The world is facing a tough challenge regarding fulfilling human energy needs. Scientists are motivated to find alternative ways to the fossil fuel at a lower cost with little or no environmental pollution. Among the available renewable resources, the solar energy is an alternative energy to fossil fuel. Scientists are engaged in mimicking the photosynthesis to create the new energy devices such as dye sensitized solar cells. The fundamental theory and properties of the dye sensitized solar cells is given in the first chapter. In this research, the application of the different methods for surface alteration of SnO2 with water soluble porphyrins and phthalocyanine is studied. Using optical absorbance and steady state fluorescence studies, the formation of porphyrins and phthalocyanine discuss on the SnO2 surface is shown. Moreover, the different results of photoelectrochemical cells are show on chapter 2 to understand the porphyrin and phthalocyanine modified on SnO2 as electron injector. In summary, the application porphyrin and phthalocyanine of dimers as a broad band capturing photosensitized dye is discussed.

Over the past decade, intensive academic and commercial interests have been paid on compounds possessing photochemical properties, namely for their preparation, chemical properties, high efficiency and potential low-cost. Compounds having intense photochemical properties gained great interest due to wide range of potential applications. The sensitizers are one of the key components for high power-conversion efficiency in the dye sensitized solar cells (DSSCs). They are the core components in the organic light-emitting devices (OLEDs) due to their ability to emit light with the wavelengths largely red- shifted from their absorption wavelength. Ruthenium based sensitizers have been tagged “molecular light switches” because, although the fluorescence of these complexes in aqueous solutions is negligible, it increases of greater than 10000 fold in the presence of DNA. Many polypyridyl and dipyrido phenazine ruthenium complexes have achieved high power conversion efficiencies and therefore are of practical interest. Several research groups stated that the dipyrido phenazine ligand may be thought of as comprising two components: a bipyridyl unit and a phenazine unit. These two subunits behave essentially separately, with many molecular orbitals being localised over only one subunit and a redox properties of central phenazine moiety in the dipyrido phenazine ligand are important for the photochemical applications. Therefore a phenazine ligand was selected as a model for the present investigation. The chemistry of phenazine ligand is mostly limited to the late transition metal and f - element complexes. Our laboratory has a rich backgroung in the aluminum and early transition metal chemistry. The aluminum chemistry and early transition metal chemistry are of great interest since aluminum and early transition metal complexes are environmentally friendlier and cheaper than the late transition metal compounds. Another drawback of the ruthenium-based sensitizers is the lack of absorption in the red region of the visible spectrum, and also low molar extinction coefficients. An essential requirement for efficient conversion of solar energy is the good spectral match of the sensitizer absorption to the emission spectrum of solar radiation. In this regard, the ruthenium sensitizers’ spectral response in the lower energy regions is not sufficient. The current project has three parts. In the first part we collected and reviewed known literature regarding the certain classes of non-innocent ligands containing the six-membered carbon- nitrogen heterocycles and regarding the ligands potentially important for the photochemical applications. We also reviewed all available to the data information about the complexes supported by the phenazine ligand. In the second part we have investigated interaction of alkylaluminum compounds and phenazine and observed reduction of phenazine accompanied by formation of dialuminum cage type compounds containing two formally mononegative phenazine ligand. The derivatization of phenazine has been also observed. It resulted in formation of compounds having a stable organic radical. In a third part of our project we have explored interaction of phenazine or thiophenazine with the alkylaluminum compounds and chromium dichloride. The reaction in the three component system resulted in reduction of phenazine ligand and lead to the heterometallic Cr(II) - aluminum complexes containing a formally dinegative phenazine or thiophenazine ligands. When a large excess of triethylaluminum was taken, reduction of phenazine and chromium has been observed leading to the heterometallic multinuclear Cr(I) - aluminum complex containing a formally dinegative phenazine ligands and two chromium atoms in one complex in the rare oxidation state one.

