FundaÃÃo Cearense de Apoio ao Desenvolvimento Cientifico e TecnolÃgico / O descarte de efluentes tÃxteis em Ãguas superficiais representa um sÃrio problema ambiental e de saÃde pÃblica devido, principalmente, à presenÃa de corantes na sua composiÃÃo, muitos dos quais sÃo potencialmente tÃxicos e carcinogÃnicos. A remoÃÃo de cor e a mineralizaÃÃo de seus subprodutos à uma das maiores dificuldades enfrentadas pelas estaÃÃes de tratamento de efluentes das indÃstrias desse segmento. Nesta pesquisa, buscou-se avaliar o tratamento de efluentes tÃxteis em sistemas anaerÃbios de um e dois estÃgios, estudar opÃÃes de pÃs-tratamento por processos biolÃgicos aerÃbios e de oxidaÃÃo avanÃada, e utilizar testes de ecotoxicidade no estudo dos diversos efluentes produzidos. Foram realizados experimentos com sistemas anaerÃbios de um (R1) e dois estÃgios (R2) tratando esgotos tÃxteis real e sintÃticos. Nestes experimentos, foram avaliados o efeito da concentraÃÃo do corante, concentraÃÃo do doador de elÃtrons externo, o tempo de detenÃÃo hidrÃulica (TDH) e o efeito do mediador redox antraquinona-2,6-dissulfonato (AQDS) na eficiÃncia de descoloraÃÃo. Outros dois sistemas anaerÃbios de um estÃgio (R3 e R4) foram operados em paralelo, alimentados com esgoto tÃxtil real com TDH de 12h a fim de avaliar o efeito do AQDS na descoloraÃÃo de efluentes reais. Durante o pÃs-tratamento aerÃbio, foi avaliada a aplicaÃÃo de um reator de lodos ativados em batelada seqÃencial com ciclo total de 24h, operando com os efluentes, sintÃtico e real, previamente tratados no reator UASB. Avaliou-se, tambÃm, a aplicaÃÃo do processo de oxidaÃÃo avanÃada (POA) do tipo UV/H2O2 como opÃÃo de pÃs-tratamento dos efluentes tÃxteis tratados no reator UASB, tanto em relaÃÃo à descoloraÃÃo quanto na mineralizaÃÃo dos subprodutos gerados na reduÃÃo dos corantes. A avaliaÃÃo da toxicidade dos efluentes foi realizada pelos ensaios de toxicidade aguda utilizando a Daphnia magna como organismo teste. Os resultados dessa pesquisa revelaram que o sistema anaerÃbio de dois estÃgios mostrou-se mais estÃvel que o sistema de um estÃgio quando operado como o esgoto real e sintÃtico com os corantes Congo Red (CR) e Reactive Black 5 (RB5) e mais eficiente para o corante RR2 na ausÃncia de AQDS. Entretanto, na presenÃa do AQDS a eficiÃncia de descoloraÃÃo do Reactive Red 2 (RR2) foi elevada para os dois sistemas, mascarando o efeito da separaÃÃo de fase. Para o efluente tÃxtil real, nÃo foi verificado efeito algum da aplicaÃÃo do AQDS no R3, mesmo em baixo TDH e limitada concentraÃÃo de doador de elÃtrons. O pÃs-tratamento dos efluentes real e sintÃticos no reator aerÃbio foi capaz de reduzir a DQO abaixo de valor exigido pela portaria 154/02 da SEMACE. O processo de oxidaÃÃo avanÃada com UV/ H2O2 mostrou-se eficaz na remoÃÃo de cor e DQO dos efluentes tÃxtil real e sintÃticos. Os testes de toxicidade aguda ratificaram o potencial tÃxico dos efluentes tÃxteis e os subprodutos de sua degradaÃÃo assim como a capacidade de mineralizaÃÃo das aminas em sistemas seqÃenciais anaerÃbio/aerÃbio. / Disposal of textile effluents in surface waters represents a serious environmental and public health problem mainly due to the presence of dyes in their composition, many of which are potentially toxic and carcinogenic. The color removal and mineralization of byproducts is the major difficulty faced by the wastewater treatment plants of these industries. This thesis studied the treatment of textile effluents in one-stage and two-stage anaerobic systems, post-treatment options by using aerobic biological and advanced oxidation processes, and use the ecotoxicity tests for the various effluents produced. Experiments were performed in one-stage (R1) and two-stage (R2) anaerobic systems treating real and synthetic