No description available.

Crystals of the title compound are monoclinic with a= 8.314 (5), b= 22.723 (9), c= 12.589 (6) A, /3= 123.0 (2t, Z=4, space group P2dc. The structure was determined by Patterson and Fourier methods and refined by full-matrix least squares to a final R of 0.030 for 2043 independent reflexions. The U atom has pentagonal bipyramidal coordination and the N-methylacetylacetoneamine is bonded to U via O. There are two intramolecular N-H. . .0 hydrogen bonds which govern the geometry of the adduct molecule.

Symmetric nonaqueous redox flow batteries (RFBs) use negative and positive battery solutions of the same solution composition to operate at high cell voltages. This research effort targets these systems since they offer performance improvements derived from using nonaqueous systems and symmetric active species. Nonaqueous solutions permit significantly higher cell voltages than state-of-the-art aqueous RFBs and symmetric active species chemistries reduce the required complexity of cell reactors. Both performance advantages correspond to significant cost improvements beyond already commercially competitive aqueous RFB chemistries. This document focuses on two classes of symmetric nonaqueous RFB chemistries: coordination complexes such as vanadium acetylacetonate [V(acac)₃] or chromium acetylacetonate [Cr(acac)₃], and organic active species such as 9,10-diphenylanthracene (DPA). V(acac)₃ delivers reversible electrochemistry that supports a 2.2 V equilibrium cell potential, but there are some gaps in the understanding of its degradation mechanisms. Cr(acac)₃ supports redox reactions that suggest cell potentials above 4 V, but shows signs of irreversibility in voltammetry experiments and is not yet well understood. Finally, the DPA system could be interesting because it does not use metal active species, and its voltammetry promises cell potentials above 3 V. Yet DPA suffers from low solubility in nonaqueous solvents that limit its practicality. These three systems show promise for symmetric nonaqueous RFBs and offer avenues for further improvement. Voltammetry and spectroelectrochemical electrolysis experiments on the metal coordination complexes clarify the mechanisms behind the voltammetry on these symmetric chemistries. Ligand dissociation causes the irreversible behavior observed in voltammetry on Cr(acac)₃. The same experiments reaffirm the expected cyclability of V(acac)₃. Chemical functionalization of the DPA center is performed to investigate the solubility and reactivity of various derivatives. Functionalizing DPA with ethylene glycol chains to form 'DdPA' significantly increases solubility limits from 0.6 mM and 44 mM for DPA in acetonitrile and 1,2-dimethoxyethane, respectively, to 12 mM and 0.21 M for DdPA in the same solvents. At the same time, DdPA retains redox activity that promises 3 V cell potentials. Ultimately, a custom, nonaqueous-compatible redox flow reactor was designed and used to test the performance of V(acac)₃, DPA, and DdPA under various operating conditions. Contradicting previous reports, V(acac)₃ delivers stable cycling over the 21- cycle experimental protocol. Exploration over a range of flow rates and current densities give energy and power densities up to 1.09 WhL^-1 and 0.16 Wcm^-2, respectively, for the battery solution compositions examined. These experiments further predict values up to 28 WhL^-1 and at least 0.22 Wcm^-2 for optimized V(acac)₃ battery solutions. DPA and DdPA deliver the highest operating potential observed from organic nonaqueous RFBs, discharging at 3 V and 2.9 V, but require further work to understand degradation in the systems.

