This dissertation focuses on the synthesis and electrochemical testing of new electrolyte salts for rechargeable multivalent ion batteries. In chapters 2 and 3 the synthesis of Mg and Ca hexafluoropnictogenate salts as well as the electrochemical behaviour of Mg(PF6)2 is presented. Pure samples of Mg(EF6)2 (E = P, As, and Sb) can be synthesized using Mg metal and NOPF6/NOSbF6 in CH3CN or via a ammonium salt deprotonation route using Me3NHAsF6 and Bu2Mg. The NOPF6 method was extended to the Ca variant, but isolation of a pure Ca(PF6)2 material required the presence of a crown ether. Electrochemical and microscopy measurements of THF-CH3CN solutions of Mg(PF6)2 show that the electrolyte good electrochemical stability and can facilitate the plating/stripping of Mg. Further, this electrolyte system can be cycled in a full cell using the Chevrel phase Mo6S8 cathode. The electrochemical stability of the AsF6− and SbF6− salts is lower than that of the PF6− salt and electrolyte decomposition is observed when cycling on Mg electrodes. In chapter 4 the development of a series of Mg aluminates [Mg(AlOR4)2] using a general synthetic platform based on Mg(AlH4)2 and various alcohols is presented. Preliminary electrochemical studies performed on these aluminate salts in dimethoxyethane identify the phenoxy and perfluoro-tert-butoxy derivatives as promising electrolyte systems. Electrochemical cycling of these electrolytes using gold and Mg electrodes show that systems containing chloride, brought through to the product from the starting material in the form of NaCl, exhibit lower plating/stripping overpotentials and higher Coulombic efficiencies than systems from which chloride had been removed. Further, these two electrolytes can be used in Mg full cells containing the Chevrel phase cathode. Solid-state 23Na NMR analysis as well as DFT calculations show that chloride-containing electrolytes facilitate the co-insertion of Na into the cathode material. In chapter 5 the hydroboration of pyridines and CO2 in the presence of pinacolborane is presented. An optimized system employing NH4BPh4 and HBpin is developed and a mechanism of pyridine hydroboration is proposed based on multinuclear NMR spectroscopy. The catalytic reaction was found to be catalyzed by a boronium salt, which was structurally characterized in the solid-state by single crystal X-ray diffraction. This new catalytic method is shown to be tolerant to a number of functional groups in the 3-position on pyridine as well as quinoline, and CO2, producing the hydroboration products in good yields.

In this study, a bidentate ligand, 6-ferrocenyl-2,2&#039 / -bipyridine, was prepared by the reaction of lithiated ferrocene with bipyridine. The ligand was identified by 1H, 13C- NMR and HMQC and UV-Vis spectroscopies. Then, bidentate molecule was reacted with pentacarbonylbis-(trimethylsilylethyne)tungsten(0). The ligand substitution reaction in CH2Cl2 yielded the new complex, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The isolated and purified complex was fully characterized by elemental analysis, IR, UV-Vis, MS, 1H and 13C- NMR spectroscopies. Tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) was also formed by ligand substitution reaction of 6-ferrocenyl-2,2&#039 / -bipyridine with pentacarbonyl(THF)chromium(0) which was prepared by photolytic substitution of CO from hexacarbonyl chromium(0) in THF. However, tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)chromium(0) could not be isolated by column chromatography. Electrochemistry of 6-ferrocenyl-2,2&#039 / -bipyridine and tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0) was studied by cyclic voltammetry and controlled potential electrolysis combined with UV-Vis. The ligand exhibits a reversible reduction and a reversible oxidation belonging to bipyridine and ferrocene moieties, respectively. One reversible reduction, two irreversible oxidation and a reversible oxidation were observed for tetracarbonyl(6-ferrocenyl-2,2&#039 / bipyridine)tungsten(0). The reversible reduction was attributed to bipyridine whereas two irreversible oxidations were assigned to tungsten centers and reversible oxidation to iron center.