textile wastewaters. In these experiments, we evaluated the dye concentration effect, as well as external electron donor concentration, hydraulic retention time (HRT) and the redox mediator anthraquinone-2,6-disulfonate (AQDS) effect on color removal efficiency. Two other one-stage anaerobic systems (R3 and R4) were operated in parallel at the HRT of 12 hours and fed with real textile wastewater to assess the AQDS effect on the decolourisation of real textile effluents. During the aerobic post-treatment, we evaluated the application of sequencing batch reactor (SBR) with 24 hours total cycle to treat synthetic and real textile wastewaters pre-treated in the UASB reactor. We also evaluated the application of UV/H2O2 advanced oxidation process (AOP) to treat real textile wastewaters pre-treated in the UASB reactor, both in terms of color removal and mineralization of byproducts generated upon dye reduction. The evaluation of the effluents toxicity was performed by acute toxicity tests using Daphnia magna as test organism. The results revealed that the two-stage anaerobic system was more stable than the one-stage system for both real and the synthetic dyes Congo Red (CR) and Reactive Black 5 (RB5), and more efficient for the dye RR2 in absence of AQDS. However, in the presence of AQDS, color removal efficiency of RR2 was higher for both systems, masking the effect of phase separation. For real textile wastewater, it was not observed any effect of the AQDS application on R3, even when a short HRT or low electron donor concentration was applied. The aerobic and AOP post-treatments were able to reduce the effluents COD to values lower than the limits defined at the Legislation n 154 of SEMACE. The UV/H2O2 AOP-type was effective in removing color and COD from both real and synthetic textile effluents. The acute toxicity tests revealed the toxic potential of textile effluents and their by-products as well as the aromatic amines mineralization in anaerobic/aerobic systems.

Neste trabalho, foram sintetizados complexos de cobre e ferro, com ligantes imínicos, obtidos a partir de 2-acetilpiridina e 2-(2-aminoetilpiridina) (apyepy), ou 2-acetilpiridina e 2-(aminometil)benzimidazol (apyambi), e com ligantes comerciais (ácido nitrilotriacético ou picolínico), capazes de catalisar a oxidação de poluentes, como benzeno, tolueno, etilbenzeno e xilenos (BTEX). Foi utilizado o tolueno como composto-modelo destes poluentes, que foi degradado com o uso de peróxido de hidrogênio, persulfato de sódio, ácido peracético ou peróxidos de metais alcalinos como agentes oxidantes. Os ligantes imínicos foram obtidos a partir de precursores carbonílicos e amínicos adequados, através de reações de condensação, e os correspondentes complexos metálicos de cobre(II), ferro(II) ou ferro(III) foram isolados utilizando métodos usuais de nosso laboratório. A caracterização dos compostos foi feita através de diversas técnicas analíticas e espectroscópicas: UV/Vis, infravermelho (IV) e de ressonância paramagnética eletrônica (EPR). Posteriormente, foi feita a inserção desses complexos de ferro e de cobre sintetizados em matrizes inorgânicas de niobatos e a verificação de sua reatividade em comparação com as mesmas espécies em solução. Monitorou-se a degradação do tolueno pelo peróxido de hidrogênio por cromatografia gasosa e os resultados obtidos indicaram boa atividade catalítica dos complexos, tanto em solução como inseridos em matrizes de niobato. Em solução, os complexos imínicos foram mais ativos que os de ligantes comerciais. Os compostos de ferro com ambos os ligantes imínicos mostraram-se melhores catalisadores que os correspondentes de cobre e um dos ligantes testados foi o mais eficiente (apyepy) com ambos os metais. A inserção em niobatos, aparentemente, preserva