Esta tese tem como objetivo contribuir para o conhecimento e desenvolvimento das células solares sensibilizadas por corantes, através da elaboração de novas espécies supramoleculares e de estudos fundamentais de caracterização do filme de TiO2-P25 e da interface TiO2-Corante pela técnica de microscopia Raman confocal. Os estudos de microcopia Raman confocal da distribuição das fases cristalinas rutilo e anatase em filmes de TiO2-P25 (Degussa) mostraram que a fase rutilo está presente em agregados de diferentes tamanhos (de 250 nm a 3 µm) distribuídos na fase anatase e que estes agregados permaneceram mesmo após os processos de preparação da suspensão coloidal. Na presença do corante N3, verificou-se que a irradiação com laser em 532 nm, usando potência acima de 25 mW cm-2, provoca a absorção e posterior combustão do filme interfacial, com drásticas mudanças na morfologia visualizadas por microscopia Raman confocal, revelando a ocorrência da transformação de anatase em rutilo na região de incidência do feixe de laser. Outro ponto investigado nesta tese, foi a síntese e aplicação de novos sensibilizadores supramoleculares em células solares sensibilizadas por corante (DSC), visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Além dos trabalhos com novas porfirinas supramoleculares, reproduzidas no apêndice, esta tese apresenta um estudo detalhado de uma série, formada por três espécies diméricas, constituídas pelas unidades [Ru(dcbH2)Cl]+ e [Ru(dmb)2Cl]+, unidas por ligantes ponte com dimensões lineares crescentes, isto é: bpy, bpe e bpeb (dcbH2= ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, dmb= 4,4\'-dimetil-2,2\'- bipiridina, bpy= 4,4\'-bipiridina, bpe= trans-1,2-bis(4-piridil)-etileno e bpeb= trans-1,4- bis[2-(piridil)etenil]-benzeno). O rendimento global das DSCs correspondentes cresceram com o aumento do tamanho da ponte, passando de 2,78 % para o corante dim-Ru-bpy, para 2,89 e 3,25 % nos corantes dim-Ru-bpe e dim-Rbpeb, respectivamente. Foi observado que os valores de Jsc e η têm correlação linear com a distância de separação do buraco e da superfície do eletrodo de TiO2, ratificando que o processo de retardação da recombinação de carga, causado pelo aumento da ponte, é um fator muito importante para esta classe de compostos. Os resultados de IPCE mostraram que a unidade [Ru(dmb)2Cl(P)]+ também é responsável pela fotoinjeção de elétrons no TiO2. Assim, a excitação de qualquer uma das unidades, sempre acaba formando a espécie TiO2(e-)-Ru-Ru(h+) no filme interfacial. Os resultados confirmam as expectativas esperadas no planejamento energético vetorial, no qual o HOMO foi centrado na unidade distante da superfície e o LUMO ficou sobre a dcbH2 diretamente ancorada no superfície do TiO2. / This thesis encompasses our efforts to improve the knowledge and contribute to the development of dye-sensitized solar cells, by focusing on supramolecular design of new dyes and on critical aspects of the morphology of the TiO2-P25 and TiO2-Dye interfaces, as probed by confocal Raman microscopy. According to Raman imaging of the crystalline phase distribution of TiO2-P25 (Degussa) rutile was present as aggregates of different sizes (from 250 nm to 3 µm) dispersed in the 25 nm anatase powder, persisting even after applying criterious procedures for generating uniform colloidal suspensions. In addition, the irradiation of TiO2-P25 films containing adsorbed N3 dye, using a 532 nm laser (power over to 25 mW cm-2) led to the absorption and instantaneous combustion of the dye, promoting drastic local changes associated with the anatase to rutile conversion. The design and application of new supramolecular sensitizers in DSC has also been pursued, aiming an improvement of efficiency by slowing down the electron-hole recombination process, while enhancing the light harvesting effects in the visible range by means of vectorial electron/energy transfer. Studies concerning another efficient supramolecular porphyrin dye, have also been performed and published (Appendix). As the main subject, a series of dimeric species have been reported. They were based on the [Ru(dcbH2)Cl]+ and [Ru(dmb)2Cl]+ units connected by linear bridging ligands of increasing lengths, such as: bpy, bpe and bpeb (dcbH2= 2,2\'-bipyridine-4,4\'-dicarboxylic acid, dmb= 4,4\'-dimethyl-2,2\'-bipyridine, bpy= 4,4\'-bipyridine, bpe= trans-1,2-bis(4- pyridyl)-ethylene e bpeb= trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene). The overall yield of the corresponding DSCs increased with the bridging ligand length, from 2.78 % for dim-Ru-bpy, to 2.89 % and 3.25 % for dim-Ru-bpe and dim-Ru-bpeb, respectively. The electrochemical parameters associated with the short circuit current exhibited a linear correlation with the hole separation distance between the TiO2 electrode and the binuclear dye terminal, confirming that the retardation of charge recombination through the increasing distance is indeed a relevant factor for this series of compounds. The IPCE results indicated that the [Ru(dmb)2Cl(P)]+ unit is also involved in electron transfer, such that the dye excitation always leads the TiO2(e-)-Ru-Ru(h+) species. This conclusion confirmed the success of the supramolecular design and vectorial transfer strategy, in which the HOMO center was placed far away from the surface, but in communication with the LUMO center located at the dcbH2 group anchored on TiO2.

