugresistant bacterium. Bacterial sensitivity towards antibiotics and Ag-SiO2NC was studied using standard disc diffusion and death rate assay, respectively. The effect of Ag-SiO2NC on cell wall integrity was monitored using SDS assay and fatty acid profile analysis while the effect on metabolism and genetic stability was assayed microscopically, using CTC viability staining and comet assay, respectively. P. aeruginosa was found to be resistant to β-lactamase, glycopeptidase, sulfonamide, quinolones, nitrofurantoin and macrolides classes of antibiotics. Complete mortality of the bacterium was achieved with 80 μgml-1 concentration of Ag-SiO2NC. The cell wall integrity reduced with increasing time and reached a plateau of 70 % in 110 min. Changes were also noticed in the proportion of fatty acids after the treatment. Inside the cytoplasm, a complete inhibition of electron transport system was achieved with 100 μgml-1 Ag-SiO2NC, followed by DNA breakage. The study thus demonstrates that Ag-SiO2NC invades the cytoplasm of the multiple drug-resistant P. aeruginosa by impinging upon the cell wall integrity and kills the cells by interfering with electron transport chain and the genetic stability

Catalysis by Modified Pillared Clays and Porous Clay Heterostructures

In this venture three distinct class of catalysts such as, pillared clays and transition metal loaded pillared clays , porous clay heterostructures and their transition metal loaded analogues and DTP supported on porous clay heterostructures etc. were prepared and characterized by various physico chemical methods. The catalytic activities of prepared catalysts were comparatively evaluated for the industrially important alkylation, acetalization and oxidation reactions.The general conclusions drawn from the present investigation are  Zirconium, iron - aluminium pillared clays were synthesized by ion exchange method and zirconium-silicon porous heterostructures were Summary and conclusions 259 prepared by intergallery template method. Transition metals were loaded in PILCs and PCHs by wet impregnation method.  Textural and acidic properties of the clays were modified by pillaring and post pillaring modifications.  The shift in 2θ value to lower range and increase in d (001) spacing indicate the success of pillaring process.  Surface area, pore volume, average pore size etc. increased dramatically as a result of pillaring process.  Porous clay heterostructures have higher surface area, pore volume, average pore diameter and narrow pore size distribution than that of pillared clays.  The IR spectrum of PILCs and PCHs are in accordance with literature without much variation compared to parent montmorillonite which indicate that basic clay structure is retained even after modification.  The silicon NMR of PCHs materials have intense peaks corresponding to Q4 environment which indicate that mesoporous silica is incorporated between clay layers.  Thermo gravimetric analysis showed that thermal stability is improved after the pillaring process. PCH materials have higher thermal stability than PILCs.  In metal loaded pillared clays, up to 5% metal species were uniformly dispersed (with the exception of Ni) as evident from XRD and TPR analysis. Chapter 9 260  Impregnation of transition metals in PILCs and PCHs enhanced acidity of catalysts as evident from TPD of ammonia and cumene cracking reactions.  For porous clay heterostructures the acidic sites have major contribution from weak and medium acid sites which can be related to the Bronsted sites as evident from TPD of ammonia.  Pillared clays got more Lewis acidity than PCHs as inferred from α- methyl styrene selectivity in cumene cracking reaction.  SEM images show that layer structure is preserved even after modification. Worm hole like morphology is observed in TEM image of PCHs materials  In ZrSiPCHS, Zr exists as Zr 4+ and is incorporated to silica pillars in the intergallary of clay layers as evident from XPS analysis.  In copper loaded zirconium pillared clays, copper exists as isolated species with +2 oxidation state at lower loading. At higher loading, Cu exists as clusters as evident from reduction peak at higher temperatures in TPR.  In vanadium incorporated PILCs and PCHs, vanadium exist as isolated V5+ in tetrahedral coordination which is confirmed from TPR and UVVis DRS analysis.  In cobalt loaded PCHs, cobalt exists as CoO with 2+ oxidation state as confirmed from XPS.  Cerium incorporated iron aluminium pillared clay was found to be the best catalyst for the hydroxylation of phenol in aqueous media due to the additional surface area provided by ceria mesopores and its redox properties. Summary and conclusions 261  Cobalt loaded zirconium porous clay heterostructures were found to be promising catalyst for the tertiary butylation of phenol due to higher surface area and acidic properties.  Copper loaded pillared clays were found to be good catalyst for the direct hydroxylation of benzene to phenol.  Vanadium loaded PCHs catalysts were found to be efficient catalysts for oxidation of benzyl alcohol.  DTP was firmly fixed on the mesoporous channels of PCHs by Direct method and functionalization method.  DTP supported PCHs catalyst were found to be good catalyst for acetalization of cyclohexanone with more than 90% conversion.