Over the past decade, intensive academic and commercial interests have been paid on compounds possessing photochemical properties, namely for their preparation, chemical properties, high efficiency and potential low-cost. Compounds having intense photochemical properties gained great interest due to wide range of potential applications. The sensitizers are one of the key components for high power-conversion efficiency in the dye sensitized solar cells (DSSCs). They are the core components in the organic light-emitting devices (OLEDs) due to their ability to emit light with the wavelengths largely red- shifted from their absorption wavelength. Ruthenium based sensitizers have been tagged “molecular light switches” because, although the fluorescence of these complexes in aqueous solutions is negligible, it increases of greater than 10000 fold in the presence of DNA. Many polypyridyl and dipyrido phenazine ruthenium complexes have achieved high power conversion efficiencies and therefore are of practical interest. Several research groups stated that the dipyrido phenazine ligand may be thought of as comprising two components: a bipyridyl unit and a phenazine unit. These two subunits behave essentially separately, with many molecular orbitals being localised over only one subunit and a redox properties of central phenazine moiety in the dipyrido phenazine ligand are important for the photochemical applications. Therefore a phenazine ligand was selected as a model for the present investigation. The chemistry of phenazine ligand is mostly limited to the late transition metal and f - element complexes. Our laboratory has a rich backgroung in the aluminum and early transition metal chemistry. The aluminum chemistry and early transition metal chemistry are of great interest since aluminum and early transition metal complexes are environmentally friendlier and cheaper than the late transition metal compounds. Another drawback of the ruthenium-based sensitizers is the lack of absorption in the red region of the visible spectrum, and also low molar extinction coefficients. An essential requirement for efficient conversion of solar energy is the good spectral match of the sensitizer absorption to the emission spectrum of solar radiation. In this regard, the ruthenium sensitizers’ spectral response in the lower energy regions is not sufficient. The current project has three parts. In the first part we collected and reviewed known literature regarding the certain classes of non-innocent ligands containing the six-membered carbon- nitrogen heterocycles and regarding the ligands potentially important for the photochemical applications. We also reviewed all available to the data information about the complexes supported by the phenazine ligand. In the second part we have investigated interaction of alkylaluminum compounds and phenazine and observed reduction of phenazine accompanied by formation of dialuminum cage type compounds containing two formally mononegative phenazine ligand. The derivatization of phenazine has been also observed. It resulted in formation of compounds having a stable organic radical. In a third part of our project we have explored interaction of phenazine or thiophenazine with the alkylaluminum compounds and chromium dichloride. The reaction in the three component system resulted in reduction of phenazine ligand and lead to the heterometallic Cr(II) - aluminum complexes containing a formally dinegative phenazine or thiophenazine ligands. When a large excess of triethylaluminum was taken, reduction of phenazine and chromium has been observed leading to the heterometallic multinuclear Cr(I) - aluminum complex containing a formally dinegative phenazine ligands and two chromium atoms in one complex in the rare oxidation state one.

The photophysical properties of a series of Zn (II) porphyrins adsorbed onto a semiconductor were investigated using steady-state absorbance and emission measurements. The ability of the porphyrins to undergo triplet-triplet annihilation (TTA), a photophysical process through which photons in the red and near-infrared (NIR) regions of the optical spectrum can be converted into higher energy photons (upconversion), was explored. Aggregation capabilities were determined to verify possibility of these molecules to undergo triplet-triplet annihilation (TTA). TTA has significant potential for increasing the efficiency of dye-sensitized solar cells (DSSCs) by upconverting photons in the energy rich NIR region of the solar spectrum. A key requirement for efficient TTA is aggregation of the sensitizer dye, and in this thesis, we have examined the aggregation of porphyrins in TiO2-based sol-gel films. Solution phase absorption and emission studies were conducted using zinc (II) tetraphenylporphyrin and three of its functionalized derivatives, tetra(4-aminophenyl)porphyrin Zn(II), tetra(4-carboxyphenyl)porphyrin Zn(II), and tetra(4-sulfonatophenyl)porphyrin Zn(II), to evaluate their potential as DSSC sensitizers on TiO2 thin films. Mesoporous TiO2 thin films were synthesized, using a polymer-templating sol-gel route, and characterized with tunneling electron microscopy (TEM), atomic force microscopy (AFM), and UV-Vis absorbance measurements. Spectroscopy measurements were also carried out on porphyrin-sensitized TiO2 thin films and compared to solution-based results. A simple DSSC was constructed and used to further explore the application of zinc (II) porphyrin sensitizers in photovoltaic applications.