Esta tese tem como objetivo contribuir para o conhecimento e desenvolvimento das células solares sensibilizadas por corantes, através da elaboração de novas espécies supramoleculares e de estudos fundamentais de caracterização do filme de TiO2-P25 e da interface TiO2-Corante pela técnica de microscopia Raman confocal. Os estudos de microcopia Raman confocal da distribuição das fases cristalinas rutilo e anatase em filmes de TiO2-P25 (Degussa) mostraram que a fase rutilo está presente em agregados de diferentes tamanhos (de 250 nm a 3 µm) distribuídos na fase anatase e que estes agregados permaneceram mesmo após os processos de preparação da suspensão coloidal. Na presença do corante N3, verificou-se que a irradiação com laser em 532 nm, usando potência acima de 25 mW cm-2, provoca a absorção e posterior combustão do filme interfacial, com drásticas mudanças na morfologia visualizadas por microscopia Raman confocal, revelando a ocorrência da transformação de anatase em rutilo na região de incidência do feixe de laser. Outro ponto investigado nesta tese, foi a síntese e aplicação de novos sensibilizadores supramoleculares em células solares sensibilizadas por corante (DSC), visando diminuir os processos de recombinação e melhor aproveitamento do espectro solar através da estabilização do corante foto-oxidado e da transferência vetorial de elétron/energia. Além dos trabalhos com novas porfirinas supramoleculares, reproduzidas no apêndice, esta tese apresenta um estudo detalhado de uma série, formada por três espécies diméricas, constituídas pelas unidades [Ru(dcbH2)Cl]+ e [Ru(dmb)2Cl]+, unidas por ligantes ponte com dimensões lineares crescentes, isto é: bpy, bpe e bpeb (dcbH2= ácido-2,2\'-bipiridina-4,4\'-dicarboxílico, dmb= 4,4\'-dimetil-2,2\'- bipiridina, bpy= 4,4\'-bipiridina, bpe= trans-1,2-bis(4-piridil)-etileno e bpeb= trans-1,4- bis[2-(piridil)etenil]-benzeno). O rendimento global das DSCs correspondentes cresceram com o aumento do tamanho da ponte, passando de 2,78 % para o corante dim-Ru-bpy, para 2,89 e 3,25 % nos corantes dim-Ru-bpe e dim-Rbpeb, respectivamente. Foi observado que os valores de Jsc e η têm correlação linear com a distância de separação do buraco e da superfície do eletrodo de TiO2, ratificando que o processo de retardação da recombinação de carga, causado pelo aumento da ponte, é um fator muito importante para esta classe de compostos. Os resultados de IPCE mostraram que a unidade [Ru(dmb)2Cl(P)]+ também é responsável pela fotoinjeção de elétrons no TiO2. Assim, a excitação de qualquer uma das unidades, sempre acaba formando a espécie TiO2(e-)-Ru-Ru(h+) no filme interfacial. Os resultados confirmam as expectativas esperadas no planejamento energético vetorial, no qual o HOMO foi centrado na unidade distante da superfície e o LUMO ficou sobre a dcbH2 diretamente ancorada no superfície do TiO2. / This thesis encompasses our efforts to improve the knowledge and contribute to the development of dye-sensitized solar cells, by focusing on supramolecular design of new dyes and on critical aspects of the morphology of the TiO2-P25 and TiO2-Dye interfaces, as probed by confocal Raman microscopy. According to Raman imaging of the crystalline phase distribution of TiO2-P25 (Degussa) rutile was present as aggregates of different sizes (from 250 nm to 3 µm) dispersed in the 25 nm anatase powder, persisting even after applying criterious procedures for generating uniform colloidal suspensions. In addition, the irradiation of TiO2-P25 films containing adsorbed N3 dye, using a 532 nm laser (power over to 25 mW cm-2) led to the absorption and instantaneous combustion of the dye, promoting drastic local changes associated with the anatase to rutile