Studies on catalysis by transition metal promoted sulphated zirconia

The present project was a systematic investigation of the physico-chemical properties and catalytic activity of some transition metal promoted sulphated zirconia systems. The characterisation and catalytic activity results were compared with that of pure Zr02 and simple sulphated zirconia systems. Sulphated zirconia samples were prepared by a controlled impregnation technique. In the case of metal incorporated systems, a single step impregnation was carried out using required amounts of sulphuric acid and metal salt solutions. As a preliminary step, optimisation of calcination temperature and sulphate content was achieved. For further studies, the optimised sulphate loading of 10 ml per gram of hydrous zirconium oxide and a calcination temperature of 700°C was employed. Metal incorporation had a positive influence on the physico-chemical properties. Vapour phase cumene conversion served as a test reaction for acidity. Some industrially important reactions like Friedel-Crafts reaction, phenol hydroxylation, nitration, etc. were selected to test the catalytic activity of the prepared systems.

Synthesis, characterization and catalytic activity of Nd203 supported V205 catalysts

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.

Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations

Catalysis is a mature field with extensive practical applications in today's society.indeed,the catalysis of petroleum refining,fine chemical synthesis and emission control demands the production of catalysts in bulk quantities.Future improvement of these well established processes is likely to be incremental.On the other hand,the continuous demand for new products will require additional novel and innovative processes.The need for pollution abatement and prevention also imposes new demands on catalysis, and new processes are periodically advanced for the control of emission of gases as well as for remediation processes such as the cleaning of underground waters. The number of problems where catalysis can have a big impact is constantly growing.In general,science stimulated by the technology has enriched the field of catalysis in a way that has had broad and lasting value.The thesis"Transition metal and rare earth metal modified sol-gel titania: a versatile catalyst for organic transformations" accounts the preparation and characterization studies of both transition metals and rare earth metals modified sol-gel titania and its applications in industrially useful organic reactions.

Zeolite encapsulated complexes of ruthenium: synthesis, characterisation and catalytic activity studies

The work presented in this thesis is mainly centered on the synthesis and characterization of some encapsulated transition metal complexes and the catalytic activity of the synthesized complexes in certain organic reactions.thesis deals with the catalytic activity of ruthenium-exchanged zeolite and the zeolite encapsulated complexes of SSC, SOD, SPD, AA, ABA, DMG, PCO, PCP, CPO and CPP in the hydroxylation of phenol using hydrogen peroxide. The products were analyzed with a GC to determine the percentage conversion and the chromatograms indicate the presence of different products like hydroquinone, catechol,benzoquinone, benzophenone etc. The major product formed is hydroquinone. From the screening studies, RuYSSC was found to be the most effective catalyst for phenol hydroxylation with 94.4% conversion and 76% hydroquinone selectivity. The influence of different factors like reaction time, temperature, amount of catalyst, effect of various solvents and oxidant to substrate ratio in the catalytic activity were studied in order to find out the optimum conditions for the hydroxylation reaction. The influence of time on the percentage conversion of phenol was studied by conducting the reactions for different durations varying from one hour to four hours. There is an induction period for all the complexes and the length of the induction period depends on the nature of the active components. Though the conversion of phenol and selectivity for hydroquinone. increases with time, the amount of benzoquinone formed decreases with time. This is probably due to the decomposition of benzoquinone formed during the initial stages of the reaction into other degradation products like benzophenones. The effect of temperature was studied by carrying out the reaction at three different temperatures, 30°C, 50°C and 70°C. Reactions carried at temperatures higher than 70°C result either in the decomposition of the products or in the formation of tarry products. Activity increased with increase in the amount of the catalyst up to a certain level. However further increase in the weight of the catalyst did not have any noticeable effect on the percentage conversion. The catalytic studies indicate that the oxidation reaction increases with increase in the volume of hydrogen peroxide till a certain volume. But further increase in the volume of H202 is detrimental as some dark mass is obtained after four hours of reaction. The catalytic activity is largely dependent on the nature of the solvent and maximum percentage conversion occurred when the solvent used is water. The intactness of the complexes within the zeolite cages enhances their possibility of recycling and the activities of the recycled catalysts show only a slight decrease when compared to the fresh samples .

