Zeolite-encapsulated Co(II), Ni(II) and Cu(II) complexes as catalysts for partial oxidation of benzyl alcohol and ethylbenzene

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.

Ni(II) and Ru(II) Schiff base complexes as catalysts for the reduction of benzene

Two new complexes, [MII(L)(Cl)(H2O)2]·H2O (where M=Ni or Ru and L = heterocyclic Schiff base, 3- hydroxyquinoxaline-2-carboxalidene-4-aminoantipyrine), have been synthesized and characterized by elemental analysis, FT-IR, UV–vis diffuse reflectance spectroscopy, FAB-MASS, TG–DTA, AAS, cyclic voltammetry, conductance and magnetic susceptibility measurements. The complexes have a distorted octahedral structure andwere found to be effective catalysts for the hydrogenation of benzene. The influence of several reaction parameters such as reaction time, temperature, hydrogen pressure, concentration of the catalyst and concentration of benzenewas tested. A turnover frequency of 5372 h−1 has been found in the case of ruthenium complex for the reduction of benzene at 80 ◦C with 3.64×10−6 mol catalyst, 0.34 mol benzene and at a hydrogen pressure of 50 bar. In the case of the nickel complex, a turnover frequency of 1718 h−1 has been found for the same reaction with 3.95×10−6 mol catalyst under similar experimental conditions. The nickel complex shows more selectivity for the formation of cyclohexene while the ruthenium complex is more selective for the formation of cyclohexane

Zeolite Encapsulated Complexes Of Fe,Co,Ni,Cu And Pd:Synthesis , Characterization And Catalysis-2003

This thesis deals with the synthesis, characterization and catalysis activity studies of some zeolite encapsulated complexes. Encapsulation inside the zeolite cages makes the catalysts more stable. Further, the framework prevents the complexes from dimerising. Catalysis by metal complexes encapsulated in the cavities of zeolites and other molecular sieves has many features of homogeneous, heterogenous and enzymatic catalysis. Serious attempts has been made to gain product selectivity in catalysis .The catalytic activity shown by the encapsulated complexes can be correlated to the structure of the active site inside the zeolite pore. It deals with the studies on the partial oxidation of benzyl alcohol to benzaldehyde. The oxidatio was carried out using hydrogen peroxide as oxidant in presence of PdYDMG and CuYSPP as catalysts. The product (benzaldehyde) was detected using TLC and confirmed using GC.The catalytic activity of the complexes was tested for oxidation under various conditions. The operating conditions like the amount of the catalyst, reaction time, oxidant to substrate ratio, reaction temprature, and solvents have been optimized. No further oxidation products were obtained on continuing the reaction for four hours beyond the optimum time. Maximum conversion was obtained at room temperature and the percentage conversion decreased with increase in temperature. Activity was found to be dependent on the solvent used. With increasing awareness about the dangers of environmental degradation, research in chemistry is getting increasing geared to the development of “green chemistry,” by designing environmentally friendly products and processes that bring down the generation and use of hazardous substances.

A PVC Plasticized Sensor for Ni(II) Ion Based on a Simple Ethylenediamine Derivative

new PVC membrane ion selective electrode which is highly selective towards Ni(II) ions was constructed using a Schiff base containing a binaphthyl moiety as the ionophore. The sensor exhibited a good Nernstian response for nickel ions over the concentration range 1.0 × 10–1 – 5.0 × 10–6 M with a lower limit of detection of 1.3 × 10–6 M. It has a fast response time and can be used for a period of 4 months with a good reproducibility. The sensor is suitable for use in aqueous solutions in a wide pH range of 3.6 – 7.4 and works satisfactorily in the presence of 25% (v/v) methanol or ethanol. The sensor shows high selectivity to nickel ions over a wide variety of cations. It has been successfully used as an indicator electrode in the potentiometric titration of nickel ions against EDTA and also for the direct determination of nickel content in real samples: effluent samples, chocolates and hydrogenated oils.

Ruthenium complexes of Schiff base ligands as efficient catalysts for catechol–hydrogen peroxide reaction

Zeolite Y-encapsulated ruthenium(III) complexes of Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde and 1,2- phenylenediamine, 2-aminophenol, or 2-aminobenzimidazole (RuYqpd, RuYqap and RuYqab, respectively) and the Schiff bases derived from salicylaldehyde and 1,2-phenylenediamine, 2-aminophenol, or 2-aminobenzimidazole (RuYsalpd, RuYsalap and RuYsalab, respectively) have been prepared and characterized. These complexes, except RuYqpd, catalyze catechol oxidation by H2O2 selectively to 1,2,4-trihydroxybenzene. RuYqpd is inactive. A comparative study of the initial rates and percentage conversion of the reaction was done in all cases. Turn over frequency of the catalysts was also calculated. The catalytic activity of the complexes is in the order RuYqap > RuYqab for quinoxaline-based complexes and RuYsalap > RuYsalpd > RuYsalab for salicylidene-based complexes. The reaction is believed to proceed through the formation of a Ru(V) species.