o catalisador e mantém sua atividade por mais tempo, mostrando que a inserção em niobatos beneficia o processo / In this work, iron and copper complexes were synthesized, with imine ligands obtained from 2-acetylpyridine and 2-(2-aminethylpiridine) (apyepy), or 2- acetylpyridine and 2- (aminomethyl)benzimidazole (apyambi) and commercial ligands (nitriletriacetic and picolinic acids) that are able to catalyze the oxidation of pollutant compounds as benzene, , ethylbenzene and xilenes (BTEX). Toluene was used as model compound of those pollutants, and its degradation was verified by using hydrogen peroxide, alkaline peroxide, sodium persulfate, or peracetic acid as oxidant agent. The imine ligands were obtained from adequate carbonyl and amine precursors, in condensation reactions, and the corresponding copper(II), iron(II) and iron(III) complexes were isolated by usual methods developed in our laboratory. Their characterization was carried out by analytical and spectroscopic techniques (UV/Vis, IR and EPR). Those complexes were then inserted in inorganic matrices (niobates) e its reactivity were compared to that of the analogous species in solution. Toluene degradation by hydrogen peroxide was monitored by gas chromatography, and the results showed good catalytic activity of all the complexes, both in solution and inserted into niobate matrices. In solution, the imine complexes were more efficient than the species with commercial ligands. The iron compounds with both imine ligands acted as better catalysts than the corresponding copper species, and for both metals those with the ligand apyepy were the most efficient in both cases. The insertion in niobates apparently preserves the catalyst and maintains its activity for longer, attesting that the insertion ameliorated the process.

Wastewaters from textile industry contain organic dyes, which cannot be easily treated by biological methods. Therefore, pretreatment by an advanced oxidation process (AOP) is needed in order to produce more readily biodegradable compounds and to remove color and chemical oxygen demand (COD) simultaneously. In this research, ozone (O3) is combined with hydrogen peroxide (H2O2) for the advanced oxidation of an azo dye solution, namely aqueous solution of Acid Red 151, which is called as &ldquo / Peroxone process&rdquo / . The aim of the study is to enhance the ozonation efficiency in treating the waste dye solution. The effects of pH, initial dye and initial ozone concentrations and the concentration ratio of initial H2O2 to initial O3 on color and COD removals were investigated. Also, the kinetics of O3-dye reaction in the presence of H2O2 was approximately determined. As a result of the experimental study, it was seen that an increase in the initial dye concentration at a constant pH and initial ozone concentration did not change the COD % removal significantly, from a statistical analysis of the data. The results obtained at pH values of 2.5 and 7 gave higher oxidation efficiencies in terms of color and COD removals compared to those at pH of 10. The best initial molar ratio of H2O2 to O3 was found to be 0.5, which yielded highest treatment efficiency for each pH value studied. The results of the excess dye experiments suggest that the ozonation of Acid Red 151 follows an average first order reaction with respect to ozone at pH=2.5 and pH=7 whereas it is around 0.56 at pH=10. By Initial Rate Method, the orders with respect to individual reactants of O3 and dye were determined as one, the total order of the reaction being two for all the studied pH. As a conclusion, a further study of the peroxone process at a pH of 10 can be recommended to determine the reaction kinetics and mechanism at this pH, where radicals play an important role.

