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.

Micellar catalysis for partial oxidation of toluene to benzoic acid in supercritical CO2: effects of fluorinated surfactants

One of the key hindrances on development of solid catalysts containing cobalt species for partial oxidation of organic molecules at mild conditions in conventional liquid phase is the severe metal leaching. The leached soluble Co species with a higher degree of freedom always out-performs those of solid supported Co species in oxidation catalysis. However, the homogeneous Co species concomitantly introduces separation problems. We have recently reponed for the first time, a new oxidation catalyst system for the oxidation of organic molecules in supercritical CO2 using the principle of micellar catalysis. [CF3(CF2)(8)COO](2)Co.xH(2)O (the fluorinated anionic moiety forms aqueous reverse micelles carrying water-soluble Co2+ cations in scCO(2)) was previously shown to be extremely active for the oxidation of toluene in the presence of sodium bromide in water-CO2 mixture, giving 98% conversion and 99% selectivity to benzoic acid at 120 degreesC. In this study, we show that the effects of varying the type of surfactant counterions and the length of the surfactant chains on catalysis. It is found that the use of [CF3(CF2)(8)COO](2)Mg.yH(2)O/Co(II) acetate is as effective as the [CF3(CF2)(8)COO](2)Co.xH(2)O and the fluorinated chain length used has a subtle effect on the catalytic rate measured. It is also demonstrated that this new type of micellar catalyst in scCO(2) can be easily separated via CO2 depressurisation and be reused without noticeable deactivation. (C) 2003 Elsevier B.V. All rights reserved.

Characterization and catalytic activity of iron(III) mono(4-N-methyl pyridyl)-tris(halophenyl) porphyrins in homogeneous and heterogeneous systems

The synthesis, characterization and catalytic activity of the cationic iron porphyrins Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 in the epoxidation of (Z)-cyclooctene by PhIO in homogeneous solution and supported on silica gel (SG), imidazole propyl gel (IPG) or SG modified with 2-(4-sulfonatophenyl)ethyl groups (SiSO3) have been accomplished. When supported on IPG, both cationic FeP bind to the support via Fe-imidazole coordination. Fe[M(4-N-MePy)TDCPP]IPG contains a mixture of low-spin bis-coordinated (FeP)-P-III and high-spin mono-coordinated (FeP)-P-III species, whereas Fe[M(4-N-MePy)TFPP]IPG only contains high-spin mono-coordinated (FeP)-P-III. These FePIPG catalysts also contain (FeP)-P-II species, whose presence was confirmed by EPR spectroscopy using NO as a paramagnetic probe. Both cationic FePs coordinate to SG through Fe-O ligation and they are present as high-spin (FeP)-P-III species. The cationic FePs supported on SiSO3- are also high-spin (FeP)-P-III species and they bind to the support via electrostatic interaction between the 4-N-methylpyridyl groups and the SO3- groups present on the matrix. In homogeneous solution, both Fe[M(4-N-MePy)TDCPP]Cl-2 and Fe[M(4-N-MePy)TFPP]Cl-2 have similar catalytic activity to Fe(TDCPP)Cl and Fe(TFPP)Cl, leading to cis-epoxycyclooctane yields of 92%. When supported on inorganic matrices,both FePs lead to epoxide yields comparable to their homogeneous analogues and their anchoring enables catalyst recovery and re-use. Recycling of Fe[M(4-N-MePy)TDCPP]SiSO3- shows that this FeP maintains its activity in a second reaction. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Manganese(III) porphyrins: Catalytic activity and intermediate studies in homogeneous systems

We studied how solvent, stirring method, PhIO/MnP molar ratio, presence of water and axial ligand affect the catalytic activities of Mn(TPP)Cl, Mn(MNPP)Cl, Mn(TDCPP)Cl and Mn(TFPP)Cl in the oxidation of cyclohexane by PhIO. A study of the catalytic intermediates in the reaction between Mn(TPP)Cl or Mn(TDCPP)Cl and PhIO was also carried out by UV-Vis and EPR spectroscopies. The reaction of Mn(TPP)Cl with PhIO showed the formation of a mixture of species Mn-IV(OP+ and Mn-V(O)P as intermediates, which were confirmed by the deconvolution of the UV-Vis spectra. Addition of imidazole as cocatalyst favoured the formation of the intermediate species Mn-V(O)P, evidenced by the UV-Vis band at 408 nm. The corresponding EPR spectra gave evidence that in the presence of imidazole, Mn-IV(OP+ species are formed only in very low amounts. For Mn(TDCPP)Cl the dominating intermediate species is Mn-IV(OP+. Addition of imidazole to halogen-substituted MnP systems does not result in increase of the C-ol yields because very stable bis-imidazole-MnP complexes are formed. Anchoring of such MnP on imidazole propyl gel (IPG) results in better catalytic activity because in this case, the catalyst is mono-coordinated to the support and imidazole favours the formation of the intermediate species Mn-V(O)P.

