Selective Methyl Tert-Butyl Ether Synthesis over Metal Exchanged Pillared Clays

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.

Wet peroxide oxidation of phenol over mixed pillared montmorillonites

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.

Characterisation of the acid-base properties of pillared montmorillonites

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.

"Catalysis by pillared montmorillonites exchanged with transition metals"

The present work is oriented to obtain a comparative evaluation of the physicochemical properties and catalytic activities of iron, aluminium and iron aluminium mixed pillared montmorillonites and their transition metal exchanged analogues. Reactions of industrial importance like Friedel Crafts alkylations, catalytic wet peroxide oxidation of phenol and MTBE synthesis have been selected for the present study. The thesis is structured into seven chapters. First chapter deals with a brief introduction and literature survey on pillared clays. Second chapter explains the materials and methods employed in the work. Results and discussions on the characterisation techniques are described in the third chapter. The subsequent three chapters describe the catalytic activities of pillared clays in the industrially important reactions. Last chapter comprises the summary of the investigations and the conclusions drawn from the earlier chapters

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.

Immobilisation of eta(3)-allyidicarbonyl complexes of Mo-II with bidentate nitrogen ligands within aluminium-pillared clays

Molybdenum(II) complexes [MOX(CO)(2)(eta(3)-allyl)(CH3CN)(2)] (X = Cl or Br) were encapsulated in an aluminium-pillared natural clay or a porous clay heterostructure and allowed to react with bidentate diimine ligands. All the materials obtained were characterised by several solid-state techniques. Powder XRD, and Al-27 and Si-29 MAS NMR were used to investigate the integrity of the pillared clay during the modification treatments. C-13 CP MAS NMR, FTIR, elemental analyses and low-temperature nitrogen adsorption showed that the immobilisation of the precursor complexes was successful as well as the in situ ligand-substitution reaction. The new complex [MoBr(CO)(2)(eta(3)-allyl)(2-aminodipyridyl)] was characterised by single-crystal X-ray diffraction and spectroscopic techniques, and NMR studies were used to investigate its fluxional behaviour in solution. The prepared materials are active for the oxidation of cis-cyclooctene using tert-butyl hydroperoxide as oxidant, though the activity of the isolated complexes is higher. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).

New layered double hydroxides intercalated with substituted pyrroles. 2. 3-(Pyrrol-1-yl)-propanoate and 7-(pyrrol-1-yl)-heptanoate LDHs

We report the synthesis and characterization of organic-inorganic hybrid materials: Zn-2-Al-LDHs (layered double hydroxides) containing 3-(1H-pyrrol-1-yl)-propanoate and 7-(1H-pyrrol-l-yl)-heptanoate as the interlayer anions. The LDHs were synthesized by the co-precipitation method at constant pH followed by hydrothermal treatment for 72 h. The materials were characterized by PXRD, C-13 CP-MAS NMR, TGA, and ESR. The basal spacing found by PXRD technique is coincident with the formation of bilayers of the intercalated anions. The solid state C-13 NMR showed that the interlayered anions remain identical after intercalation. ESR data suggest that the monomers connect each other in a limited number of guests when a thermal treatment is applied. The inorganic LDH sheets delay the temperature of degradation of the monomers. (c) 2006 Elsevier Ltd. All rights reserved.

Fenton-like processes and adsorption using iron oxide-pillared clay with magnetic properties for organic compound mitigation

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Zr-Laponite pillared clay-based nickel catalysts for methane reforming with carbon dioxide

Zr-Laponite pillared clays were prepared and used as supports of nickel catalysts for the methane reforming reaction with carbon dioxide to synthesis gas. The structural and textural characteristics of supports and catalysts were systematically examined by N-2 adsorption/desorption and X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron spectroscopy (TEM) techniques. The catalytic performance and carbon deposition were investigated. It is found that Zr-Laponite pillared clays are promising catalyst supports for carbon dioxide reforming of methane. The pore structure and surface properties of such supports greatly affect the catalytic behaviors of catalysts derived. Carbon deposition on catalysts was also affected by the property and structure of supports. The sintering of nickel metal and zirconia was another factor responsible for catalyst deactivation. This new-type nickel supported catalyst Ni/Zr-Laponite(8), with well-developed porosity, gave a higher initial conversion and a relatively long-term stability, and is therefore a promising catalyst for potential application to carbon dioxide reforming of methane to synthesis gas. (C) 2002 Elsevier Science B.V All rights reserved.

