This thesis focuses on developing support materials for direct methanol fuel cell (DMFC) catalysts. The approach involves using graphene based materials including reduced graphene oxide (rGO), reduced graphene oxide-activated carbon (rGO-AC) hybrid and reduced graphene oxide-silicon carbide (rGO-SiC) hybrid as a support for Pt and Pt-Ru nanoparticles. Pt/rGO and Pt-Ru/rGO catalysts were synthesized by three chemical reduction methods: (1) modified polyol, (2) ethylene glycol (EG) reduction and (3) mixed reducing agents (EG + NaBH4) methods. The synthesized catalysts were characterized by physical and electrochemical techniques. The results demonstrated that Pt/rGO-3 and Pt-Ru/rGO-3 catalyst synthesized with Method-3 exhibit higher electrochemical active surface area (ECSA) than the other rGO supported and Vulcan supported commercial electrocatalysts. In addition, Pt/rGO-3 and Pt-Ru/rGO-3 catalysts showed better oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activities, respectively. The DMFC tests under different cell temperature (30, 50 and 70°C) and methanol concentration (1, 2 and 4 M) conditions further demonstrated the higher catalytic activity of the catalysts. The peak power density obtained with Pt/rGO-3 cathode and Pt-Ru/rGO-3 anode catalysts at 70°C with 1 M methanol was 63.3 mW/cm2 which is about 59 % higher than that of commercial Pt/C and Pt-Ru/C catalysts. The enhanced performance was attributed to the highly accessible and uniformly dispersed nanoparticles on rGO support with large surface area and high conductivity. Pt/rGO-AC (reduced graphene oxide-activated carbon) and Pt-Ru/rGO-AC catalysts were synthesized with various rGO:AC support ratios by using biomass derived AC. The results showed that the catalysts with content of 20 wt. % AC support (Pt/rGO-AC20 and Pt-Ru/rGO-AC20) exhibited higher ECSA, better catalytic activity and stability among all the tested catalysts. With 1 M methanol and 70°C cell temperature, the MEA with Pt/rGO-AC20 cathode and Pt-Ru/rGO-AC anode catalysts gave 19.3 % higher peak power density (75.5 mW/cm2), than that of Pt/rGO-3 and Pt-Ru/rGO-3 catalysts. The better DMFC performance was due to the incorporation of AC particles into rGO structure which builds electron-conductive paths between rGO sheets, facilitates the transport of reactant and products and provides higher specific surface area for the uniform distribution of nanoparticles. Pt/rGO-SiC catalysts were synthesized with variable silicon carbide (SiC) content in the hybrid support. Pt/rGO-SiC10 (10 wt. % of SiC support) catalyst showed higher ECSA and better catalytic activity compared to the Pt/SiC, Pt/rGO-3 and Pt/rGO-SiC20 catalysts. In addition, the Pt/rGO-SiC10 gave 14.2 % higher DMFC performance than the Pt/rGO-3 catalyst in terms of power density. The high performance can be attributed to the insertion of the SiC nanoparticles into rGO structure that improves the conductivity and stability of the catalyst by playing a spacer role between rGO layers. In summary, the overall results showed that the catalytic performance of the catalysts followed the trend in terms of support material: rGO-AC20 > rGO-SiC10 > rGO > Vulcan. The study demonstrated that the novel rGO-AC and rGO-SiC hybrids are promising catalyst supports for direct methanol fuel cell applications.

FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / Sete novos precursores de a-aminoÃcidos foram preparados atravÃs da reaÃÃo de alquilaÃÃo do acetoamidocianoacetato de etila 112 utilizando bromo-hexano, cloreto de benzila, brometo de alila, 9-(clorometil)-antraceno, brometo de 3-nitrobenzila, brometo de 4-nitrobenzila, brometo de 4- metoxibenzila e brometo de 2-metilnaftaleno como agentes alquilantes via CatÃlise de TransferÃncia de Fase (CTF). Tais reaÃÃes foram realizadas a 70oC, utilizando cloreto de benziltributilamÃnio como catalisador. ApÃs 5h de reaÃÃo, foram obtidos os compostos 113a-h com rendimentos que variaram de moderados a bons (24-74%), (Esquema I). A reaÃÃo de alquilaÃÃo do acetoamidocianoacetato de etila 112 com cloreto de benzila foi realizada utilizando os seguintes catalisadores quirais: Brometo de N-benzilmetilefedrÃnio (31a), Cloreto de (8R,9S)-N-9-metilantracenilcinchonidÃnio (34b), Cloreto de (8S,9R)-N-9-metilantracenilquinÃnio (34a), Cloreto de (8R,9S)-N-benzilmetilcinchonidÃnio (32b), Brometo de N-(benzilmetil)-O-alil-efedrÃnio (31g), Cloreto de (8S,9R)-NbenzilmetilcinchonÃnio (33b), Brometo de N-(9-metilantracenil)-O-alilcinchonidÃnio (34e) e Cloreto de (8S,9R)-N-9-metilantracenilcinchonÃnio (34d). NÃo foi observada induÃÃo assimÃtrica para as reaÃÃes utilizando os catalisadores supracitados na produÃÃo do precursor de a-aminoÃcido 113b. Ainda que nÃo tenha ocorrido induÃÃo assimÃtrica, bons rendimentos (83%) foram obtidos com os catalisadores 34e e 34d. Com base nos resultados obtidos a partir do programa de modelagem molecular Gaussian 03 foi possÃvel propor um modelo de aproximaÃÃo enolato-catalisador que justifica a falta de induÃÃo assimÃtrica observada com a utilizaÃÃo dos catalisadores quirais testados.a-aminoÃcidos 114 foram obtidos a partir dos precursores 113 atravÃs de hidrÃlise Ãcida, em rendimentos que variaram de moderados a bons (68-93%), (Esquema II). / Seven novel a-aminoacids precursors were prepared by the alkylation reaction of ethyl acetamidocyanoacetate 112 using bromohexane, benzyl chloride, allyl bromide, 9-(chloro-methyl)antracene, 3-nitrobenzyl bromide, 4-nitrobenzyl bromide, 4-metoxibenzyl bromide and 2-methyl-naphtyl bromide as alkylating agents via Phase Transfer Catalysis (PTC). These reaction were performed at 70oC using benzyltributyl ammonium chloride as catalyst. After 5h, compounds 113a-h were obtained in moderated to good yields (24-74%), Scheme I. The alkylation reaction of ethyl acetamidocyanoacetate 112 with benzyl chloride was carried out using chiral catalysts phase transfer as: Nbenzylmethylephedrinium bromide (31a), (8R,9S)-N-9-methylantracenylcinchonidinium chloride (34b), (8S,9R)-N-9-methylantracenylquininium chloride (34a), (8R,9S)-Nbenzylmethylcinchonidinium chloride (32b), N-(benzilmethyl)-O-allylephedrinium bromide (31g), (8S,9R)-N-benzylmethylcinchoninium chloride (33b), N-(9-methylantracenyl)-O-allyl-cinchonidinium bromide (34e) and (8R,9S)-N-9-methylantracenylcinchoninium chloride (34d). No asymmetric induction was observed using the aforementioned catalysts for the production of a-aminoacid optically active precursor 113b. Although no asymmetric induction was observed, good yields (83%) were obtained with catalysts 34e and 34d.Based on the data obtained from molecular modeling program Gaussian 03, it was possible to propose a model for the enolate-catalyst pair, that is in accordance with the lack of asymmetric induction for the reactions performed in the presence of the chiral catalysts. a-aminoacids 114 were obtained from precursors 113 by acid hydrolysis with moderate to good yields (68-93%), (Scheme II).