Cooperative effects of H+ and H- hydrido carbonyl ruthenium derivatives; role of homogeneous and heterogeneous protonic and lewis acids in catalytic hydrocarbonylation reactions

The role played by H+ hydrido iodocarbonyl and H- hydrido carbonyl ruthenium catalysts in the different catalytic steps of hydroformylation and hydroesterification of olefins, and in the homologation of alcohols has been investigated. The H- hydrido carbonyl species are mainly involved in the activation of olefins and in the hydrogenation of the acyl intermediates to aldehydes and alcohols, whereas the H+ hydrido iodocarbonyl derivatives are involved in the activation of alcohols and other oxygenated substrates, and in their carbonylation to esters. The cooperation between the two species, possible under particular reaction conditions, results in an improvement of the selectivity towards homologation (carbonylation plus hydrogenation) products. Heterogeneous Lewis acid promoters, easily recyclable from the reaction mixture, have also been successfully used in the hydrocarbonylation of alcohols, resulting in an increase of the carbonylation and homologation products. A reaction pathway in agreement with the experimental results is discussed. © 1989.

Structural and textural studies of NiO impregnation in mesoporous ZrO2-CeO2 for catalysis applications.

The synthesis of zirconia-based ordered mesoporous structures for catalytic applications is a research area under development. These systems are also potential candidates as anodes in intermediate temperature solid oxide fuel cells (it-SOFC) due to an enhancement on their surface area [1-4]. The structural features of mesoporous zirconia-ceria materials in combination with oxygen storage/release capacity (OSC) are crucial for various catalytic reactions. The direct use of hydrocarbons as fuel for the SOFC (instead of pure H2), without the necessity of reforming and purification reactors can improve global efficiency of these systems [4]. The X-ray diffraction data showed that ZrO2-x%CeO2 samples with x>50 are formed by a larger fraction of the cubic phase (spatial group Fm3m), while for x<50 the major crystalline structure is the tetragonal phase (spatial group P42/nmc). The crystallite size of the cubic phase increases with increase in ceria content. The tetragonal crystallite size decreases when ceria content increases. After impregnation, the Rietveld analysis showed a NiO content around 60wt.% for all samples. The lattice parameters for the ZrO2 tetragonal phase are lower for higher ZrO2 contents, while for all samples the cubic NiO and CeO2 parameters do not present changes. The calculated densities are higher for higher ceria content, as expected. The crystallite size of NiO are similar (~20nm) for all samples and 55nm for the NiO standard. Nitrogen adsorption experiments revealed a broader particle size distribution for higher CeO2 content. The superficial area values were around 35m2/g for all samples, the average pore diameter and pore volumes were higher when increasing ceria content. After NiO impregnation the particle size distribution was the same for all samples, with two pore sizes, the first around 3nm and a broader peak around 10nm. The superficial area increased to approximately 45m2/g for all samples, and the pore volume was also higher after impregnation and increased when ceria content increased. These results point up that the impregnation of NiO improves the textural characteristics of the pristine material. The complementary TEM/EDS images present a homogeneous coating of NiO particles over the ZrO2-x%CeO2 support, showing that these samples are excellent for catalysis applications. [1] D. Y. Zhao, J. Feng, Q. Huo, N. Melosh, G. H. Fredrickson, B. F. Chmelka, G. D. Stucky, Science 279, 548-552 (1998). [2] C. Yu, Y. Yu, D. Zhao, Chem. Comm. 575-576 (2000). [3] A. Trovarelli, M. Boaro, E. Rocchini, C. de Leitenburg, G. Dolcetti, J. Alloys Compd. 323-324 (2001) 584-591. [4] S. Larrondo, M. A. Vidal, B. Irigoyen, A. F. Craievich, D. G. Lamas, I. O. Fábregas, et al. Catal. Today 107–108 (2005) 53-59.