Submitted by RODRIGO SANTOS (rodrigo_ilct@yahoo.com.br) on 2016-01-27T16:19:53Z No. of bitstreams: 1 Dissertação Rodrigo Morais Menezes dos Santos.pdf: 4136391 bytes, checksum: 50ec17cef563517b2a5199c9c72d9a0f (MD5) / Approved for entry into archive by Sandra Manzano de Almeida (smanzano@marilia.unesp.br) on 2016-01-27T18:53:38Z (GMT) No. of bitstreams: 2 santos_rmm_me_araiq_int.pdf: 4136391 bytes, checksum: 50ec17cef563517b2a5199c9c72d9a0f (MD5) santos_rmm_me_araiq_par.pdf: 1040758 bytes, checksum: a18d1d9fa74ec9c42cb002b3084f4a61 (MD5) / Made available in DSpace on 2016-01-27T18:53:38Z (GMT). No. of bitstreams: 2 santos_rmm_me_araiq_int.pdf: 4136391 bytes, checksum: 50ec17cef563517b2a5199c9c72d9a0f (MD5) santos_rmm_me_araiq_par.pdf: 1040758 bytes, checksum: a18d1d9fa74ec9c42cb002b3084f4a61 (MD5) Previous issue date: 2016-01-15 / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / A contaminação de recursos hídricos por diversos poluentes orgânicos, como os corantes têxteis, tem causado sérios problemas ambientais. Alguns processos de descontaminação utilizam materiais sólidos para adsorção/sorção, com características apropriadas para a implantação em escala industrial, apresentando alta eficiência e baixo custo. Os Processos Avançados de Oxidação (AOP), como a fotocatálise heterogênea, também têm sido empregados na descontaminação de águas, convertendo os poluentes orgânicos em substâncias mais facilmente degradáveis, inertes ou inofensivas. Materiais multifuncionais como os Hidróxidos Duplos Lamelares (HDL) e seus derivados se mostram promissores tanto em processos adsortivos como fotocatalíticos. No presente trabalho foi dado enfoque ao processo de adsorção de um azocorante têxtil, utilizando HDL do sistema ZnAl-CO3 e o óxido misto obtido no tratamento térmico a 450°C. Os materiais apresentaram características interessantes e alta capacidade de remoção do corante. As isotermas de adsorção apresentaram boa correlação com o modelo de Langmuir e o cálculo de seus parâmetros revelou que a capacidade máxima adsortiva do material calcinado foi cerca de 6 vezes superior ao material não calcinado, 1587,1 mg⋅g-1 e 261,8 mg⋅g-1, respectivamente. A maior capacidade de adsorção/sorção foi atribuída ao melhoramento das propriedades texturais e ao comportamento da “regeneração” da estrutura HDL pelo precursor calcinado. Os resultados revelaram que o controle cinético do processo é uma etapa de adsorção química, e os parâmetros termodinâmicos calculados mostraram que o processo de adsorção é espontâneo e endotérmico. Os experimentos de conversão fotocatalítica de corante mostraram que os derivados da calcinação dos HDL são materiais promissores para serem utilizados nos AOP. A formação do nanocompósito ZnAl2O4/ZnO no material calcinado a 850°C, mostrou os melhores resultados de conversão, pela estratégia de acoplamento de bandas para separação de cargas, que diminui os problemas relacionados com a recombinação dos portadores de carga, além da maior absorbância no UV. Dessa forma, os resultados obtidos mostram a multifuncionalidade desses materiais, e fornecem novas evidências sobre a reconstrução de HDL pelo “efeito memória”, tópico de intensa discussão na literatura. / The contamination of water resources by several organic pollutants, including textile dyes, which have caused serious environmental problems. Solid materials for adsorption with appropriate features to be employed in industrial scale, such as high efficiency and low cost have been used in some decontamination processes. The Advanced Oxidation Processes (AOP) including heterogeneous photocatalysis, have also been used in water treatment, converting the organic pollutants into easily degradable, inert or harmless substances. Multifunctional materials, such as the Layered Double Hydroxides (LDH) and their derivatives, show potential in both adsorptive and photocatalytic processes. In this work the textile azo dye adsorption process using a ZnAl-CO3 LDH and the mixed oxide obtained from thermal treatment at 450 °C were focused. The materials presented interesting features and high removal capacity for the dye. The adsorption isotherms showed good correlation with the Langmuir isotherm model and the calculated parameters revealed that the maximum adsorption capacity of the calcined material was about 6 times higher than the non-calcined material, 1587.1 mg⋅g-1 and 261.8 mg⋅g-1, respectively. The higher adsorption capacity was assigned to the improvement of the textural properties