A reatividade dos complexos do tipo [RuCl2(PPh3)2(amina)], onde a amina = 3,5-dimetilpiperidina (complexo 1) ou piperidina (complexo 2), foi investigada na polimerização via metátese por abertura de anel (ROMP) de norborneno (NBE) e norbornadieno (NBD), na presença de etildiazoacetato (EDA), como fonte de carbeno, em CHCl3. O objetivo foi observar a combinação dos efeitos eletrônicos e estéricos da PPh3 com uma amina como ligantes ancilares na reatividade em ROMP. Os resultados com o complexo 1 foram comparados aos resultados obtidos com o complexo 2. Na ROMP de NBE, o complexo 1 proporcionou um rendimento de 70% de poliNBE (Mn = 8,3 &times; 104 g/mol; IPD = 2,03), enquanto o complexo 2 promoveu reação quantitativa (Mn = 1,2 x 105 g/mol; IPD = 1,90) com razões molares [NBE]/[Ru] = 5000 e [EDA]/[Ru] = 48 e 1,1 &micro;mol de Ru por 5 min a 25 &deg;C. Os poliNBEs apresentaram um &sigma;c = 0,38, determinado por RMN de 13C{1H} e uma Tg = 37 &deg;C, determinada através das análises de DSC e DMTA. Na ROMP de NBD com o complexo 1 obteve-se rendimento quantitativo, com IPD = 2,62 com razão molar [NBD]/[Ru] = 5000 por 20 min a 25 &deg;C, enquanto que a reação com o complexo 2 resultou em um rendimento de 55%, com IPD = 2,16 nas mesmas condições. Concluiu-se que a presença dos dois grupos metila no anel piperidina no complexo 1 proporcionou um aumento no período de indução para produzir a espécie metal carbeno, o que justifica os menores rendimentos na ROMP de NBE quando comparado com o complexo 2. No entanto, o maior sinergismo eletrônico amina&rarr;Ru&rarr;monômero contribuiu para uma melhor ativação de olefinas mais difíceis de serem polimerizadas como o NBD, como ocorre no caso com o complexo 1.<br />Poli[NBE]-co-[NBD] foram obtidos via ROMP com os complexos 1 e 2 como iniciadores. As reações de copolimerização foram realizadas utilizando uma quantidade fixa de NBE ([NBE]/[Ru] = 5000) com diferentes concentrações de NBD ([NBD]/[Ru] = 500, 1000, 1500 e 2000) em CHCl3, iniciadas com EDA à temperatura ambiente. A presença de NBD nas cadeias de poliNBE foi caracterizada por RMN de 1H e de 13C{1H} para todos os casos onde a quantidade de NBD foi variada, suportando a formação de poli[NBD]-co-[NBD]. Considerando que a microestrutura do poli[NBD]-co-[NBD] não foi influenciada pela quantidade de NBD nem pelo tipo de iniciador, os valores de Mn e de IPD foram otimizados quando se aumentou a concentração de NBD no meio reacional. O aumento da quantidade de NBD propiciou um aumento na densidade de entrecruzamento resultando em um aumento na Tg e no módulo de armazenamento (E\'). A análise morfológica da superfície dos polímeros por MEV mostrou uma estrutura altamente porosa para os poliNBEs sintetizados e indicou uma diminuição no tamanho desses poros para os poli[NBD]-co-[NBD] isolados, alcançando uma superfície totalmente lisa com a composição [NBE]5000[NBD]2000, para ambos os catalisadores. / The reactivity of the new complex [RuCl2(PPh3)2(3,5-Me2piperidine)], complex 1, was investigated for ring opening metathesis polymerization (ROMP) of norbornene (NBE) and norbornadiene (NBD) in the presence of ethyl diazoacetate (EDA) in CHCl3. The aim is to observe the combination of PPh3 and an amine as ancillary