Ligand tethering by ion-exchange for the immobilization of homogeneous catalysts

A Rh phosphine complex, derived from the Wilkinson’s catalyst, has been immobilized by ion-exchange on the ammonium form of a Al-MCM-41 sample. Ammonium ions have been exchanged by cholamine ions, which act as an amine ligand, and then the Wilkinson’s catalyst has been immobilized by substitution of a phosphine ligand by the anchored amine. This is a novel immobilization procedure, as a ligand, instead of the whole complex, is tethered to the support by ion exchange. The obtained hybrid catalyst has been characterized by Elemental Analysis, DRIFTS and XPS. The quantitative exchange of ammonium by cholamine and coordination of Rh to amines has been observed. Most of the anchored Rh is considered to be coordinated to the ligand tethered to the support and a small proportion seems to be interacting with the protonated ligand or with the support surface. The catalyst has been tested in the hydrogenation of cyclohexene and in the hydroformylation of 1-octene. In the first case the catalyst is active and reusable, while a strong Rh leaching takes place in the second one.

Recent developments in heterogeneous catalysis for the sustainable production of biodiesel

The quest for energy security and widespread acceptance of the anthropogenic origin of rising CO2 emissions and associated climate change from combusting fossil derived carbon sources, is driving academic and commercial research into new routes to sustainable fuels to meet the demands of a rapidly rising global population. Biodiesel is one of the most readily implemented and low cost, alternative source of transportation fuels to meet future societal demands. However, current practises to produce biodiesel via transesterification employing homogeneous acids and bases result in costly fuel purification processes and undesired pollution. Life-cycle calculations on biodiesel synthesis from soybean feedstock show that the single most energy intensive step is the catalytic conversion of TAGs into biodiesel, accounting for 87% of the total primary energy input, which largely arises from the quench and separation steps. The development of solid acid and base catalysts that respectively remove undesired free fatty acid (FFA) impurities, and transform naturally occurring triglycerides found within plant oils into clean biodiesel would be desirable to improve process efficiency. However, the microporous nature of many conventional catalysts limits their ability to convert bulky and viscous feeds typical of plant or algal oils. Here we describe how improved catalyst performance, and overall process efficiency can result from a combination of new synthetic materials based upon templated solid acids and bases with hierarchical structures, tailored surface properties and use of intensified process allowing continuous operation.

Fundamental Pd0/PdII redox steps in cross-coupling reactions:homogeneous, hybrid homogeneous-heterogeneous to heterogeneous mechanistic pathways for C-C couplings

C–C bond-forming, cross-coupling reactions of organohalides with nucleophilic compounds, catalysed by palladium, are amongst the most important chemical reactions available to the synthetic chemist. The intimate mechanisms of these reactions, involving Pd0/PdII redox steps, have been of great historical interest and continue to be so. The myriad of possible mechanisms is reviewed in this chapter. The interplay of mononuclear Pd species with higher order Pd species, e.g. nanoclusters/nanoparticles are considered as being equally important in cross-coupling reaction mechanisms. A focus is placed on trichotomic behaviour of cross-coupling catalytic manifolds, from homogeneous to hybrid homogeneous–heterogeneous to truly heterogeneous behaviour. For the latter, surface chemistry and metal atom leaching (and various experimental techniques) are broadly discussed. It is now clear that mechanism for general cross‐coupling reactions, that is as presented to undergraduate students studying Chemistry degrees across the world, is undoubtedly more complex than first thought. New opportunities for catalyst design have therefore emerged in the area of Pd nanoparticles and nanocatalysis, with some wonderful applications especially in chemical biology, providing a snapshot of what the future might hold.

Fundamental investigations of enantioselective heterogeneous catalysis

Enantioselective catalysis is an increasingly important method of providing enantiomeric compounds for the pharmaceutical and agrochemical industries. To date, heterogeneous catalysts have failed to match the industrial impact achieved by homogeneous systems. One successful approach to the creation of heterogeneous enantioselective catalysts has involved the modification of conventional metal particle catalysts by the adsorption of chiral molecules. This article examines the contribution of effects such as chiral recognition and amplification to these types of system and how insight provided by surface science model studies may be exploited in the design of more effective catalysts.