and to the LDH-structure recovery from the calcined precursor. The results showed kinetic control of the process is a chemical adsorption step, and the calculated thermodynamic parameters showed the adsorption process is spontaneous and endothermic. The dye photocatalytic conversion experiments presented that the derivatives of the LDH calcination are promising materials to be used in the AOP. The formation of a ZnAl2O/ZnO nanocomposite from calcination at 850 °C showed the best conversion results from the coupling semiconductors for charge separation strategy that diminish some problems associated with charge carrier recombination and its higher UV absorbance. Thus, the results show the multi-functionality of these materials, giving some light to the discussion about LDH recovery by "memory effect" that remains a topic of intense debate in the literature. / FAPESP: 2013/25043-4

Neste trabalho, foram sintetizados complexos de cobre e ferro, com ligantes imínicos, obtidos a partir de 2-acetilpiridina e 2-(2-aminoetilpiridina) (apyepy), ou 2-acetilpiridina e 2-(aminometil)benzimidazol (apyambi), e com ligantes comerciais (ácido nitrilotriacético ou picolínico), capazes de catalisar a oxidação de poluentes, como benzeno, tolueno, etilbenzeno e xilenos (BTEX). Foi utilizado o tolueno como composto-modelo destes poluentes, que foi degradado com o uso de peróxido de hidrogênio, persulfato de sódio, ácido peracético ou peróxidos de metais alcalinos como agentes oxidantes. Os ligantes imínicos foram obtidos a partir de precursores carbonílicos e amínicos adequados, através de reações de condensação, e os correspondentes complexos metálicos de cobre(II), ferro(II) ou ferro(III) foram isolados utilizando métodos usuais de nosso laboratório. A caracterização dos compostos foi feita através de diversas técnicas analíticas e espectroscópicas: UV/Vis, infravermelho (IV) e de ressonância paramagnética eletrônica (EPR). Posteriormente, foi feita a inserção desses complexos de ferro e de cobre sintetizados em matrizes inorgânicas de niobatos e a verificação de sua reatividade em comparação com as mesmas espécies em solução. Monitorou-se a degradação do tolueno pelo peróxido de hidrogênio por cromatografia gasosa e os resultados obtidos indicaram boa atividade catalítica dos complexos, tanto em solução como inseridos em matrizes de niobato. Em solução, os complexos imínicos foram mais ativos que os de ligantes comerciais. Os compostos de ferro com ambos os ligantes imínicos mostraram-se melhores catalisadores que os correspondentes de cobre e um dos ligantes testados foi o mais eficiente (apyepy) com ambos os metais. A inserção em niobatos, aparentemente, preserva o catalisador e mantém sua atividade por mais tempo, mostrando que a inserção em niobatos beneficia o processo / In this work, iron and copper complexes were synthesized, with imine ligands obtained from 2-acetylpyridine and 2-(2-aminethylpiridine) (apyepy), or 2- acetylpyridine and 2- (aminomethyl)benzimidazole (apyambi) and commercial ligands (nitriletriacetic and picolinic acids) that are able to catalyze the oxidation of pollutant compounds as benzene, , ethylbenzene and xilenes (BTEX). Toluene was used as model compound of those pollutants, and its degradation was verified by using hydrogen peroxide, alkaline peroxide, sodium persulfate, or peracetic acid as oxidant agent. The imine ligands were obtained from adequate carbonyl and amine precursors, in condensation reactions, and the corresponding copper(II), iron(II) and iron(III) complexes were isolated by usual methods developed in our laboratory. Their characterization was carried out by analytical and spectroscopic techniques (UV/Vis, IR and EPR). Those complexes were then inserted in inorganic matrices (niobates) e its reactivity were compared to that of the analogous species in solution. Toluene degradation by hydrogen peroxide was monitored by gas chromatography, and the results showed good catalytic activity of all the complexes, both in solution and inserted into niobate matrices. In solution, the imine complexes were more efficient than the species with commercial ligands. The iron compounds with both imine ligands acted as better catalysts than the corresponding copper species, and for both metals those with the ligand apyepy were the most efficient in both cases. The insertion in niobates apparently preserves the catalyst and maintains its activity for longer, attesting that the insertion ameliorated the process.