ligands in the reactivity for ROMP. Thus, the results with the complex 1 were compared to the results obtained when the amine is piperidine (complex 2). Reaction with the complex 1 provides 70% yield of isolated polyNBE (Mn = 8.3 &times; 104 g/mol; PDI = 2.03), whereas the complex 2 provides quantitative reaction (Mn = 1.2 &times; 105 g/mol; PDI = 1.90) with [NBE]/[Ru] = 5000, [EDA]/[Ru] = 48 and 1.1 &micro;mol of Ru for 5 min at 25 &deg;C. The resulting polymers showed a &sigma;c = 0,38, determined by 13C NMR, and Tg =37 &deg;C, determined by DSC and DMTA. For ROMP of NBD, the complex 1 showed quantitative yield with PDI = 2.62 when [NBD]/[Ru] = 5000 for 20 min at 25 &deg;C, whereas the reaction with the complex 2 reached 55% with PDI = 2.16 in the same conditions. It is concluded that the presence of the two methyl groups in the piperidine ring provides an increase in the induction period to produce the Ru-carbene species justifying better polyNBE results with the complex 2, and a greater amine&rarr;Ru&rarr;monomer synergism which contributed to the best activation of olefin with greater difficulty of being polymerized as NBD, as in the case with the complex 1.<br />Copolymers of NBE with NBD were obtained via ROMP with the complexes 1 and 2 as initiators. The copolymerizations reactions were performed using a fixed quantity of NBE ([NBE]/[Ru] = 5000) with different concentrations of NBD ([NBD]/[Ru] = 500, 1000, 1500 and 2000) in CHCl3, initiated with EDA at room temperature. The presence of NBD in the polyNBE chains was characterized by 1H and 13C NMR. Whereas the copolymer microstructure was influenced neither by the NBD quantity nor by the initiator type, the Mn and PDI values were improved when increasing the NBD quantity in the medium. When raising the NBD amount, DMA results indicated increased cross-linking with increasing Tg and E\' storage modulus, as well as the fact that SEM micrographs indicated decreased pore sizes in the porous isolated copolymers.

No description available.

Mesoporous aggregates of nanocrystalline zeolites with MFI and BEA frameworks have been synthesized using a one-pot and single structure directing agent method. The effect of different reaction conditions, such as temperature, time, pH and water content, on the particle size, surface area and mesopore volume has been studied. Nanocrystalline and mesoporous ZSM-5, β and Y zeolites were modified with different transition metals and the resulting single- and double metal containing catalyst materials were characterized. Nanocrystalline Silicalite-1 zeolite samples with varying particle size were functionalized with different organosilane groups and the cytotoxic activity of the zeolite nanocrystals was studied as a function of particle size, concentration, organic functional group type, as well as the type of cell line. Framework stability of nanocrystalline NaY zeolite was tested under different pH conditions. The synthesized zeolites used in this work were characterized using a variety of physicochemical methods, including powder X-ray diffraction, Solid State NMR, nitrogen sorption, electron microscopy, Inductively Coupled Plasma - Optical Emission Spectroscopy and X-ray Photoelectron Spectroscopy.

