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Abstract: | 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. |
URI: | http://dyuthi.cusat.ac.in/purl/4977 |
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Dyuthi-T2048.pdf | (6.606Mb) |
Abstract: | 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. |
URI: | http://dyuthi.cusat.ac.in/purl/2317 |
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Dyuthi-SS85.pdf | (666.1Kb) |
Abstract: | Wet peroxide oxidation (WPO) of phenol is an effective means for the production of diphenols, which are of great industrial importance. An added advantage of this method is the removal of phenol from wastewater effluents. Hydroxylation of phenol occurs efficiently over mixed iron aluminium pillared montmorillonites. An initial induction period is noticed in all cases. A thorough study on the reaction variables suggests free radical mechanism for the reaction. |
URI: | http://dyuthi.cusat.ac.in/purl/2269 |
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Dyuthi-SS59.pdf | (583.0Kb) |
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