Adsorption Calorimetry for Energy Conversion Technologies: Applications in Organic Photovoltaics, Catalysis, and Atomic Layer Deposition

Thesis (Ph.D.)--University of Washington, 2016-07

Thermal decomposition of mercerized linter cellulose and its acetates obtained from a homogeneous reaction

Cellulose acetates with different degrees of substitution (DS, from 0.6 to 1.9) were prepared from previously mercerized linter cellulose, in a homogeneous medium, using N,N-dimethylacetamide/lithium chloride as a solvent system. The influence of different degrees of substitution on the properties of cellulose acetates was investigated using thermogravimetric analyses (TGA). Quantitative methods were applied to the thermogravimetric curves in order to determine the apparent activation energy (Ea) related to the thermal decomposition of untreated and mercerized celluloses and cellulose acetates. Ea values were calculated using Broido's method and considering dynamic conditions. Ea values of 158 and 187 kJ mol-1 were obtained for untreated and mercerized cellulose, respectively. A previous study showed that C6OH is the most reactive site for acetylation, probably due to the steric hindrance of C2 and C3. The C6OH takes part in the first step of cellulose decomposition, leading to the formation of levoglucosan and, when it is changed to C6OCOCH3, the results indicate that the mechanism of thermal decomposition changes to one with a lower Ea. A linear correlation between Ea and the DS of the acetates prepared in the present work was identified.

Melting and freezing of spherical bismuth nanoparticles confined in a homogeneous sodium borate glass

The melting temperature and the crystallization temperature of Bi nanoclusters confined in a sodium borate glass were experimentally determined as functions of the cluster radius. The results indicate that, on cooling, liquid Bi nanodroplets exhibit a strong undercooling effect for a wide range of radii. The difference between the melting temperature and the freezing temperature decreases for decreasing radius and vanishes for Bi nanoparticles with a critical radius R = 1.9 nm. The magnitude of the variation in density across the melting and freezing transitions for Bi nanoparticles with R = 2 nm is 40% smaller than for bulk Bi. These experimental results support a basic core-shell model for the structure of Bi nanocrystals consisting of a central crystalline volume surrounded by a structurally disordered shell. The volume fraction of the crystalline core decreases for decreasing nanoparticle radius and vanishes for R = 1.9 nm. Thus, on cooling, the liquid nanodroplets with R < 1.9 nm preserve, across the liquid-to-solid transformation, their homogeneous and disordered structure without crystalline core.

High-temperature X-ray powder diffraction study of the tetragonal-cubic phase transition in nanocrystalline, compositionally homogeneous ZrO2-CeO2 solid solutions

Crystal structure of compositionally homogeneous, nanocrystalline ZrO2-CeO2 solutions was investigated by X-ray powder diffraction as a function of temperature for compositions between 50 and 65 mol % CeO2 center dot ZrO2-50 and 60 mol % CeO2 solid solutions, which exhibit the t'-form of the tetragonal phase at room temperature, transform into the cubic phase in two steps: t'-to-t '' followed by t ''-to-cubic. But the ZrO2-65 mol % CeO2, which exhibits the t ''-form, transforms directly to the cubic phase. The results suggest that t'-to-t '' transition is of first order, but t ''-to-cubic seems to be of second order. (C) 2008 International Centre for Diffraction Data.

Nanostructured Films Based on Carbon Nanotubes and Cobalt for the Electrocatalytic Reduction of H(2)O(2)

This paper presents the fabrication of a nanothick Co-modified film electrochemically synthesized on layer-by-layer (LbL) structures made with dendrimer polyamidoamine/carbon nanotubes (PAMAM/CNT), and its electrocatalytic properties toward H(2)O(2) reduction. Scanning electron microscopy indicated the formation of a homogeneous, 14 nm thick Co film. The porous nature of the PAMAM/CNT LbL film allowed the electrolyte access to the bottom of the electrode, generating a homogenous Co electrodeposit. In addition, the nanostructure based on Co-modified PAMAM/CNT LbL exhibited high electrocatalytic activity for H(2)O(2) reduction when compared to the Co-free PAMAM/CNT LbL film, which demonstrates the suitability of the system studied for biosensing. (C) 2011 The Electrochemical Society. [DOI: 10.1149/1.3602200] All rights reserved.