Made available in DSpace on 2014-06-11T19:30:18Z (GMT). No. of bitstreams: 0 Previous issue date: 2011-06-20Bitstream added on 2014-06-13T21:00:48Z : No. of bitstreams: 1 nielsen_gf_me_bauru.pdf: 1826165 bytes, checksum: 6fa4e6c04592e7eb812d72fe4f9a2db3 (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Filmes finos de alumina vêm sendo amplamente estudados em função de suas propriedades físicas e químicas. Em aplicações industriais, filmes de alumina são utilizados, por exemplo, em ferramentas de corte e em circuitos microeletrônicos. Neste trabalho empregou-se o processo de PECVD (do inglês, Plasma Enhanced Chemical Vapor Deposition) para sintetizar fimes contendo óxido de alumínio. Os filmes foram depositados a partir de plasmas excitados por radiofrequencia (13,56 MHz) em misturas de acetilacetonato de alumínio e argônio. Uma configuração experimental inédita foi empregada para permitir a incorporação de alumínio nos filmes: o pó do organometálico foi colocado diretamente no eletrodo por onde um plasma de argônio foi excitado. A pulverização catódica aliada a sublimação do organometálico faz com que haja, em determinadas condições, a deposição de filmes contendo alumina. Foram avaliados os efeitos da pressão do plasma e da potência do sinal de excitação nas propriedades dos filmes resultantes. A técnica de perfilometria foi utilizada para determinar a espessura da camada depositada. Difração de raios X (DRX), com a incidência de ângulos rasantes, foi empregada para investigar a estrutura do material. As técnicas de espectroscopia de absorção no infravermelho por transformada de Fourier (FTIR) e espectroscopia de energia dispersiva (EDS) foram respectivamente utilizadas para analisar a estrutura e a composição química dos filmes. A morfologia das amostras preparadas sobre aço-inoxidável foi analisada por microscopia eletrônica de varredura (MEV) enquanto a dureza foi avaliada por nanoindentação. Foram obtidos filmes amorfos com espessuras de até 7 μm que contêm carbono, alumínio, oxigênio e hidrogênio. Observou-se que as proporções de alumínio e carbono são altamente dependentes da energia cinética dos íons presentes no plasma... / Recently aluminium oxide thin films have been widely studied due to their important physical and chemical properties. Depositions in cutting tools and in microelectronic circuits are examples of industrial applications of industrial applications of aluminum oxide films. In this work, alumina-containing films were prepared by PECVD (Plasma Enhanced Chemical Vapor Deposition) using a new configuration of the plasma system; the metalorganic powder was placed directly on the powered electrode while the substrates were mounted on the grounded topmost electrode. The plasma was excited by applying radiofrequency (13.56 MHz) power to the lower electrode in an argon atmosphere. The sputtering combined with the sublimation of organometallic compound enabled the growth of an alumina-containing organic layer. The effect of the plasma excitation parameters on the properties of the resulting films was studied. Film thickness was measured using profilometry. Grazing angle incidence X-ray diffractometry (GAXRD) was used to determine the structure of the films. Fourier trasnform Infrared Spectroscopy (FTIR) and energy dispersive spectroscopy (EDS) techniques were used to analyze chemical structure and coposition, respectively. The surface morphology was analyzed by scanning electron microscopy (SEM) while film hardness was evaluated by nanoindentation Amorphous organic films were deposited with thicknesses of up to 7 μm. The films were composed of aluminum, carbon, oxygen and hydrogen, the proportions of carbon and aluminum being strongly dependent on the kinetic energy of the ions. The film surface was uniform but presented particulares and, in some cases, wrinkles. The proportion of such defects depends on the plasma excitation parameters