conversion. The design and application of new supramolecular sensitizers in DSC has also been pursued, aiming an improvement of efficiency by slowing down the electron-hole recombination process, while enhancing the light harvesting effects in the visible range by means of vectorial electron/energy transfer. Studies concerning another efficient supramolecular porphyrin dye, have also been performed and published (Appendix). As the main subject, a series of dimeric species have been reported. They were based on the [Ru(dcbH2)Cl]+ and [Ru(dmb)2Cl]+ units connected by linear bridging ligands of increasing lengths, such as: bpy, bpe and bpeb (dcbH2= 2,2\'-bipyridine-4,4\'-dicarboxylic acid, dmb= 4,4\'-dimethyl-2,2\'-bipyridine, bpy= 4,4\'-bipyridine, bpe= trans-1,2-bis(4- pyridyl)-ethylene e bpeb= trans-1,4-bis[2-(4-pyridyl)ethenyl]-benzene). The overall yield of the corresponding DSCs increased with the bridging ligand length, from 2.78 % for dim-Ru-bpy, to 2.89 % and 3.25 % for dim-Ru-bpe and dim-Ru-bpeb, respectively. The electrochemical parameters associated with the short circuit current exhibited a linear correlation with the hole separation distance between the TiO2 electrode and the binuclear dye terminal, confirming that the retardation of charge recombination through the increasing distance is indeed a relevant factor for this series of compounds. The IPCE results indicated that the [Ru(dmb)2Cl(P)]+ unit is also involved in electron transfer, such that the dye excitation always leads the TiO2(e-)-Ru-Ru(h+) species. This conclusion confirmed the success of the supramolecular design and vectorial transfer strategy, in which the HOMO center was placed far away from the surface, but in communication with the LUMO center located at the dcbH2 group anchored on TiO2.

Dye sensitized solar cells (DSSCs) have typically been produced using organic liquids such as acetonitrile as the electrolyte solvent. In real world situations water can permeate into the cell through sealing materials and is also likely to be introduced during the fabrication process. This is a problem as the introduction of water into cells optimized to use an organic solvent tends to be detrimental to cell performance. In this work DSSCs which are optimized to use water as the main electrolyte solvent are produced and characterized. Optimization of aqueous DSSCs resulted in cells with efficiencies up to 3.5% being produced. In terms of characterization, it is generally seen in this work that aqueous DSSCs produce a lower photocurrent but similar photovoltage compared to DSSCs made using acetonitrile and reasons for this are examined in detail. The decreased ability of the aqueous electrolyte to wet the nanoporous TiO2 compared to an acetonitrile electrolyte is found to be a key difficulty and several possible solutions to this problem are examined. By measuring the photocurrent output of aqueous cells as a function of xy position it can be seen that there is some dye dissolution near to the electrolyte filling holes. This is thought to be linked to pH and the effect of 4-tert-butylpyridine and may also decrease the photocurrent. It is found that there is little difference between the two types of cells in terms of the conduction band position and the reaction of electrons in the semiconductor with triiodide in the electrolyte, explaining the similarity in photovoltage. By altering the pH of the electrolyte in an aqueous cell it is found to be possible to change the TiO2 conduction band position in the DSSC. This has a significant effect on the open circuit voltage and short circuit current of the cell, though the pH range available is limited by the fact that dye desorbs at high pH values.