Thesis advisor: Amir H. Hoveyda / Chapter One Development of Simple Organic Molecules as Catalysts for Enantioselective Allyl Additions to N-Phosphinoylaldimines and Isatins A new catalytic protocol for the enantioselective addition of organoborates to imines and carbonyls is described. This novel method, which does not require transition metals utilizes a modular and easily accessed aminophenol to dictate the stereochemistry of the products. Allyl-additions to N-phosphinoylaldimines and isatins, as well as allenyl-additions to isatins are studied and literature relevant to these transformations is discussed. Additionally, two separate methods for obtaining "crotyl-type" addition products to aldimines; one requiring α-chiral allylboronates and the other requiring a zinc-alkoxide, are discussed. Studies to elucidate the mechanism of this catalytic protocol are also contained in this chapter. Chapter Two Enantioselective Additions to Fluorinated Ketones: A Platform for Studying the Interaction Between Organofluorine and a Small Molecule Utilizing the new protocol discussed in Chapter One, allyl- and allenyl-groups are added enantioselectively to ketones containing a fluorinated substituent. Myriad tertiary alcohols are synthesized, demonstrating the value of this method. This study also allows for examining how organofluorine containing compounds bind to other organic molecules, which is a current topic of intense interest in the field of medicinal chemistry. Mechanistic studies support the idea that, in many cases, the fluorine of the substrate is electrostatically attracted to the ammonium-ion in the catalyst. Chapter Three Enantioselective Additions of Organoboronates to Ketones and Alphaketoesters Promoted by an Aminophenol Containing Catalyst Modification of the aminophenol disclosed in Chapter One allows for increased enantioselectivity for the allyl-addition to both simple ketones (such as acetophenone) and alphaketoesters. For simple ketones, a critical component of the optimal catalyst is replacing the tert-butyl group ortho to the phenol with the sterically large triphenylsilyl group. For alphaketoesters, this tert-butyl group was replaced with the sterically smaller metyl group. Rationale for why these contradictory changes in the catalyst structure lead to higher enantioselectivity for reactions with these two classes of ketones is discussed. Chapter Four Ag-Catalyzed Enantioselective Vinylogous Mannich Reactions of γ-Substituted Siloxyfurans with Aldimines A previously disclosed Ag-catalyzed enantioselective vinylogous Mannich reaction (EVM) with α-, β-, and unsubstituted siloxyfurans is extended to include γ-substituted siloxyfurans. This method, which generates a tertiary stereogenic center concurrent with an adjacent to a quaternary stereogenic center, requires a rarely used 2-thiomethylaniline N-protecting group for the aldimines. / Thesis (PhD) — Boston College, 2014. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

The objective of this thesis is to aid in the development of Remedial Extraction And Catalytic Hydrodehalogenation (REACH), a green remediation technology used to remove and destroy halogenated hydrophobic organic compounds from soil. REACH has no secondary waste streams, uses an environmentally benign solvent, and aims to catalytically destroy rather than transfer the organic contaminants into a different phase. In this thesis, a bench-top semicontinuous model of the proposed remediation technology was constructed and used to extract the model contaminant, 1,2,4,5-tetrachlorobenzene, from soil and to convert it to an acceptable end product, cyclohexane. Palladium was used as a catalyst for hydrodehalogenation, which converted the tetrachlorobenzene to benzene. Rhodium was used to catalyze the hydrogenation of benzene to cyclohexane. A novel method, ultraviolet solvent treatment, was proposed to mitigate catalyst deactivation that occurs because of extracted chemicals contained in the contaminated soil. The goal of this treatment is to degrade organic matter that is suspected of causing catalyst deactivation. The REACH process was found to successfully extract TeCB from the soil, but only partial conversion from TeCB to cyclohexane occurred. Catalyst deactivation was the suspectedcause of the low amount of conversion observed. Hydrogen limitation was also tested as a cause of limited conversion, but was not found to be a contributor. Ultraviolet solvent treatment was tested as a means of mitigating catalyst deactivation. However, the treatment was not effective in making a profound difference in stopping the catalyst from deactivating. The experiments conducted in this research show that REACH has the potential to become a viable technology for cleaning soil contaminated with halogenated organic compounds. However, future research needs to be done to greatly reduce the severity of catalyst deactivation and to determine with which other halogenated organic compounds the technology works well.