Synthesis and Characterisation of New Transition Metal Complexes of Schiff Bases Derived from 3-hydroxyquinoxaline-2- carboxaldehyde and Application of Some ofthese Complexes as Hydrogenation and Oxidation Catalysts

The thesis deals with studies on the synthesis, characterisation and catalytic applications of some new transition metal complexes of the Schiff bases derived from 3-hydroxyquinoxaline 2-carboxaldehyde.. Schiff bases which are considered as ‘privileged ligands’ have the ability to stabilize different metals in different oxidation states and thus regulate the performance of metals in a large variety of catalytic transformations. The catalytic activity of the Schiff base complexes is highly dependant on the environment about the metal center and their conformational flexibility. Therefore it is to be expected that the introduction of bulky substituents near the coordination sites might lead to low symmetry complexes with enhanced catalytic properties. With this view new transition metal complexes of Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde have been synthesised. These Schiff bases have more basic donor nitrogen atoms and the presence of the quinoxaline ring may be presumed to build a favourable topography and electronic environment in the immediate coordination sphere of the metal. The aldehyde was condensed with amines 1,8-diaminonaphthalene, 2,3-diaminomaleonitrile, 1,2-diaminocyclohexane, 2-aminophenol and 4-aminoantipyrine to give the respective Schiff bases. The oxovanadium(IV), copper(II) and ruthenium(II)complexes of these Schiff bases were synthesised and characterised. All the oxovanadium(IV) complexes have binuclear structure with a square pyramidal geometry. Ruthenium and copper form mononuclear complexes with the Schiff base derived from 4- aminoantipyrine while binuclear square planar complexes are formed with the other Schiff bases. The catalytic activity of the copper complexes was evaluated in the hydroxylation of phenol with hydrogen peroxide as oxidant. Catechol and hydroquinone are the major products. Catalytic properties of the oxovanadium(IV) complexes were evaluated in the oxidation of cyclohexene with hydrogen peroxide as the oxidant. Here allylic oxidation products rather than epoxides are formed as the major products. The ruthenium(II) complexes are found to be effective catalysts for the hydrogenation of benzene and toluene. The kinetics of hydrogenation was studied and a suitable mechanism has been proposed.

Organic Synthesis Mediated by Heterogeneous Catalysts

Catalysis is a technologically important field which determines the quality of life in future. Catalyst research in pharmaceutical industry,fine chemical synthesis and emission control demands supported catalysts in bulk quantities.In the present work it was observed that clay supported catalysts mentioned in various chapters could also be used for the synthesis of similar molecules. The K10Ti catalyst can be used for the synthesis similar substituted imidazole derivatives under solvent free conditions and synthetically important Mannich bases of substrates containing various substitutes.Al-pillared saponite can be used for acetalation of other polyhydroxy compounds like glycerol,mannitol etc.Cu-Pd KSF catalyst has found application in C-C bond forming reactions which can be applied to other reactions and similar methods can be adopted for the synthesis of other catalyst by changing the transition metals. Montmorillonite K10 catalysed synthesis of triarylpyridines can be extended to the synthesis tetrasubstuted pyroles.K10Ti can also be utilized for the synthesis of similar heterocycles.

A Low-Energy Ion Scattering (LEIS) Study of the Influence of the Vanadium Concentration on the Activity of Vanadium-Niobium Oxide Catalysts for the Oxidative Dehydrogenation of Propane

A series of vanadium-niobium oxide catalysts in which the vanadia content varies between 0.3 and 18mol%was prepared by coprecipitation. These catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), low-energy ion scattering (LEIS), and by catalytic testing in the oxidative dehydrogenation reaction of propane. The results of the surface analysis by XPS and LEIS are compared. It is concluded that the active site on the catalyst surface contains 2.0 ± 0.3 vanadium atoms on average. This can be understood byassuming the existenceof two or three different sites:isolated vanadium atoms, pairs of vanadium atoms, or ensembles of three vanadium atoms. At higher vanadium concentration more vanadium clusters with a higher activity are at the surface.LEIS revealed that as the vanadium concentration in the catalyst increases, vanadium replaces niobium at the surface. At vanadium concentrations above 8 mol%, new phases such as P-(Nb, V)20S which are less active because vanadium is present in isolated sites are formed, while the vanadium surface concentration shows a slight decrease

Structural, topographical and magnetic evolution of RF-sputtered Fe-Ni alloy based thin films with thermal annealing

Metglas 2826 MB having a nominal composition of Fe40Ni38Mo4B18 is an excellent soft magnetic material and finds application in sensors and memory heads. However, the thin-film forms of Fe40Ni38Mo4B18 are seldom studied, although they are important in micro-electro-mechanical systems/nano-electromechanical systems devices. The stoichiometry of the film plays a vital role in determining the structural and magnetic properties of Fe40Ni38Mo4B18 thin films: retaining the composition in thin films is a challenge. Thin films of 52 nm thickness were fabricated by RF sputtering technique on silicon substrate from a target of nominal composition of Fe40Ni38Mo4B18. The films were annealed at temperatures of 400 °C and 600 °C. The micro-structural studies of films using glancing x-ray diffractometer (GXRD) and transmission electron microscope (TEM) revealed that pristine films are crystalline with (FeNiMo)23B6 phase. Atomic force microscope (AFM) images were subjected to power spectral density analysis to understand the probable surface evolution mechanism during sputtering and annealing. X-ray photoelectron spectroscopy (XPS) was employed to determine the film composition. The sluggish growth of crystallites with annealing is attributed to the presence of molybdenum in the thin film. The observed changes in magnetic properties were correlated with annealing induced structural, compositional and morphological changes