Although the high cost of solar cells prevents them being a primary candidate for energy production, great attention has been paid towards them because of the depletion of the conventional energy sources–fossil fuels–and the global warming effect, and the need to provide power to remote communities disconnected from the power grid. To reduce the cost, thin film technologies for silicon solar cells have also been investigated and commercialized, but dye sensitized solar cells (DSSC) have been considered as a promising alternative even for the silicon thin films with efficiency exceeding 10%. Compared with silicon-based photovoltaic devices, DSSCs are quite complex systems that require an intimate interaction among components. Within the last few years, conclusive smart solutions have been provided to improve the efficiency of these cells, with solar efficiency that makes them potential competitors against silicon devices. The most successful systems use titanium oxide as a core material tuned to collect and transmit the electrons generated by the photo-excitation of dye molecules. However, most of the solutions demonstrated so far require a thermal treatment of the TiO2 photoelectrodes at temperatures that preclude using any flexible organic substrate. This treatment prevents development of any roll-to-roll manufacturing process, which would be the only way to achieve cost effective large scale production. In order to overcome this major drawback, a novel synthesis of TiO2 at room temperature is described in the present document. This synthesis leads to 4-6 nm nanocrystalline anatase, the desired phase of titanium oxide for photoactive applications. An intensive study was carried out to explore the properties of these nanoparticles, via a mixture design study designed to analyze the influence of the starting composition on the final TiO2 structure. The influence of a post-synthesis thermal treatment was also explored. This 4 nm nanocrystalline TiO2 exhibits a high specific surface area and a good porosity that fulfills the requirements for an efficient photoanode; a high surface area allows high dye loading, and, hence, increases photocurrent and photo-conversion efficiency. Another important result of this study is the band gap, as it confirmed that nanocrystalline anatase has an indirect band gap and a quantum confinement for a crystal size of less than 10 nm. This result, well-known for bulk materials, had been discussed in some previous publications that claimed the effectiveness of a direct band gap. Following this synthesis and the structural and spectroscopic analyzes carried out in parallel, photocatalytic study was an important tool to further explore the semiconducting properties of this material. Additionally, our material gave very promising results in photocatalytic dye degradation, compared to the commercial products, even if it was not initially synthesized for this application. We assign these performances to the improved crystallinity resulting from thermal activation, without changing the crystal size, and to the ability to optimize the surface. This photocatalytic study gave us insights into the methods that optimize the electronic structure of the titanium oxide. Hence, we decided to thermally activate the nanoparticles before the preparation of films to be inserted into DSSCs. At this stage, as the thermal activation applies to the powder, the resulting material can still be used with flexible substrates. We have successfully integrated these nanoparticles in dye sensitized solar cells. Various organic additives were added to the TiO2 paste used to prepare photoelectrode films, to increase the porosity of the film and have a crack–free film with good attachment to the substrate. We demonstrated that the dye was chemically attached to the TiO2 surface, which led to better electron transport. Different treatment methods (UV and thermal) were applied to the film to cure it from organic additives and improve the electronic connectivity between the particles. When the UV treatment was applied as a single method, i.e. without thermal treatment, the cell performance was lower, but a combination of thermal treatment and UV enhanced this performance. We compared our nanoparticles to the reference material used in most of the studies on DSSC, that is, TiO2 Degussa, with cells prepared the same way. Our nanoparticles revealed higher overall conversion efficiency. As the dye attachment to the TiO2 surface is an important parameter that enhances the cell efficiency, so we checked via ATR-FTIR how the dye attached to the TiO2 surface. In addition, FTIR, UV-Vis, and IV measurements revealed that the amount of dye adsorbed was increased through HCl treatment of the photoelectrode. We also checked the internal resistance of the cell using impedance spectroscopy, and the analysis proved a successful integration of the nanoparticles in dye–sensitized solar cells as there was an increase in both the electron life time and the recombination resistance, and a decrease in the charge transfer resistance compared to the commercial powder.