Hydrothermal Synthesis of Layered Double Hydroxides (LDHs) from Mixed MgO and Al2O3: LDH Formation Mechanism

The formation of MgA1 layered double hydroxide (LDH) from physically mixed MgO and Al2O3 oxides upon hydrothermal treatment has been extensively investigated, and a formation mechanism has been proposed. We observed that the formation of LDH from the oxide mixture occurs upon heating at 110 degreesC. In general, LDH is the major component while the minor phases are mainly determined by the initial pH of the oxide suspension as well as the MgO/Al2O3 ratio. The neutrality in the initial suspension results in a minor Mg(OH)(2) as the impure phase, while the alkalinity in the suspension keeps some MgO unreacted throughout the whole hydrothermal treatment. We suggest that MgO and Al2O3 be hydrated into Mg(OH)(2) and Al(OH)(3), respectively, in the initial stage for all samples. We further Suggest that in the neutral condition Mg(OH)2 be quickly dissociated to Mg2+ and OH- which then deposit on the surface of Al(OH)(3)/Al2O3 to form a M-Al pre-LDH material. Al(OH)(4)(-), ionized from Al(OH)(3) in the basic solution, deposits on the surface of Mg(OH)(2)/MgO to result in a similar MgAl pre-LDH material. Such a pre-LDH material is then well crystallized upon continuous heating via the diffusion of metal ions in the solid lattice. Such a dissociation-deposition-diffusion mechanism via two pathways has been supported by the phase composition, morphological features of crystallites, and [Mg]/[Al] ratios on the crystallite surface. and presumably applied to the general formation of LDHs with various synthetic methods. Such as coprecipitation, homogeneous preparation, and reconstruction.

Synthesis and characterisation of pillared clay catalysts for hydro-cracking of heavy liquid fuels

A range of chromia pillared montmorillonite and tin oxide pillared laponite clay catalysts, as well as new pillared clay materials such as cerium and europium oxide pillared montmorillonites were synthesised. Methods included both conventional ion exchange techniques and microwave enhanced methods to improve performance and/or reduce preparation time. These catalytic materials were characterised in detail both before and after use in order to study the effect of the preparation parameters (starting material, preparation method, pillaring species, hydroxyl to metal ratio etc.) and the hydro cracking procedure on their properties. This led to a better understanding of the nature of their structure and catalytic operation. These catalysts were evaluated with regards to their performance in hydrocracking coal derived liquids in a conventional microbomb reactor (carried out at Imperial College). Nearly all catalysts displayed better conversions when reused. The chromia pillared montmorillonite CM3 and the tin oxide pillared laponite SL2a showed the best "conversions". The intercalation of chromium in the form of chromia (Cr203) in the interlayer clearly increased conversion. This was attributed to the redox activity of the chromia pillar. However, this increase was not proportional to the increase in chromium content or basal spacing. In the case of tin oxide pillared laponite, the catalytic activity might have been a result of better access to the acid sites due to the delaminated nature of laponite, whose activity was promoted by the presence of tin oxide. The manipulation of the structural properties of the catalysts via pillaring did not seem to have any effect on the catalysts' activity. This was probably due to the collapse of the pillars under hydrocracking conditions as indicated by the similar basal spacing of the catalysts after use. However, the type of the pillaring species had a significant effect on conversion. Whereas pillaring with chromium and tin oxides increased the conversion exhibited by the parent clays, pillaring with cerium and europium oxides appeared to have a detrimental effect. The relatively good performance of the parent clays was attributed to their acid sites, coupled with their macropores which are able to accommodate the very high molecular mass of coal derived liquids. A microwave reactor operating at moderate conditions was modified for hydro cracking coal derived liquids and tested with the conventional catalyst NiMo on alumina. It was thought that microwave irradiation could enable conversion to occur at milder conditions than those conventionally used, coupled with a more effective use of hydrogen. The latter could lead to lower operating costs making the process cost effective. However, in practice excessive coke deposition took place leading to negative total conversion. This was probably due to a very low hydrogen pressure, unable to have any hydro cracking effect even under microwave irradiation. The decomposition of bio-oil under microwave irradiation was studied, aiming to identify the extent to which the properties of bio-oil change as a function of time, temperature, mode of heating, presence of char and catalyst. This information would be helpful not only for upgrading bio-oil to transport fuels, but also for any potential fuel application. During this study the rate constants of bio-oil's decomposition were calculated assuming first order kinetics.