Retarding effect of surface hydroxylation on titanium(IV) oxide photocatalyst in the degradation of phenol

Nanosized powders of TiO2 (anatase) were prepared by the hydrothermal method, acid-medium hydrolysis or by vacuum freeze-drying of sols, and annealing at temperatures <700-degrees-C. Photocatalytic activities of these powders in the mineralization of phenol, were evaluated in comparison to that of Degussa P25. Kinetic data indicated that surface hydroxylation had a retarding effect on the degradation of phenol. Formation of stable peroxotitanium species were observed on hydroxylated powders, whereas only V(Ti)-O- hole trap centres were detected by EPR on the heat treated samples. The data supports direct hole oxidation of the substrate preadsorbed on the photocatalyst, which is otherwise blocked by surface hydroxyls.

Role of electron transfer of quinones in hydroxylation of phenol

It was found that at neutral pH the hydroxylation reaction rate of phenol was accelerated with an increase of the amounts of 1,4-quinone (1,4-BQ), This acceleration was ascribed to the formation of semiquinone from 1,4-BQ. The semiquinone and 1,4-BQ were suggested to play a role of actual oxidant (electron transfer) in the catalytic cycle. With further reaction, most 1,4-BQ was converted into 1,4-hydroquinone (HQ) and the corresponding mechanism was proposed.

Studies on preparation of iron phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, characterization and catalytic hydroxylation of phenol

Iron phenanthroline - and 8 - hydroxyquinoline complexes /Y zeolite, denoted a FePhen/Y and FeOx/Y respectively, were prepared; The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elemental analyses, diffuse reflectance UV-Vis,SEM,BET,and XRD methods; The influence of experimental parameters upon phenol conversion and product selectivities were investigated as well.

Hydroxylation of phenol by iron(II)-phenanthroline(Phen)/MCM-41 zeolite

MCM-41 zeolite and Tron (II)-Phen/MCM-41 zeolite have been prepared and characterized by XRD, IR, NH3-TPD, HET and UV-Vis. The Iron( II)-Phen/MCM-41 zeolite+30% H2O2 system is capable for catalyzing hydroxylation of phenol.

Studies on preparation, characterization of cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, and catalytic hydroxylation of phenol

Cobalt(II) phenanthroline and 8-hydroxyquinoline complexes/Y zeolite, denoted as CoPhen/Y and CoOx/Y respectively, were prepared, The formation of the metal complexes mentioned above within the cages of Y zeolite and their crystal structures were determined by elementary analyses, TG-DTA, diffuse reflectance UV-Vis, SEM, BET and XRD methods. The influence of experimental parameters upon phenol conversion and product selectivities was investigated as well.

Hydroxylation of phenol by iron(II)-phenanthroline(Phen) MCM-41 zeolite

MCM-41 mesoporous molecular sieve and iron(II)-Phen/MCM-41 have been prepared and characterized by XRD, IR, NH3-TPD, BET and UV-Vis. The iron(II)-Phen/MCM-41 molecular sieve + 30% H2O2 system is capable of performing hydroxylation of phenol.

STUDIES ON PREPARATION OF IRON, COBALT AND COPPER PHTHALOCYANINES Y ZEOLITE - CHARACTERIZATION AND THEIR CATALYSIS FOR HYDROXYLATION OF PHENOL

Iron, cobalt and copper phthalocyanines/Y zeolite, denoted as FePcY, CoPcY and CuPcY respectively,were prepared. The formation of metal phthalocyanine compounds within the cages of Y zeolite and their crystal structures were determined by elementary analyses, IR, UV-Vis, TG, BET, and XRD methods; The influence of experimental parameters upon phenol conversion and product selectivities was investigated as well.