Esta tese de doutorado versou sobre a obtenção e caracterização do semicondutor ZnO obtido por biomimetização de membranas da cascas de ovos (MCOs) e a sua aplicação como coletor fotovoltaico do tipo sensibilizado por corante. Na síntese do ZnO, as MCOs foram submergidas em uma solução contendo os íons precursores de Zn. As membranas atuaram como um biotemplate, servindo como base para que o ZnO tivesse sua nucleação e crescimento na forma de nanocristais. Foram investigados dois diferentes precursores de Zn (nitrato de zinco hexahidratado e acetato de zinco dihidratado) e verificou-se a influência do tratamento térmico na formação do ZnO. Os materiais obtidos foram caracterizados quanto à sua morfologia, área superficial, porosidade e propriedades óticas em função do tratamento térmico praticado. Para efeito de comparação, foi obtido TiO2 por biomimetização de cascas de ovos, além de ZnO por processo de precipitação. As amostras que foram preparadas utilizando o biotemplate apresentaram como características, pequeno tamanho de domínio cristalino e larga área superficial em comparação com as amostras de ZnO preparadas por precipitação. As propriedades óticas e cristalinidade apresentadas pelo ZnO obtido por biomimetização são comparáveis às da fase anatase do TiO2 e portanto compatíveis com a aplicação em células fotovoltaicas sensibilizadas por corante (DSSC – Dye sensitized solar cells). Para a formação de um filme fino e poroso, o ZnO obtido pela biomimetização das MCOs foi então depositado pela técnica de screen printing sobre um substrato cerâmico preparado para servir como uma cerâmica solar baseada nas DSSCs. A preparação da base de uma DSSC sobre uma placa cerâmica foi possível pela deposição de uma camada metálica, produzida por aspersão térmica sobre o substrato cerâmico, e pela deposição de uma fina camada de ZnO por serigrafia. A aspersão térmica se mostrou uma técnica eficiente, obtendo uma boa ancoragem do metal aspergido sobre o substrato cerâmico esmaltado, demonstrado por análise EDS que ocorre difusão do metal depositado na camada esmaltada significando inclusive uma ancoragem química. A deposição por serigrafia da camada de ZnO porosa mostrou-se um método simples e barato obtendo-se camadas com morfologia razoável para a aplicação em DSSCs. Um melhor controle do tamanho dos poros pode ser obtido, otimizando-se ainda mais a pasta e a calcinação da peça. / This doctoral thesis dealt about the obtaining and characterization of ZnO semiconductor obtained by biomimetization of eggshell membranes (ESMs) and its application as photovoltaic collector in dye sensitized solar cells (DSSCs). In the synthesis of ZnO, the ESMs were submerged in a solution containing the precursor ions of Zn. The membranes acted as a biotemplate, serving as basis for the ZnO had their nucleation and growth in the form of nanocrystals. We investigated two different precursors of Zn (zinc nitrate hexahydrate and zinc acetate dihydrate) and verified the influence of thermal treatment on the formation of ZnO. The materials were characterized according to their morphology, surface area, porosity and optical properties, as a function of the thermal treatment practiced. For comparison, TiO2 was obtained by biomimetization of ESM, and ZnO by precipitation process. The samples that were prepared using the biotemplate presented as characteristics small crystallite size and large surface area in comparison to the samples prepared by precipitation of ZnO. The optical properties and crystallinity presented by ZnO obtained by biomimetization are comparable to those of anatase phase of TiO2 and therefore compatible with the application in dye-sensitized solar cells (DSSC - Dye sensitized solar cells). ZnO obtained by biomimetization of ESMs was then used with the screen printing technique to form a thin porous film on a ceramic substrate, prepared to serve as a solar ceramic based on DSSCs. The preparation of a DSSC basis on a ceramic substrate was possible by the deposition of a metal layer by thermal spray on the ceramic substrate, and the deposition of a thin layer of ZnO by screen printing. The thermal spray proved to be an effective technique, getting a good anchoring of the metal sprayed on the glazed ceramic substrate, demonstrated byEDS analysis that diffusion occurs of the metal into the glazed ceramic substrate meaning chemical anchoring. The deposition by screen printing of the porous ZnO layer has shown to be a simple and inexpensive method yielding layers with reasonable morphology for use in DSSCs. A better control of pore size can be obtained by optimizing even more the paste and calcination of the samples.