Functional materials, particularly metal oxides, have been the focus of much attention in solid state chemistry for many years and impact every aspect of modern life. The approach adopted in this thesis to access desirable functionality for enhanced fundamental understanding is via modifying existing materials by deploying reducing synthetic procedures. This work spans several groups of inorganic crystalline materials, but is unified by the development of new properties within host compounds of particular relevance to solid oxide fuel cell technology, which allow interstitial oxide ion conduction at elevated temperatures. The Ca₁₂Al₁₄O₃₂e₂ electride was successfully synthesized by replacing the mobile extra-framework oxygen ions with electrons acting as anions. The high concentration of electrons in the C12A7 electride gives rise to an exceptionally high electronic conductivity of up to 245 S cm⁻¹ at room temperature. Making use of the high density of electrons in Ca₁₂Al₁₄O₃₂e₂ electride, the strong N-N bonds in N₂ was found to be broken when heating Ca₁₂Al₁₄O₃₂e₂ in a N₂ atmosphere. A reaction between silicate apatites and the titanium metal yielded another completely new electride material La₉.₀Sr₁.₀(SiO₄)₆O₂.₄e₀.₂ which was found to be a semiconductor. To fully understand the role of oxygen interstitials in silicate apatites, high-resolution transmission electron microscopy (HRTEM) was employed as the main technique in probing how the oxygen nonstoichiometry is accommodated at the atomic level. Atomic-resolution imaging of interstitial oxygen in La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ proved to be a success in this thesis. Substitution of oxygen in 2a and interstitial sites with fluoride ions in La[subscript(8+y)]Sr[subscript(2- z)](SiO₄)₆O[subscript(2+(3y-2z)/2)] (0<y<2, 0<z<2) could be an approach to enriching the functionalities in the apatite structure. A wide range of fluoride substitution levels was tolerated in La[subscript(10-x)]Sr[subscript(x)](SiO₄)₆O[subscript(3-1.5x)]F[subscript(2x)] (x= 0.67, 1, 1.5, 2) and AC impedance measurements were found in support of a tentative conclusion that fluoride ions could be mobile in fluorinated apatites. The last part of this thesis was focused on a new class of fast oxide ion conductors based on Ge₅P₆O₂₅ whose performance was superior to both La₉.₀Sr₁.₀(SiO₄)₆O₂.₅ and Ca₁₂Al₁₄O₃₃ in the low temperature range.

O Departamento Acadêmico de Química e Biologia da UTFPR- Câmpus Curitiba conta hoje com 30 laboratórios dedicados a atividades de ensino e pesquisa. Atualmente, os resíduos gerados por esses laboratórios são recolhidos e seguem para disposição final. Neste trabalho, foi realizado um levantamento da atual situação da geração de resíduos químicos de laboratório no Departamento. Inicialmente os laboratórios de ensino foram selecionados para execução do trabalho por atenderem maior número de alunos e por suas atividades frequentes, sendo identificados os que atendiam maior número de alunos e onde eram executadas mais aulas práticas. Estudou-se as características dos resíduos gerados nestas aulas, com base nos planos de ensino, acompanhamento de algumas disciplinas durante a execução dos experimentos e registros do almoxarifado. Verificou-se as possibilidades de modificações experimentais, visando a prevenção da geração de resíduos, conforme enunciam os princípios da Química Verde. Desta forma, as disciplinas de Química Inorgânica e Orgânica foram consideradas com boas oportunidades de intervenção. Os roteiros experimentais dessas disciplinas foram estudados, e o inventário dos resíduos gerados por elas apontaram a geração de resíduos perigosos, segundo a NBR 10.004 da ABNT. Elaborou-se cinco novos roteiros de aulas práticas e as modificações metodológicas propostas envolveram a substituição de reagentes que pudessem originar resíduos perigosos contendo bário, chumbo, acetato de etila e clorofórmio. Realizou-se estudo na literatura, de modo a embasar teoricamente as propostas, as quais foram testadas em laboratório. Os testes realizados atingiram os objetivos propostos, comprovando a possibilidade de aplicação das modificações sugeridas. Um dos roteiros modificados foi aplicado em aula prática com o objetivo de verificar sua aplicabilidade e como os alunos receberiam as mudanças. Os alunos executaram e verificaram os fenômenos conforme os objetivos do roteiro, comprovando que o aprendizado não foi prejudicado e que o caráter didático da aula foi mantido. Concluiu-se que é possível executar as aulas práticas das disciplinas citadas prevenindo a geração de resíduos perigosos por meio de técnicas simples e aplicáveis, mantendo-se os objetivos iniciais das aulas práticas e incorporando-se princípios da Química Verde. / The Academic Department of Chemistry and Biology of UTFPR- Campus Curitiba today has 30 laboratories dedicated to teaching and research activities. Currently, waste generated by these laboratories are collected and proceed to final disposal. In this study, we conducted a survey of the current situation of the generation of laboratory chemical waste in the Department. Initially teaching laboratories were selected for execution of work for meeting more students and their frequent activity, were identified that met more students and where they were executed more practical classes. Studied the characteristics of the waste generated in these classes, based on the teaching plans, monitoring of some subjects during the execution of experiments and records the warehouse. There was the possibility of experimental changes, preventing the generation of waste, as set out the principles of green chemistry. Thus, the disciplines of Inorganic and Organic Chemistry were considered with good opportunities for intervention. The experimental manuals of these subjects were studied, and the inventory of the waste generated by them showed the generation of hazardous waste according to NBR 10004 of ABNT. We developed five new routes of practical classes and methodological changes proposed involved the replacement of reagents that could give rise to hazardous waste containing barium, lead, ethyl acetate and chloroform. It was proposed in the literature to explain theoretically proposed, which were tested in the laboratory. The tests met the proposed objectives, proving the applicability of the suggested changes. One of the modified scripts was applied in practical class in order to verify its applicability and how students receive the changes. Students performed and observed phenomena according to the objectives of the roadmap, proving that learning was not harmed and that the didactic nature of the class was held. In conclusion, you can perform the practical lessons of the disciplines mentioned preventing the generation of hazardous waste through simple and applicable techniques, maintaining the initial objectives of the practical classes and incorporating up principles of Green Chemistry.