Recent study has shown that ruthenium(III) acetylacetonate acts as a homogeneous catalyst in the hydrolysis of sodium borohydride. When two equivalents of trimethylphosphite per ruthenium is added to the reaction solution containing sodium borohydride and ruthenium(III) acetylacetonate in the mixture of water and tetrahydrofuran, the rate of hydrogen generation is practically stopped (or reduced to the level of self hydrolysis). However, the catalytic hydrogen evolution of sodium borohydride restarts at an unexpectedly high rate in a certain period of time (induction time) after addition of trimethylphosphite. Consequently, trimethylphosphite known to be a poison in the hydrolysis, is involved in the formation of a new active catalyst (ruthenium species containing trimethylphosphite ligands) which has much higher catalytic activity in comparison with sole ruthenium(III) acetylacetonate. The same rate enhancement is observed by addition of two equivalents of triphenylphosphite per ruthenium into the medium. Varying the phosphorus compound affects not only the life time of catalyst but also the kinetic and activation parameters of the hydrolysis of sodium borohydride. However, varying the mole ratio of phosphorus compound to ruthenium does not affect the rate of hydrolysis or in other words, the rate of hydrogen generation is independent of phosphite concentration. Trans- and cis-[Ru(acac)2{P(OMe)3}2] complexes do not show significant catalytic activity in hydrogen generation of sodium borohydride. However, catalytic activity of cis-isomer is highly increased in the presence of two equivalents of trimethylphosphite, showing that the active catalyst formed during hydrolysis of sodium borohydride starting with Ru(acac)3 or cis-[Ru(acac)2{P(OMe)3}2], has more than two phosphine ligands. For the first time, a ruthenium(I) complex was isolated from aqueous solution after finishing the catalytic hydrolysis of sodium borohydride starting with ruthenium(III) acetylacetonate and trimethylphosphite. Hydridotetrakis(trimethylphosphite)ruthenium(I), [Ru{P(OMe)3}4H] was isolated and characterized by single crystal X-ray diffraction, Mass, UV-visible, FTIR, 1H, 13C and 31PNMR spectroscopy. Following the catalytic reaction by UV-Visible spectroscopy shows in-situ formation of a Ru(II) species which is mostly converted back to ruthenium(III) acetylacetonate after hydrolysis reaction along with formation of [Ru{P(OMe)3}4H] complex as a minor product. Although Ru(II) species could not be isolated, adding 1 equivalent of 2,2&#039 / -bipyridine yielded [Ru(acac)(bipy){P(OMe)3}H] complex which could be isolated and characterized by Mass, UV-Visible, FTIR, 1H, 13C and 31PNMR spectroscopy. In-situ generated Ru(II) species has much higher catalytic activity in comparison with its stabilized form [Ru(acac)(bipy){P(OMe)3}H] or [Ru{P(OMe)3}4H] complex. Conclusively, the fac-[Ru(acac){P(OMe)3}3H] complex is believed to be the in-situ generated Ru(II) species and the active catalyst in the hydrolysis of sodium borohydride.

Amine boranes have recently been considered as solid hydrogen storage materials with high capability of hydrogen storage. Dimethylamine borane is one of the promising amine boranes with high theoretical gravimetric capacity of 16.9 wt%. Dimethylamine borane can undergo dehydrogenation only in the presence of a suitable catalyst at moderate temperature. In this project, throughout the dehydrogenation of dimethylamine borane (DMAB), the catalytic activity of ruthenium(III) acetylacetonate was examined for the first time. During the catalytic reaction, formation of a new in-situ ruthenium(II) species, [Ru{N2Me4}3(acac)H], is observed. Mercury poisoning experiment indicates that the in-situ ruthenium(II) species is a homogeneous catalyst in the dehydrogenation of dimethylamine borane. Kinetics of catalytic dehydrogenation of dimethylamine borane starting with ruthenium(III) acetylacetonate was investigated depending on catalyst concentration, substrate concentration and temperature. As a result, the hydrogen generation rate was found to be first-order with respect to catalyst concentration and zero-order regarding the substrate concentration. Besides, evaluation of the kinetic data yielded that the activation parameters for dehydrogenation reaction: the activation energy, Ea = 85 &plusmn / 2 kJ&bull / mol-1 / the enthalpy of activation, DH# = 82 &plusmn / 2 kJ&bull / mol-1 and the entropy of activation / DS# = -85 &plusmn / 5 J&bull / mol-1&bull / K-1. Additionally, before deactivation, [Ru{N2Me4}3(acac)H] provides 1700 turnovers over 100 hours in hydrogen evolution from the dehydrogenation of dimethlyamine borane. [Ru{N2Me4}3(acac)H] complex formed during the dehydrogenation of dimethylamine borane was isolated and characterized by UV-Visible, FTIR, 1H NMR, and Mass Spectroscopy. The isolated ruthenium(II) species was also tested as homogeneous catalyst in the dehydrogenation of dimethylamine borane.