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / This thesis describes, initially, the synthesis and photophysical characterization of new sulfides,sulphoxides and vinyl sulfones based dyes. The compounds in question were obtained in good yields and good diastereoselectivity through Horner-Wadsworth- Emmons (HWE) reactions. The compounds absorb light in the UV/Vis region, with the major transitions occurring between – * orbitals. As for the emission, the PS-1 and PS- 2 vinyl sulphides have their maximum emission bands in the blue region of the spectrum. The oxidation to their respective sulphoxides and sulfones, and the attainment of D– –A structure, causes the emission to undergo a bathochromic shift to the green region of the spectrum. These effects are most pronounced in the triphenylamine derivatives (PSO-1 and PSO2-1) and in polar solvents (positive solvatocromism). With the aid of DFT and TD-DFT calculations, it can be observed that this behaviors are related to the formation of intramolecular charge transfer states (ICT) in the excited state. Subsequently, the design, synthesis and characterization of new vinyl sulphides for possible application in dye-sensitized solar cell (DSSCs) are presented. The compounds were designed to have a D– –A structure, where the sulphides would serve as a bridge between the donor (D) and acceptor (A) blocks. The compounds studied were obtained by the HWE and Knoevenagel condensation, in good yields and good diastereoselectivity. Through preliminary photophysical analysis, it has been observed that the dyes have a wide light absorption range (250–550 nm), in particular the dyes derived from malononitrile PCN-1, PCN-2 and PSCN. In addition to being greatly influenced by the nature of the electron acceptor group. These characteristics are in line with that expected for application in DSSCs and are similar to several sensitizing dyes reported in the literature. / Nesta tese descreve-se, inicialmente, a síntese e a caracterização fotofísica de novos corantes derivados de sulfetos, sulfóxidos e sulfonas vinílicas. Os compostos em questão foram obtidos em bons rendimentos e boa diastereosseletividade, através de reações de Horner-Wadsworth-Emmons (HWE). As propriedades fotofísicas dos corantes estudados mostraram-se bastante interessantes. Os compostos absorvem luz na região do UV/Vis, sendo que as principais transições ocorrem entre orbitais – *. Quanto a emissão, os sulfetos vinílicos PS-1 e PS-2 têm suas bandas máximas de emissão na região azul do espectro. A oxidação para seus respectivos sulfóxidos e sulfonas, e a obtenção de estrutura do tipo D– –A, faz com que a emissão sofra um deslocamento batocrômico para a região verde do espectro. Estes efeitos são mais acentuados nos derivados da trifenilamina (PSO-1 e PSO2-1) e em solvente polares (solvatocromismo positivo). Com o auxílio de cálculos DFT e TD-DFT, pode-se constatar que estes comportamentos estão relacionados à formação de estados de transferência de carga intramolecular (ICT) no estado excitado. Posteriormente, são apresentados o design, síntese e caracterização de novos sulfetos vinílicos para possível aplicação em células solares sensibilizadas (DSSCs). Os compostos foram desenhados para possuírem estrutura do D– –A, onde os sulfetos vinílicos serviriam como uma “ponte” -conjugada para os blocos doador (D) e aceptor (A). Os compostos estudados foram obtidos através da reação de HWE e condensação de Knoevenagel, em bons rendimentos e boa diastereosseletividade. Através da análise fotofísica preliminar, observou-se que os corantes possuem uma ampla faixa de absorção de luz (250– 550 nm), sobretudo os corantes derivados da malononitrila PCN-1, PCN-2 e PSCN. Além de serem bastante influenciados pela natureza do grupo aceptor de elétrons. Estas características estão de acordo com o esperado para aplicação em DSSCs e, são semelhantes a diversos corantes sensibilizadores reportados na literatura.