Bismuth molybdates have long been known as active catalysts for selective oxidation of olefins. There are several phases of bismuth molybdates but only three of them are known to be active for partial oxidation of propylene to acrolein, namely, α, β, and γ bismuth molybdates. A significant amount of work has been carried out and reported in the literature, aiming to understand the reaction mechanisms so as to control the reaction process. It has been revealed that the oxidation reaction follows the redox mechanisms and lattice oxygen plays a key role as the main oxygen source for the reaction and controls the catalyst performance. The properties of the lattice oxygen are influenced by the bulk crystalline structure of the catalyst. Therefore, it is possible that the crystal structure influences the performance of the catalyst in promoting the partial oxidation reaction. However, there appears to be a lack of detailed reports in the literature on the relationship between the bulk crystal structure and the activity and selectivity of the catalyst for the partial oxidation reaction. The work reported in this thesis has been designed to achieve an improved understanding of the catalyst structure in relation to the activity and selectivity of the catalyst for the partial oxidation of propylene to acrolein. / In order to fulfil the objectives of this study, several investigation steps have been taken, namely 1) acquiring and analysing the catalyst structural parameters under real reaction conditions as well as at room temperature by means of neutron diffraction and X-ray diffraction, 2) obtaining kinetics from experimentation using a packed-bed reactor operating under differential reactor mode so as to eliminate the mass diffusion effect, and 3) developing and proposing reaction mechanisms which contain events that occur on the crystalline structure of the catalysts, particularly lattice oxygen, during the reaction. Characterisation of the structure of the catalysts has been carried out by means of In-situ neutron diffraction, which has the ability to probe the crystal structure at atomic level. The structure is characterised under simulated reaction conditions to investigate the dynamics of the crystal structure, particularly lattice oxygen, during the reaction. The In-situ diffraction studies have uncovered the relationship between the crystal structure of bismuth molybdates and their selectivity and activity towards the catalytic partial oxidation of propylene to acrolein. The possible active lattice oxygen in the bismuth molybdate structures has been identified. The active lattice oxygen ions are responsible for maintaining redox balance in the crystal lattice and thus control the catalyst activity and selectivity. Mobile oxygen ions in the three bismuth molybdate crystal phases are different. The mobile oxygen ions are O(1), O(11), and O(12) in the α phase; O(3), O(11), O(16), and O(18) in the β phase; and O(1) and O(5) in the γ phase. / The mobile lattice oxygen ions are proposed to be the source of the oxidising oxygen responsible for the selective oxidation of propylene to acrolein. One common feature of all mobile oxygen ions, from a catalyst crystal structure point of view, is that they are all related to molybdenum ions rather than bismuth ions in the lattice. By modifying the physical and chemical environment of the molybdenum oxide polyhedra, it is possible to modify the catalyst selectivity and activity. The diffraction diagnoses have also shown that molybdenum oxide polyhedra in all bismuth molybdate are unsaturated. In contrast, the bismuth oxide polyhedra are over charged. The co-existence of molybdenum ions that are co-ordinately unsaturated with bismuth ions that are over valence-charged promote the formation of allyl radical such as those found in the partial oxidation of propylene to acrolein. The molybdenum ions become propylene-adsorbing sites while the bismuth ions are the active sites to attract hydrogen from the adsorbed propylene, leading to the formation of the allyl intermediate. Oxygen ions from the mobile lattice oxygen are a more moderate oxidant than molecular oxygen. With their mild activity, the partially