Le principal objectif de la thèse est l'optimisation d'un procédé d'oxydation avancée par la mise en œuvre des outils de l'automatique moderne.Le procédé considéré concerne l'ozonation catalytique utilisé pour traiter les eaux résiduaires industrielles. L'optimisation de ce procédé consiste à contrôler l'abattement des polluants tout en minimisant le coût de fonctionnement du procédé. La mesure en ligne de la concentration en polluant est fournie par l'absorbance, grandeur corrélée à la DCO. Le procédé est alors considéré comme un système à une entrée, la puissance du générateur d'ozone, et deux sorties, l'ozone dans les évents et l'absorbance.L'identification du procédé a mené à l'estimation d'un modèle linéaire pour construire les lois de commande et d'un modèle non-linéaire, de type modèle de Wiener, pour tester les correcteurs en simulation avant les essais expérimentaux.Les trois commandes testées, la commande par modèle interne, la commande optimale et la commande H∞, permettent de rejeter des perturbations sur la concentration en polluant dans les effluents à traiter. Des analyses de stabilité du système bouclé, vis-à-vis de retards sur la commande, ont été menées.Les résultats expérimentaux obtenus ont permis de conclure sur les gains significatifs apportés par ces développements.La méthodologie développée pour cette application peut être étendue à d'autres procédés afin de faciliter le développement industriel des procédés d'oxydation avancée. / The main goal of the PhD thesis focuses on the optimization of an advanced oxidation process by implementing the modern control tools.The considered process is a lab-scale pilot of industrial wastewater treatment by catalytic ozonation. The optimization of this process is achieved by controlling the pollutant abatement while minimizing the high operating costs. The online measurement of the pollutant concentration is provided by the absorbance which is correlated with COD. Therefore, the process is considered as a system with one input, the ozone generator power, and two outputs, the ozone gas concentration at the top of the reactor and the absorbance.A linear model of the process was identified. It allowed calculating the control laws. And a nonlinear model, with a so-called Wiener model structure, was also identified to test the controllers in simulation before the experiments.The three control methods applied, the internal model control, the optimal control and the H∞ control, allow rejecting disturbance on the pollutant concentration of the effluent to be treated.The stability of closed-loop system with delayed control input was analyzed.The experimental results show the significant benefits provided by this closed-loop system.The methodology developed for this application can be extended to other processes to facilitate the industrial development of advanced oxidation processes.