O Departamento Acadêmico de Química e Biologia da UTFPR- Câmpus Curitiba conta hoje com 30 laboratórios dedicados a atividades de ensino e pesquisa. Atualmente, os resíduos gerados por esses laboratórios são recolhidos e seguem para disposição final. Neste trabalho, foi realizado um levantamento da atual situação da geração de resíduos químicos de laboratório no Departamento. Inicialmente os laboratórios de ensino foram selecionados para execução do trabalho por atenderem maior número de alunos e por suas atividades frequentes, sendo identificados os que atendiam maior número de alunos e onde eram executadas mais aulas práticas. Estudou-se as características dos resíduos gerados nestas aulas, com base nos planos de ensino, acompanhamento de algumas disciplinas durante a execução dos experimentos e registros do almoxarifado. Verificou-se as possibilidades de modificações experimentais, visando a prevenção da geração de resíduos, conforme enunciam os princípios da Química Verde. Desta forma, as disciplinas de Química Inorgânica e Orgânica foram consideradas com boas oportunidades de intervenção. Os roteiros experimentais dessas disciplinas foram estudados, e o inventário dos resíduos gerados por elas apontaram a geração de resíduos perigosos, segundo a NBR 10.004 da ABNT. Elaborou-se cinco novos roteiros de aulas práticas e as modificações metodológicas propostas envolveram a substituição de reagentes que pudessem originar resíduos perigosos contendo bário, chumbo, acetato de etila e clorofórmio. Realizou-se estudo na literatura, de modo a embasar teoricamente as propostas, as quais foram testadas em laboratório. Os testes realizados atingiram os objetivos propostos, comprovando a possibilidade de aplicação das modificações sugeridas. Um dos roteiros modificados foi aplicado em aula prática com o objetivo de verificar sua aplicabilidade e como os alunos receberiam as mudanças. Os alunos executaram e verificaram os fenômenos conforme os objetivos do roteiro, comprovando que o aprendizado não foi prejudicado e que o caráter didático da aula foi mantido. Concluiu-se que é possível executar as aulas práticas das disciplinas citadas prevenindo a geração de resíduos perigosos por meio de técnicas simples e aplicáveis, mantendo-se os objetivos iniciais das aulas práticas e incorporando-se princípios da Química Verde. / The Academic Department of Chemistry and Biology of UTFPR- Campus Curitiba today has 30 laboratories dedicated to teaching and research activities. Currently, waste generated by these laboratories are collected and proceed to final disposal. In this study, we conducted a survey of the current situation of the generation of laboratory chemical waste in the Department. Initially teaching laboratories were selected for execution of work for meeting more students and their frequent activity, were identified that met more students and where they were executed more practical classes. Studied the characteristics of the waste generated in these classes, based on the teaching plans, monitoring of some subjects during the execution of experiments and records the warehouse. There was the possibility of experimental changes, preventing the generation of waste, as set out the principles of green chemistry. Thus, the disciplines of Inorganic and Organic Chemistry were considered with good opportunities for intervention. The experimental manuals of these subjects were studied, and the inventory of the waste generated by them showed the generation of hazardous waste according to NBR 10004 of ABNT. We developed five new routes of practical classes and methodological changes proposed involved the replacement of reagents that could give rise to hazardous waste containing barium, lead, ethyl acetate and chloroform. It was proposed in the literature to explain theoretically proposed, which were tested in the laboratory. The tests met the proposed objectives, proving the applicability of the suggested changes. One of the modified scripts was applied in practical class in order to verify its applicability and how students receive the changes. Students performed and observed phenomena according to the objectives of the roadmap, proving that learning was not harmed and that the didactic nature of the class was held. In conclusion, you can perform the practical lessons of the disciplines mentioned preventing the generation of hazardous waste through simple and applicable techniques, maintaining the initial objectives of the practical classes and incorporating up principles of Green Chemistry.