oxidised products are the main products such as acrolein and formaldehyde when oxygen ions react with the allyl intermediate while more complete combustion products such as carbon oxides and organic acids become the side products. / Investigation into the kinetics and reaction mechanisms has revealed the aforementioned evidence to support the role of the mobile lattice oxygen ions in the partial oxidation of propylene to acrolein. The kinetic experiments have employed the power rate law to model the kinetic data. The model shows that the reaction orders in propylene and oxygen concentrations are a function of the reaction temperature. The reaction order in propylene increases with reaction temperature, from 0.6 at 300°C to 1.0 at 450°C for all the bismuth molybdate catalysts, while the reaction order in oxygen decreases from 0.6 at 300°C to 0 at 450°C. The activation energies are 99.7, 173, and 97.7 kJ.mol-1 for α-Bi2Mo3O12, β-Bi2Mo2O9, and γ-Bi2MoO6, respectively. The changes in reaction orders with respect to propylene and oxygen indicate that the reaction occurs through the redox mechanisms, using the mobile lattice oxygen. The structural dynamics identified earlier explains the decrease in the acrolein selectivity at high temperatures (ca above 390°C). At these temperatures, the mobile oxygen becomes more mobile and more active. As a result, as the mobility of the oxygen ions increase, their reactivity also increases. The increase in the oxygen reactivity leads to unselective, complete oxidation reaction, forming the complete oxidation products CO2 and H2O. The reduction-reoxidation of bismuth molybdate is controlled by the diffusion of oxygen ions in the lattice, because the reduction sites do not have to be adjacent to the oxidation sites. The oxygen diffusion rate is in turn controlled by how mobile the lattice oxygen ions are. / Hence, the mobile oxygen ions discussed earlier control the catalyst activity in catalysing the reaction of propylene partial oxidation. The examination of several reaction mechanism models has given further evidence that the propylene partial oxidation to acrolein occurs via the redox mechanism. In this mechanism, the rate of acrolein formation depends on the degree of fully oxidised sites in the bismuth molybdate. The oxidised sites affect the apparent reaction orders in propylene and oxygen and thus control the kinetics of partial oxidation of propylene to acrolein. The more easily the reduced catalysts are reoxidised, the more active the catalysts in converting propylene to acrolein. A set of reaction steps has been proposed, which adequately reassembles the reaction mechanism. Side product reactions are also identified and included in the mechanisms. The present thesis has revealed a much detailed insight into the role of lattice oxygen in the catalytic partial oxidation of propylene to acrolein over bismuth molybdates and established the relationship between structure and activity and selectivity of the catalyst. This work has laid a foundation for future catalyst design to be based on structural knowledge of the catalysts.

Abstract Cobalt-based complexes are widely used in industry and organic synthesis as catalysts for the oxidation of hydrocarbons. The Co/Mn/Br (known as "CAB system") catalyst system is effective for the oxidation of toluene. The Co/Mn/Br/Zr catalyst system is powerful for the oxidation of p-xylene, but not for the oxidation of toluene. [Co3O(OAc)5(OH)(py)3][PF6] (Co 3+ trimer 5) is more effective than [Co3O(OAc)6(py)3][PF6] (Co 3+ trimer 6) as a catalyst in the CAB catalyst system. Higher temperatures favour the oxidation of toluene. Zr 4+ does not enhance the oxidation of toluene. Zr 4+ could inhibit the oxidation of toluene in the combination of Co/Br/Zr, Co/Mn/Zr or Co/Zr. NHPI enhances the formation of benzyl alcohol, but the formation of other by-products is a problem for industrial processes. Complex(es) between cobalt, manganese and zirconium might be formed during the catalytic reaction. However, attempts at the preparation of complexes consisting of Co/Zr or Mn/Zr or Co3ZrP or Co8Zr4 clusters failed. The oxidation of cyclohexane to cyclohexanone and cyclohexanol is of