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2016-11-03T14:15:07Z No. of bitstreams: 1 SANTOS_Fabio_2015.pdf: 7866329 bytes, checksum: ae986dab3375f6b5f2e34e0b103331dd (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-03T14:15:20Z (GMT) No. of bitstreams: 1 SANTOS_Fabio_2015.pdf: 7866329 bytes, checksum: ae986dab3375f6b5f2e34e0b103331dd (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2016-11-03T14:15:28Z (GMT) No. of bitstreams: 1 SANTOS_Fabio_2015.pdf: 7866329 bytes, checksum: ae986dab3375f6b5f2e34e0b103331dd (MD5) / Made available in DSpace on 2016-11-03T14:15:39Z (GMT). No. of bitstreams: 1 SANTOS_Fabio_2015.pdf: 7866329 bytes, checksum: ae986dab3375f6b5f2e34e0b103331dd (MD5) Previous issue date: 2015-04-17 / Não recebi financiamento / This work involves the construction of a portable equipment device for electrochemical polymerization of an Intrinsically Conductive Polymer - PIC. Using a rotary circular electrode, this method’all allows the production of various polymers especialy PIC's parameterize, controlling and monitoring all the process, so that a polymer can be prepared with maximum efficiency. As it is a portable equipment, it is possible to share with the universities labs and research centers that are working with conductive polymers and or other tips of polymers with can be inter interested in electrochemical synthesis. Using this method, you can ensuring the well contours specified parameters, the produced quantity for the preparation of the tests are larger, allowing a better characterization of the samples and production of products. The studied Conductive Polymer for the qualification of portable equipment was Polyaniline "PAni", this was characterized by the Fourier transform infrared region - FTIR, scanning electron microscopy – SEM, spectroscopy ultraviolet and Visible - UVVIS, thermogravimetric analysis – TGA, analysis by cyclic voltammetric and conductivity volumetric by the method at two tips. / Este trabalho consiste na construção de um equipamento portátil para polimerização eletroquímica de um Polímero Intrinsecamente Condutor - PIC. Utilizando-se de um eletrodo circular rotativo, esse método permitirá a produção de diversos polímeros em especiais os PIC’s, parametrizando, controlando e monitorando todo o processo, de forma que possa ser elaborado um polímero com máxima eficiência. Por se tratar de um equipamento portátil, acredita-se que possa ser difundido entre os laboratórios de demais universidades e centros de pesquisas que estão trabalhando com polímeros condutores e/ou outra classe de polímeros que possuem interesse na síntese eletroquímica. Com esse método, além de garantir os parâmetros de contornos bem especificados, a quantidade produzida para elaboração dos ensaios são maiores, permitindo uma melhor caracterização das amostras e na produção de produtos. O Polímero Condutor estudado, para a qualificação do equipamento portátil foi a Polianilina “PAni”, este foi caracterizado através das técnicas de espectroscopia na região de infravermelho com transformada de Fourier - FTIR, microscopia eletrônica de varredura – MEV, espectroscopia na região do ultravioleta e visível – UV-VIS, análise termogravimétrica – TGA, análise por voltametria cíclica, e condutividade elétrica volumétrica pelo método de duas pontas.

A polianilina é dos polímeros condutores mais estudados e com diversas aplicações, dentre elas o uso no recobrimento de aços para proteção à corrosão. Este trabalho objetivou encontrar as condições de eletrossíntese de polianilinas em meio aquoso neutro e a avaliação de proteção à corrosão, tendo como substrato o aço inox 304. As polianilinas eletrossintetizadas foram uma forma pura (PAni) e outra modificada com a adição de melamina (PAni/MM). Dentre as justificativas deste trabalho está a necessidade de aprofundar os escassos estudos em eletrossínteses em meio aquoso neutro. Neste trabalho, são apresentados as condições de eletrossíntese das polianilinas, a caracterização preliminar das polianilinas por UV-visível, FTIR e MEV, ensaios de polarização potenciodinâmica e impedância eletroquímica do aço inox 304 sem e com filmes das polianilinas para avaliar a resistência à corrosão em meio aquoso de NaCl 0,5 mol/L. O trabalho mostrou que a eletrossíntese das polianilinas em meio aquoso neutro é viável. Além disso, foi verificada a seguinte ordem do potencial de corrosão, do menor para o maior: aço inox 304 puro, aço inox 304 com PAni e aço inox 304 com PAni/MM. / Polyaniline is one of the most studied conducting polymers and with various applications, including use on steels for corrosion protection. This work aimed to find the conditions for electrosynthesis of polyanilines in neutral aqueous media and to evaluated the corrosion protection of 304 stainless steel. The electrosynthesizeds polyanilines were one pure form (PAni) and one with the addition of melamine (PAni/MM). One of the justifications of this work is the need to deepen the scarce studies in electrosynthesis in neutral aqueous media. In this work, we will see the conditions for electrosynthesis of polyanilines, the UV-visible, FTIR and SEM polyanilines preliminary characterization, the potentiodynamic polarization experiments and impedance spectroscopy of 304 stainless steel without and with films from polyanilines for evaluate the corrosion resistance in NaCl 0,5 mol/L aqueous media. This work showed that electrosynthesis of polyanilines is feasible in neutral aqueous media. In addition, it was verified the following order of corrosion potencial, from lowest to highest: pure 304 stainless steel, 304 stainless steel with PAni and 304 stainless with PAni/MM.