Polyethylene (PE) is one of the most popular polymers used in daily life. However, saturated hydrocarbons cannot absorb the energy of light reaching to earth, so degradation process is rather slow which in return cause disposal problems. On the other hand, it was observed that in presence of oxygen and impurities in the polymer matrix, degradation can be rendered to shorter time intervals. This study covers investigation of effect of three different additives in UV induced oxidative degradation of polyethylene. In this work vanadium (III) acetylacetonate, serpentine and Cloisite 30B were used as additives both together and alone to follow photodegradation of polyethylene. Amount of vanadium (III) acetylacetonate was kept constant at 0.2 wt%, while serpentine and Cloisite 30B were used between 1 and 4 wt%. All compositions were prepared by using Brabender Torque Rheometer, and shaped as thin films by compression molding. Samples were irradiated by UV light up to 500 hours. Mechanical and spectroscopic measurements were carried out in certain time intervals to monitor the degradation. It can be concluded that all combinations of three additives showed the fastest degradation behavior compared to pure PE. In the absence of vanadium (III) acetylacetonate the degradation was slowed and fluctuations were observed in the residual percentage strain at break values. There was not a significant change in tensile strength of all samples. Carbonyl index values followed by FTIR were always in increasing manner. Thermal properties were also investigated by DSC Thermograms and they did not change significantly.

Gegenstand der vorliegenden Arbeit ist der Entwurf und die Realisierung kristalliner organisch-anorganischer Festkörper mit wohldefinierten Hohlraumstrukturen auf der Grundlage von Metallkoordinationen. Basierend auf generellen Prinzipien des Crystal Engineering wurden anhand von drei Typen oligofunktioneller Liganden und ausgewählter koordinationschemischer Synthesemethoden neue polymere Komplexverbindungen hergestellt, die im Hinblick auf Koordinationsgeometrie und Liganddimensionalität strukturspezifische Unterschiede aufweisen. Diese sind durch Anwendung von strukturanalytischen Methoden belegt. Untersuchungsergebnisse der polymeren Komplexe als Rezeptoren für leichtflüchtige Lösungsmittel lassen erkennen, dass sich die erzeugten Koordinationspolymere potentiell als Beschichtungen in massensensitiven Sensoren eignen. Weiterhin konnte durch strukturgeometrische Untersuchungen an Modellkomplexen eine strukturelle Grundlage für den zukünftigen Entwurf von Koordinationspolymeren geschaffen werden.

Ruthenium(III) acetylacetonate was employed for the first time as homogeneous catalyst in the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was not reduced by sodium borohydride under the experimental conditions and remains unchanged after the catalysis, as shown by FT-IR and UV-Vis spectroscopic characterization. Poisoning experiments with mercury, carbon disulfide or trimethylphosphite provide compelling evidence that ruthenium(III) acetylacetonate is indeed a homogenous catalyst in the hydrolysis of sodium borohydride. Kinetics of the ruthenium(III) acetylacetonate catalyzed hydrolysis of sodium borohydride was studied depending on the catalyst concentration, substrate concentration and temperature. The hydrogen generation was found to be first order with respect to both the substrate concentration and catalyst concentration. The activation parameters of this reaction were also determined from the evaluation of the kinetic data: activation energy / Ea = 25.6 &amp / #61617 / &amp / #61472 / 1.3 kJ.mol-1, the enthalpy of activation / &amp / #8710 / H# = 24.6 &plusmn / 1.2 kJ.mol-1 and the entropy of activation &amp / #8710 / S# = -170 &plusmn / 5 J&amp / #61655 / mol-1&amp / #61655 / K-1. Ruthenium(III) acetylacetonate provides the lowest activation energy ever found for the hydrolysis of sodium borohydride. Ruthenium(III) acetylacetonate was found to be highly active catalyst providing 1183 total turnovers in the hydrolysis of sodium borohydride over 180 min before they are deactivated. The recorded turnover frequency (TOF) is 6.55 min-1.