Organometallic precursors for pillared clay synthesis

The synthetic hectorite, laponite has been used within the paper industry to produce mildly conducting paper for use in electrographic printing. The aim of this research was to modify laponite in order to improve the electrical conductivity. In a continuation of a previous investigation involving organotin intercalation of laponite, the organotin precursor (p-CH3,OC6H4)4Sn was synthesised and characterised using Mass Spectroscopy, Infrared Spectroscopy and elemental analysis. Results of intercalation with this compound and a range of organobismuth and organoantimony compounds suggested that a halide content within the precursor was necessary for improvement in conductivity to be observed. Organometallic intercalation of a range of organotellurium compounds with laponite provided evidence that a hydrolysis reaction on the clay surface followed by the release of hydrochloric acid was an important first step if a reaction was to occur with the clay. Atomic Absorption Spectroscopy studies have shown that the acid protons underwent exchange with the interlayer sodium ions in the clay to varying degrees. Gas-liquid Chromatography and Infrared Spectroscopy revealed that the carbon-tellurium bond remained intact. Powder X-ray diffraction revealed that there had been no increase in the basal spacing. The a.c. conductivity of the modified clays in the form of pressed discs was studied over a frequency range of 12Hz - 100kHz using two electrode systems, silver paste and stainless steel. The a.c. conductivity consists of two components, ionic and reactive. The conductivity of laponite was increased by intercalation with organometallic compounds. The most impressive increase was gained using the organotellurium precursor (p-CH3OC6H4)2TeCl2. Conductivity investigations using the stainless steel electrode where measurements are made under pressure showed that in the case of laponite, where poor particle-particle contact exists at ambient pressure, there is a two order of magnitude increase in the measured a.c. conductivity. This significant increase was not seen in modified laponites where the particle-particle contact had already been improved upon. Investigations of the clay surface using Scanning Electron Microscopy suggested that the improvement in particle-particle contact is the largest factor in the determination of the conductivity. The other important factor is the nature and the concentration of the interlayer cations. A range of clays were synthesised in order to increase the concentration of sodium interlayer cations. A sol-gel method was employed to carry out these syntheses. A conductivity evaluation showed that increasing the concentration of the sodium cations within the clay led to an increase in the conductivity.

Silylation of layered double hydroxides via a calcination−rehydration route

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by 29Si cross-polarization magic-angle spinning nuclear magnetic resonance (29Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a “rodlike” aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T2 and T3 types of linkage between adjacent silane molecules as indicated in the 29Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 °C as observed in IES spectra.

Silylation of layered double hydroxides via an induced hydrolysis method

A series of layered double hydroxides (LDHs) based composites were synthesized by using induced hydrolysis silylation method (IHS), surfactant precursor method, in-situ coprecipitation method, and direct silylation method. Their structures, morphologies, bonding modes and thermal stabilities can be readily adjusted by changing the parameters during preparation and drying processing of the LDHs. The characterization results show that the direct silylation reaction cannot occur between the dried LDHs and 3-aminopropyltriethoxysilane (APS) in an ethanol medium. However, the condensation reaction can proceed with heating process between adsorbed APS and LDHs plates. While using wet state substrates with and without surfactant and ethanol as the solvent, the silylation process can be induced by hydrolysis of APS on the surface of LDHs plates. Surfactants improve the hydrophobicity of the LDHs during the process of nucleation and crystallization, resulting in fluffy shaped crystals; meanwhile, they occupy the surface –OH positions and leave less “free –OH” available for the silylation reaction, favoring formation of silylated products with a higher population in the hydrolyzed bidentate (T2) and tridentate (T3) bonding forms. These bonding characteristics lead to spherical aggregates and tightly bonded particles. All silylated products show higher thermal stability than those of pristine LDHs.

Mechanism of interaction of hydrocalumites (Ca/Al-LDH) with methyl orange and acidic scarlet GR

The development of new materials for water purification is of universal importance. Among these types of materials are layered double hydroxides (LDHs). Non-ionic materials pose a significant problem as pollutants. The interaction of methyl orange (MO) and acidic scarlet GR (GR) adsorption on hydrocalumite (Ca/Al-LDH-Cl) were studied by X-ray diffraction (XRD), infrared spectroscopy (MIR), scanning electron microscope (SEM) and near-infrared spectroscopy (NIR). The XRD results revealed that the basal spacing of Ca/Al-LDH-MO was expanded to 2.45 nm, and the MO molecules were intercalated with a inter-penetrating bilayer model in the gallery of LDH, with 49o tilting angle. Yet Ca/Al-LDH-GR was kept the same d-value as Ca/Al-LDH-Cl. The NIR spectrum for Ca/Al-LDH-MO showed a prominent band around 5994 cm-1, assigned to the combination result of the N-H stretching vibrations, which was considered as a mark to assess MO- ion intercalation into Ca/Al-LDH-Cl interlayers. From SEM images, the particle morphology of Ca/Al-LDH-MO mainly changed to irregular platelets, with a “honey-comb” like structure. Yet the Ca/Al-LDH-GR maintained regular hexagons platelets, which was similar to that of Ca/Al-LDH-Cl. All results indicated that MO- ion was intercalated into Ca/Al-LDH-Cl interlayers, and acidic scarlet GR was only adsorped upon Ca/Al-LDH-Cl surfaces.