Esta tese de doutorado versou sobre a obtenção e caracterização do semicondutor ZnO obtido por biomimetização de membranas da cascas de ovos (MCOs) e a sua aplicação como coletor fotovoltaico do tipo sensibilizado por corante. Na síntese do ZnO, as MCOs foram submergidas em uma solução contendo os íons precursores de Zn. As membranas atuaram como um biotemplate, servindo como base para que o ZnO tivesse sua nucleação e crescimento na forma de nanocristais. Foram investigados dois diferentes precursores de Zn (nitrato de zinco hexahidratado e acetato de zinco dihidratado) e verificou-se a influência do tratamento térmico na formação do ZnO. Os materiais obtidos foram caracterizados quanto à sua morfologia, área superficial, porosidade e propriedades óticas em função do tratamento térmico praticado. Para efeito de comparação, foi obtido TiO2 por biomimetização de cascas de ovos, além de ZnO por processo de precipitação. As amostras que foram preparadas utilizando o biotemplate apresentaram como características, pequeno tamanho de domínio cristalino e larga área superficial em comparação com as amostras de ZnO preparadas por precipitação. As propriedades óticas e cristalinidade apresentadas pelo ZnO obtido por biomimetização são comparáveis às da fase anatase do TiO2 e portanto compatíveis com a aplicação em células fotovoltaicas sensibilizadas por corante (DSSC – Dye sensitized solar cells). Para a formação de um filme fino e poroso, o ZnO obtido pela biomimetização das MCOs foi então depositado pela técnica de screen printing sobre um substrato cerâmico preparado para servir como uma cerâmica solar baseada nas DSSCs. A preparação da base de uma DSSC sobre uma placa cerâmica foi possível pela deposição de uma camada metálica, produzida por aspersão térmica sobre o substrato cerâmico, e pela deposição de uma fina camada de ZnO por serigrafia. A aspersão térmica se mostrou uma técnica eficiente, obtendo uma boa ancoragem do metal aspergido sobre o substrato cerâmico esmaltado, demonstrado por análise EDS que ocorre difusão do metal depositado na camada esmaltada significando inclusive uma ancoragem química. A deposição por serigrafia da camada de ZnO porosa mostrou-se um método simples e barato obtendo-se camadas com morfologia razoável para a aplicação em DSSCs. Um melhor controle do tamanho dos poros pode ser obtido, otimizando-se ainda mais a pasta e a calcinação da peça. / This doctoral thesis dealt about the obtaining and characterization of ZnO semiconductor obtained by biomimetization of eggshell membranes (ESMs) and its application as photovoltaic collector in dye sensitized solar cells (DSSCs). In the synthesis of ZnO, the ESMs were submerged in a solution containing the precursor ions of Zn. The membranes acted as a biotemplate, serving as basis for the ZnO had their nucleation and growth in the form of nanocrystals. We investigated two different precursors of Zn (zinc nitrate hexahydrate and zinc acetate dihydrate) and verified the influence of thermal treatment on the formation of ZnO. The materials were characterized according to their morphology, surface area, porosity and optical properties, as a function of the thermal treatment practiced. For comparison, TiO2 was obtained by biomimetization of ESM, and ZnO by precipitation process. The samples that were prepared using the biotemplate presented as characteristics small crystallite size and large surface area in comparison to the samples prepared by precipitation of ZnO. The optical properties and crystallinity presented by ZnO obtained by biomimetization are comparable to those of anatase phase of TiO2 and therefore compatible with the application in dye-sensitized solar cells (DSSC - Dye sensitized solar cells). ZnO obtained by biomimetization of ESMs was then used with the screen printing technique to form a thin porous film on a ceramic substrate, prepared to serve as a solar ceramic based on DSSCs. The preparation of a DSSC basis on a ceramic substrate was possible by the deposition of a metal layer by thermal spray on the ceramic substrate, and the deposition of a thin layer of ZnO by screen printing. The thermal spray proved to be an effective technique, getting a good anchoring of the metal sprayed on the glazed ceramic substrate, demonstrated byEDS analysis that diffusion occurs of the metal into the glazed ceramic substrate meaning chemical anchoring. The deposition by screen printing of the porous ZnO layer has shown to be a simple and inexpensive method yielding layers with reasonable morphology for use in DSSCs. A better control of pore size can be obtained by optimizing even more the paste and calcination of the samples.