Direct oxidation of benzene to phenol on manganese pyrophosphate with hydrogen peroxide

A solid catalyst manganese pyrophosphate based on non-sieves to oxidize benzene to phenol with oxidant hydrogen peroxide has shown good conversion with good selectivity in CH3CN at 65 degrees C investigating water contact angle data of three manganese salts, it is found manganese pyrophosphate has certain repulsive water character. It is further to be confirmed by benzene and phenol adsorption experiments onto catalyst surface by GC. With benzene/H2O2 ratio of 1, the benzene conversion of 13.8% with phenol selectivity of 85.0% was achieved. It is noteworthy that no any products are obtained using manganese pyrophosphate as catalyst in the oxidation of phenol in CH3CN solvent.

Hydroxylation d’halogénures d’aryle utilisant la chimie en flux continu et développement d’une nouvelle méthodologie de synthèse de 3-aminoindazoles

L’attrait des compagnies pharmaceutiques pour des structures cycliques possédant des propriétés biologiques intéressantes par les compagnies pharmaceutiques a orienté les projets décrits dans ce mémoire. La synthèse rapide, efficace, verte et économique de ces structures suscite de plus en plus d’attention dans la littérature en raison des cibles biologiques visées qui deviennent de plus en plus complexes. Ce mémoire se divise en deux projets ciblant la synthèse de deux structures aromatiques importantes dans le monde de la chimie médicinale. Dans un premier temps, l’amélioration de la synthèse de dérivés phénoliques a été réalisée. L’apport de la chimie en flux continu dans le développement de voies synthétiques plus vertes et efficaces sera tout d’abord discuté. Ensuite, une revue des antécédents concernant l’hydroxylation d’halogénure d’aryle sera effectuée. Finalement, le développement d’une nouvelle approche rapide de synthèse des phénols utilisant la chimie en flux continu sera présenté, suivi d’un survol de ses avantages et ses limitations. Dans un deuxième temps, le développement d’une nouvelle méthodologie pour la formation de 3-aminoindazoles a été réalisé. Tout d’abord, un résumé de la littérature sur la synthèse de différents indazoles sera présenté. Ensuite, une présentation de deux méthodes efficaces d’activation de liens sera effectuée, soit l’activation d’amides par l’anhydride triflique et l’activation de liens C–H catalysée par des métaux de transition. Finalement, le développement d’une nouvelle méthodologie pour la synthèse de 3-aminoindazole utilisant ces deux approches sera discuté.

Interference of inorganic ions on phenol degradation by the Fenton reaction

The addition of Cu2+ ions to the classical Fenton reaction (Fe2+ plus H2O2 at pH 3) is found to accelerate the degradation of organic compounds. This synergic effect causes an approximately 15 % additional reduction of the total organic carbon (TOC), representing an overall improvement of the efficiency of the mineralization of phenol. Although Fe2+ exhibits a high initial rate of degradation, the degradation is not complete due to the formation of compounds refractory to the hydroxyl radical. The interference of copper ions on the degradation of phenol by the Fenton reaction was investigated. In the presence of Cu2+, the degradation is slower, but results in a greater reduction of TOC at the end of the reaction (t = 120 min). In the final stages of the reaction, when the Fe3+ in the solution is complexed in the form of ferrioxalate, the copper ions assume the role of the main catalyst of the degradation.

Mechanistic Implications of Zinc(II) Ions on the Degradation of Phenol by the Fenton Reaction

A study of the interference of Zn2+ ions on phenol degradation by Fenton reaction (Fe2+/Fe3(+) + H2O2) is reported. One of the first intermediates formed in the reaction, catechol, can reduce Fe3+ to Fe2+ and, in the presence of H2O2 initiates an efficient catalytic redox cycle. In the initial stages of the reaction, this catechol-mediated cycle becomes the principal route of thermal degradation of phenol and its oxidation products. The Zn2+ ion addition enhances the persistence time of catechol, probably by stabilization of the corresponding semiquinone radical via complexation.