Algal infestation in water bodies causes the release of soluble organic compounds that impact negatively on the taste and odour of the water. With increasing pollution in water bodies and increasing nutrient loading from agricultural activities, most water reservoirs in South Africa and around the world have become affected by this problem. In this study, an advanced oxidation process (AOP), namely, photocatalysis was evaluated for its potential to degrade aromatic compounds; and taste and odour causing bi-cyclic compounds originating from algae. Semiconductor photocatalysis is an environmentally friendly technology requiring no chemical inputs which is capable of completely mineralising organic pollutants to CO2 and H2O thereby eliminating production of unwanted by-products. Although processes involved in the photo-degradation have been reported for a wide range of pollutants, the degradative pathway in this process has not been fully established. In this study, compounds including phenol, 2-chlorophenol, 4-chlorophenol and nitrophenol were successfully eliminated from simulated wastewater. Degradation of geosmin at an environmentally significant initial concentration of 220 ng/L to levels below the lowest detectable concentration was achieved with an optimum catalyst concentration of 60 mg/L at a rate of 14.78 ng/L/min. Higher catalysts loading above 60 mg/L resulted in a decrease in degradation rates. An increase in initial geosmin concentration resulted in a decrease in rates. Ionic species commonly found in surface waters (HCO3 -, and SO4 2-) significantly reduced the efficiency of geosmin degradation. Degradation of geosmin produced acyclic intermediates from ring fission tentatively identified as 3,5-dimethylhex-1-ene, 2,4-dimethylpentan-3-one, 2-methylethylpropanoate and 2-heptanal. The results obtained indicate that the degradation of organic pollutants in aqueous solution is as a result of synergic action from hydroxyl radicals, positive holes and direct photolysis by UV radiation, though the predominant pathway of degradation is via hydroxyl radicals in solution. Major aromatic intermediates of phenol degradation include catechol, resorcinol and hydroquinone produced in the order catechol > resorcinol > hydroquinone. All three are produced within 2 minutes of photocatalytic reaction of phenol and remain in solution until all phenol is degraded in aerated systems. Production of resorcinol in non-aerated systems is transient, further supporting the hydroxyl radical dominant reaction pathway. / Thesis (PhD)--University of Pretoria, 2014. / gm2014 / Chemical Engineering / unrestricted

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert. / This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis.

Im Rahmen der vorliegenden Arbeit wurden zwei verschiedene Klassen oxidischer Nanomaterialien nasschemisch synthetisiert und strukturell-morphologisch charakterisiert. Zum einen betrifft dies TiO2-, TiO2/SiO2-, Ag/TiO2- und Pd/TiO2-Sole, welche die photokatalytisch aktive Modifikation Anatas in nanokristalliner Form enthalten und über einen solvothermalen Sol-Gel-Prozess hergestellt werden konnten. Im Hinblick auf eine potentielle Anwendung in der Desinfektionstechnologie und für den Abbau organischer Umweltschadstoffe wurde die photokatalytische Aktivität von Pulvern und Beschichtungen auf Textil durch E. coli-Abtötung bzw. Modellfarbstoffabbau untersucht. Im Weiteren wurde die antimikrobielle Aktivität pyroelektrischer LiNbO3- und LiTaO3-Pulvermaterialien unter zyklischer thermischer Anregung nachgewiesen. Diese als Pyroelektrokatalyse bezeichnete Nutzung des pyroelektrischen Effektes in einem katalytischen bzw. elektrochemischen Prozess ist dabei von grundlegender Neuheit. Aufsetzend auf den physiko-chemischen Grundlagen dieses Phänomens wurde eine Hypothese des Mechanismus entwickelt und in Analogie zur Photokatalyse diskutiert. / This thesis deals with two classes of oxidic nanomaterials that were synthesized by chemical solution routes and characterized with respect to structure and morphology. Sols of TiO2, TiO2/SiO2, Ag/TiO2 and Pd/TiO2 containing the photocatalytically active modification anatase in nanocrystalline form were prepared via a solvothermal sol-gel process. With regard to potential application in disinfection and environmental remediation technology the photocatalytic activity of powders and coatings on textile was investigated by means of E. coli decomposition and organic dye degradation. Further the antimicrobial activity of pyroelectric LiNbO3 and LiTaO3 powder materials under cyclical thermal excitation was demonstrated. In this context the application of the pyroelectric effect in a catalytic or electrochemical process – termed as pyroelectrocatalysis – is of fundamental novelty. Based on the physico-chemical principles of the phenomenon a hypothesis of the mechanism was developed and discussed in analogy with photocatalysis.