Esta tese de doutorado versou sobre a obtenção e caracterização do semicondutor ZnO obtido por biomimetização de membranas da cascas de ovos (MCOs) e a sua aplicação como coletor fotovoltaico do tipo sensibilizado por corante. Na síntese do ZnO, as MCOs foram submergidas em uma solução contendo os íons precursores de Zn. As membranas atuaram como um biotemplate, servindo como base para que o ZnO tivesse sua nucleação e crescimento na forma de nanocristais. Foram investigados dois diferentes precursores de Zn (nitrato de zinco hexahidratado e acetato de zinco dihidratado) e verificou-se a influência do tratamento térmico na formação do ZnO. Os materiais obtidos foram caracterizados quanto à sua morfologia, área superficial, porosidade e propriedades óticas em função do tratamento térmico praticado. Para efeito de comparação, foi obtido TiO2 por biomimetização de cascas de ovos, além de ZnO por processo de precipitação. As amostras que foram preparadas utilizando o biotemplate apresentaram como características, pequeno tamanho de domínio cristalino e larga área superficial em comparação com as amostras de ZnO preparadas por precipitação. As propriedades óticas e cristalinidade apresentadas pelo ZnO obtido por biomimetização são comparáveis às da fase anatase do TiO2 e portanto compatíveis com a aplicação em células fotovoltaicas sensibilizadas por corante (DSSC – Dye sensitized solar cells). Para a formação de um filme fino e poroso, o ZnO obtido pela biomimetização das MCOs foi então depositado pela técnica de screen printing sobre um substrato cerâmico preparado para servir como uma cerâmica solar baseada nas DSSCs. A preparação da base de uma DSSC sobre uma placa cerâmica foi possível pela deposição de uma camada metálica, produzida por aspersão térmica sobre o substrato cerâmico, e pela deposição de uma fina camada de ZnO por serigrafia. A aspersão térmica se mostrou uma técnica eficiente, obtendo uma boa ancoragem do metal aspergido sobre o substrato cerâmico esmaltado, demonstrado por análise EDS que ocorre difusão do metal depositado na camada esmaltada significando inclusive uma ancoragem química. A deposição por serigrafia da camada de ZnO porosa mostrou-se um método simples e barato obtendo-se camadas com morfologia razoável para a aplicação em DSSCs. Um melhor controle do tamanho dos poros pode ser obtido, otimizando-se ainda mais a pasta e a calcinação da peça. / This doctoral thesis dealt about the obtaining and characterization of ZnO semiconductor obtained by biomimetization of eggshell membranes (ESMs) and its application as photovoltaic collector in dye sensitized solar cells (DSSCs). In the synthesis of ZnO, the ESMs were submerged in a solution containing the precursor ions of Zn. The membranes acted as a biotemplate, serving as basis for the ZnO had their nucleation and growth in the form of nanocrystals. We investigated two different precursors of Zn (zinc nitrate hexahydrate and zinc acetate dihydrate) and verified the influence of thermal treatment on the formation of ZnO. The materials were characterized according to their morphology, surface area, porosity and optical properties, as a function of the thermal treatment practiced. For comparison, TiO2 was obtained by biomimetization of ESM, and ZnO by precipitation process. The samples that were prepared using the biotemplate presented as characteristics small crystallite size and large surface area in comparison to the samples prepared by precipitation of ZnO. The optical properties and crystallinity presented by ZnO obtained by biomimetization are comparable to those of anatase phase of TiO2 and therefore compatible with the application in dye-sensitized solar cells (DSSC - Dye sensitized solar cells). ZnO obtained by biomimetization of ESMs was then used with the screen printing technique to form a thin porous film on a ceramic substrate, prepared to serve as a solar ceramic based on DSSCs. The preparation of a DSSC basis on a ceramic substrate was possible by the deposition of a metal layer by thermal spray on the ceramic substrate, and the deposition of a thin layer of ZnO by screen printing. The thermal spray proved to be an effective technique, getting a good anchoring of the metal sprayed on the glazed ceramic substrate, demonstrated byEDS analysis that diffusion occurs of the metal into the glazed ceramic substrate meaning chemical anchoring. The deposition by screen printing of the porous ZnO layer has shown to be a simple and inexpensive method yielding layers with reasonable morphology for use in DSSCs. A better control of pore size can be obtained by optimizing even more the paste and calcination of the samples.