great industrial significance. For the homogeneous catalysis at 50 o C and 3 bar N2 pressure, the activity order is: Mn(OAc)3 �2H2O > Mn12O12 cluster > Co 3+ trimer 6 > [Co3O(OAc)3(OH)2(py)5][PF6]2 (Co 3+ trimer 3) > Co 3+ trimer 5 > Co(OAc)2 �4H2O > [Co2(OAc)3(OH)2(py)4][PF6]-asym (Co dimerasym) > [Co2(OAc)3(OH)2(py)4][PF6]-sym (Co dimersym); whereas [Mn2CoO(OAc)6(py)3]�HOAc (Mn2Co complex) and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. But at 120 o C and 3 bar N2 pressure, the activity order is changed to: Co dimerasym > Co(OAc)2 �4H2O > Co trimer 3 and Mn(OAc)3 �2H2O > Co 3+ trimer 6 > Mn2Co complex > Co 3+ trimer 5 > Co dimersym > Mn12O12 cluster. The molar ratio of the products was close to cyclohexanol/cyclohexanone=2/1. Mn(II) acetate and zirconium(IV) acetate hydroxide showed almost no activity under these conditions. Among those cobalt dimers and trimers, only the cobalt dimerasym survived after the stability tests, this means that [Co2(OAc)3(OH)2(py)4][PF6]-asym might be the active form for cobalt(II) acetate in the CAB system. Metal-substituted (silico)aluminophosphate-5 molecular sieves (MeAPO-5 and MeSAPO-5) are important heterogeneous catalysts for the oxidation of cyclohexane. The preparation of MeAPO-5 and MeSAPO-5 and their catalytic activities were studied. Pure MeAPO-5 and MeSAPO-5 are obtained and characterised. Four new pairs of bimetal-substituted MeAPO-5 and MeSAPO-5(CoZr, MnZr, CrZr and MnCo) were prepared successfully. Two novel trimetal-subtituted MeAPO-5 and MeSAPO-5 (MnCoZr) are reported here. Improved methods for the preparation of four monometal-substituted MeAPO-5 (Cr, Co, Mn and Zr) and for CoCe(S)APO-5 and CrCe(S)APO-5 are reported. Novel combinational mixing conditions for the formation of gel mixtures for Me(S)APO-5 syntheses have been developed. For the oxidation of cyclohexane by TBHP catalysed by MeAPO-5 and MeSAPO-5 materials, CrZrSAPO-5 is the only active MeSAPO-5 catalyst among those materials tested under conditions of refluxing in cyclohexane. Of the MeAPO-5 materials tested, whereas CrCeSAPO-5 has very little activity, CrZrAPO-5 and CrCeAPO-5 are very active catalysts under conditions of refluxing in cyclohexane. MnCoAPO-5, MnZrAPO-5 and CrAPO-5 are also active. When Cr is in the catalyst system, the product distribution is always cyclohexanone/cyclohexanol equals 2-3)/1, compared with 1/2 for other catalysts. For MeAPO-5, the activity at 150 o C and 10 bar N2 pressure is: CrZrAPO-5 > CrCeAPO-5 > CoZrAPO-5. For MeAPO-5 and MeSAPO-5, at 150 o C and 13 bar N2 pressure, the selectivity towards cyclohexanone is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5; and the selectivity towards cyclohexanol is: MnZrAPO-5 > CrZrAPO-5 > MnCoAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5. Overall the selectivity towards the oxidation of cyclohexane is: CrZrAPO-5 > CrZrSAPO-5 > CrCeAPO-5 > CrAPO-5 > MnCoAPO-5 > MnZrAPO-5. The amount of water in the system can affect the performance of CrCeAPO-5, but has almost no effect on CrZrAPO-5. Metal leaching is another concern in potential industrial applications of MeAPO-5 and MeSAPO-5 catalysts. The heterogeneous catalysts prepared in the present work showed very little metal leaching. This feature, coupled with the good selectivities and effectivities, makes them potentially very useful.

The degradation of phosphate triesters is efficiently catalyzed by organophosphate hydrolases (OPH). While a number of recent studies have focused on optimizing the rate of hydrolysis observed with the native enzyme, no dinuclear complexes that mimic the function of OPH have been reported or investigated. Our present research focuses on the synthesis of dinuclear metal complexes and on the study of their catalytic abilities. An important aspect of this research concerns the investigation of the coordination chemistry of dinuclear ligands designed to hold two metal cations in well defined positions. The ability of the different complexes to catalyze the degradation of thiophosphate triester is presented. Out of several complexes studied, ortho-metallated Pd (II) complexes have been found to display the highest catalytic activity for the hydrolysis of parathion.