Orientador: Elidiane Cipriano Rangel / Banca: Rogerio Valentim Gelamo / Banca: Sandro Doninini Mancini / O programa de Pós graduação em Ciência e Tecnologia de Materiais, PosMat, tem carater institucional e integra as atividades de pesquisa em materiais de diversos campi da UNESP / Resumo: Filmes finos de alumina vêm sendo amplamente estudados em função de suas propriedades físicas e químicas. Em aplicações industriais, filmes de alumina são utilizados, por exemplo, em ferramentas de corte e em circuitos microeletrônicos. Neste trabalho empregou-se o processo de PECVD (do inglês, Plasma Enhanced Chemical Vapor Deposition) para sintetizar fimes contendo óxido de alumínio. Os filmes foram depositados a partir de plasmas excitados por radiofrequencia (13,56 MHz) em misturas de acetilacetonato de alumínio e argônio. Uma configuração experimental inédita foi empregada para permitir a incorporação de alumínio nos filmes: o pó do organometálico foi colocado diretamente no eletrodo por onde um plasma de argônio foi excitado. A pulverização catódica aliada a sublimação do organometálico faz com que haja, em determinadas condições, a deposição de filmes contendo alumina. Foram avaliados os efeitos da pressão do plasma e da potência do sinal de excitação nas propriedades dos filmes resultantes. A técnica de perfilometria foi utilizada para determinar a espessura da camada depositada. Difração de raios X (DRX), com a incidência de ângulos rasantes, foi empregada para investigar a estrutura do material. As técnicas de espectroscopia de absorção no infravermelho por transformada de Fourier (FTIR) e espectroscopia de energia dispersiva (EDS) foram respectivamente utilizadas para analisar a estrutura e a composição química dos filmes. A morfologia das amostras preparadas sobre aço-inoxidável foi analisada por microscopia eletrônica de varredura (MEV) enquanto a dureza foi avaliada por nanoindentação. Foram obtidos filmes amorfos com espessuras de até 7 μm que contêm carbono, alumínio, oxigênio e hidrogênio. Observou-se que as proporções de alumínio e carbono são altamente dependentes da energia cinética dos íons presentes no plasma... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Recently aluminium oxide thin films have been widely studied due to their important physical and chemical properties. Depositions in cutting tools and in microelectronic circuits are examples of industrial applications of industrial applications of aluminum oxide films. In this work, alumina-containing films were prepared by PECVD (Plasma Enhanced Chemical Vapor Deposition) using a new configuration of the plasma system; the metalorganic powder was placed directly on the powered electrode while the substrates were mounted on the grounded topmost electrode. The plasma was excited by applying radiofrequency (13.56 MHz) power to the lower electrode in an argon atmosphere. The sputtering combined with the sublimation of organometallic compound enabled the growth of an alumina-containing organic layer. The effect of the plasma excitation parameters on the properties of the resulting films was studied. Film thickness was measured using profilometry. Grazing angle incidence X-ray diffractometry (GAXRD) was used to determine the structure of the films. Fourier trasnform Infrared Spectroscopy (FTIR) and energy dispersive spectroscopy (EDS) techniques were used to analyze chemical structure and coposition, respectively. The surface morphology was analyzed by scanning electron microscopy (SEM) while film hardness was evaluated by nanoindentation Amorphous organic films were deposited with thicknesses of up to 7 μm. The films were composed of aluminum, carbon, oxygen and hydrogen, the proportions of carbon and aluminum being strongly dependent on the kinetic energy of the ions. The film surface was uniform but presented particulares and, in some cases, wrinkles. The proportion of such defects depends on the plasma excitation parameters / Mestre