Esta tesis presenta un conjunto original de procedimientos para la síntesis de nanoestructuras de TiO2 y ZnO por biomimetización de membranas de cáscara de huevo obteniendo materiales valiosos para fotovoltaica como se muestra en su evaluación de rendimiento como ánodo en células solares sensibilizadas por colorante. "El manuscrito está dividido en 7 capítulos. En el primer capítulo, titulado Introducción, se presentan las bases teóricas para la comprensión de los procesos de biomimetización, membranas de cáscara de huevo, síntesis de ZnO y TiO2, y células solares sensibilizadas por colorantes (DSSC). Después del capítulo introductorio, el Capítulo 2 revela los objetivos generales y específicos de esta investigación. Posteriormente, el Capítulo 3 describe el procedimiento experimental utilizado para las síntesis y caracterizaciones de ZnO y TiO2, así como el procedimiento utilizado en el ensamblaje y la caracterización de las células fotovoltaicas. En el capítulo 4 se presentan y discuten los resultados obtenidos con las síntesis y la aplicación de los polvos como fotodoles en DSSC. En este capítulo, hemos decidido subdividirlo en secciones específicas para explicar cuestiones científicas específicas sobre el tema. En el capítulo 5 se presentan las conclusiones del estudio en vista de los diferentes aspectos: obtención de TiO2 biomimético y ZnO, diferencias entre los polvos sintetizados por biomimetización de las membranas de cáscara de huevo, y la caracterización de las células construidas con los polvos biomiméticos. / Esta tesi presenta un conjunt original de procediments per a la síntesi de nanoestructuras de TiO2 i ZnO per biomimetización de membranes de corfa d'ou obtenint materials valuosos per a fotovoltaica com es mostra en la seua avaluació de rendiment com a ànode en cèl·lules solars sensibilitzades per colorant. "El manuscrit està dividit en 7 capítols. En el primer capítol, titulat Introducció, es presenten les bases teòriques per a la comprensió dels processos de biomimetización, membranes de corfa d'ou, síntesi de ZnO i TiO2, i cèl·lules solars sensibilitzades per colorants (DSSC) . Després del capítol introductori, el Capítol 2 revela els objectius generals i específics d'esta investigació. Posteriorment, el Capítol 3 descriu el procediment experimental utilitzat per a les síntesis i caracteritzacions de ZnO i TiO2, així com el procediment utilitzat en l'acoblament i la caracterització de les cèl·lules fotovoltaiques. En el capítol 4 es presenten i discutixen els resultats obtinguts amb les síntesis i l'aplicació de les pols com fotodoles en DSSC. En este capítol, hem decidit subdividir-ho en seccions específiques per a explicar qüestions científiques específiques sobre el tema. En el capítol 5 es presenten les conclusions de l'estudi en vista dels diferents aspectes: obtenció de TiO2 biomimético i ZnO, diferències entre les pols sintetitzats per biomimetización de les membranes de corfa d'ou, i la caracterització de les cèl·lules construïdes amb les pols biomiméticos. / This thesis introduces an original set of procedures for the Synthesis of ZnO and TiO2 nanostructures by biomimetization of eggshell membranes obtaining valuable materiales for photovoltaic as shown on their performance evaluation as anode in Dye-Sensitized Solar Cells". The manuscript is divided into 7 chapters. In the first chapter, entitled Introduction, it is presented the theoretical bases for the understanding of the biomimetization processes, eggshell membranes, ZnO and TiO2 syntheses, and dye-sensitized solar cells (DSSC). After the introductory chapter, Chapter 2 reveals the general and specific objectives of this research. Subsequently, Chapter 3 describes the experimental procedure used for the syntheses and characterizations of ZnO and TiO2 as well as the procedure used in the assembly and characterization of the photovoltaic cells. In chapter 4 are presented and discussed the results obtained with the syntheses and application of the powders as photoanodes in DSSC. In this chapter, we have chosen to subdivide it into specific sections to explain specific scientific issues on the subject. In chapter 5 the conclusions of the study are presented in view of the different aspects: obtaining ZnO and biomimetic TiO2, differences between the powders synthesized by biomimetization of eggshell membranes, and the characterization of the cells constructed with the biomimetic powders. / Camaratta, R. (2018). Synthesis Of ZnO and TiO2 By Biomimetization Of Eggshell Membranes And Its Evaluation As Anode In Dye-Sensitized Solar Cells [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/113416 / TESIS