Dans les prochaines décennies, les limites des systèmes de communications optiques actuels seront atteintes à moins d'adopter de nouvelles solutions. L'une d'elles est l'utilisation d'une nouvelle plage spectrale autour de 2 µm stimulée par l'apparition des amplificateurs fibrés dopés thulium. Dans ce manuscrit, nous nous y intéresserons dans le cadre de transmissions très courtes distances sur puces photoniques. Divers matériaux, dont le dioxyde de titane, seront ainsi explorés.Ce travail de thèse a deux principaux objectifs. D'une part, il vise à démontrer que le dioxyde de titane (TiO2), matériau encore peu exploré, est prometteur pour des applications télécoms en le comparant à des plateformes plus matures. D'autre part, il tend à introduire la bande spectrale autour de 2 µm comme une solution à envisager pour les télécommunications de nouvelle génération.Plus précisément, la première partie de cette thèse a pour but de développer une technique pour coupler efficacement la lumière dans les structures en TiO2). Pour la première fois, une configuration faisant appel à un réseau métallique enterré a été évaluée numériquement avant d'être caractérisée expérimentalement. La seconde partie présente des transmissions télécoms haut-débit (10 Gbit/s) autour de µm réalisées sans erreurs dans des guides d'ondes sub-longueur d'onde ou multimodes en dioxyde de titane, silicium ou silicium-germanium. Pour terminer, des fonctions non-linéaires sont explorées sur ces puces photoniques. Il a été ainsi démontré une conversion en longueurs d'onde à 2 µm atteignant -10dB sur silicium ou la génération du premier supercontinuum s'étalant du visible à 2 µm dans un guide d'onde en TiO2. / In the next decades, the limits of current optical communication systems will be reached unless new solutions are adopted. On of them is the use of a new spectral range around 2 µm enabled by the emergence of thulium-doped fiber amplifiers. In this thesis, we will focus on it in the context of very short distances transmissions on photonic chips. Various materials, mainly titanium dioxide (TiO2), will be explored.This thesis work has two main objectives. On the one hand, it aims to demonstrate that a material relatively unexplored, titanium dioxide, is promising for telecom applications by comparing it to more mature plateforms. On the other hand, it tends to introduce the spectral band around 2 µm as a solution to be considered for next-generation communications.More precisely, the first part of this thesis aims to develop a technique to efficiently couple light in TiO2 structures. For the first time, a configuration using a buried metallic grating was evaluated numerically and then characterized experimentally. The second part presents error-free high-speed (10 Gbit/s) telecom transmissions around 2 µm carried out in subwavelength or multimode waveguides in titanium dioxide, silicon or silicon-germanium. Finally, nonlinear functions are explored on the photonic chips. Thus, it has been demonstrated a wavelength conversion at 2 µm reaching -10dB on a silicon waveguide or the first supercontinuum generation spreading from visible to 2 µm wavelength in a TiO2 waveguide.

Made available in DSpace on 2014-12-17T15:41:57Z (GMT). No. of bitstreams: 1 RobertaPMM_DISSERT.pdf: 3172444 bytes, checksum: 159d519d0473cdce848696ecb3f8e8f6 (MD5) Previous issue date: 2011-02-24 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Hybrid systems formed from polymers and transition metals have now their physical and chemical properties extensively investigated for use in electronic devices. In this work, Titanium Dioxide (TiO2) from the precursor of titanium tetrabutoxide and the composite system Poly(Ethylene Glycol)-Titanium Dioxide (TiO2-PEG) were synthesized by sol-gel method. The PEG as acquired and TiO2 and composites powders were analyzed by X-Ray Diffraction (XRD), Spectroscopy in the Infrared region with Fourier transform (IRFT), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM) and Electrochemical Impedance Spectroscopy (EIS). In the XRD analysis were observed in the TiO2 crystal faces of one of its polymorphs - anatase phase, crystal planes in Poly (Ethylene Glycol) with considerable intensity and in the composite systems the mixture of crystal faces of their precursors isolated and reduction of crystallinity. The TG / DTG suggested increasing the thermal instability of PEG in the composite powders as TiO2 is incorporated into the system. Spectral analysis presented in the infrared overlapping bands for the polymer and metal oxide, reducing the intensity of symmetric stretching of ligand groups in the main chain polymer and angular deformations; were observed using SEM micrographs of the morphological changes suffered by composite systems with the variation of the oxide concentration. Analyses by impedance spectroscopy indicated that the increased conductivity in composite occurs in line with the addition of the metal oxide concentration in the composite system / Sistemas h?bridos formados a partir de pol?meros e metais de transi??o atualmente t?m suas propriedades f?sicas e qu?micas extensivamente investigadas para aplica??o em dispositivos eletr?nicos. Neste trabalho, o Di?xido de Tit?nio (TiO2) a partir do precursor Tetrabut?xido de Tit?nio e o sistema comp?sito Poli (Etileno Glicol)-Di?xido de Tit?nio (PEG-TiO2) foram sintetizados pelo m?todo sol-gel. O PEG como adquirido e os p?s de TiO2 e comp?sitos obtidos foram analisados por Difra??o de Raios X (DRX), Espectroscopia de Absor??o na regi?o do Infravermelho com Transformada de Fourier (EIV-TF), An?lise Termogravim?trica (TG), Microscopia Eletr?nica de Varredura (MEV) e Espectroscopia de Imped?ncia Eletroqu?mica (EIE). Nas an?lises por DRX foram observadas no TiO2, faces cristalinas de um de seus polimorfos fase anat?sio, planos cristalinos no PEG com intensidade substancial e nos sistemas comp?sitos a mistura de faces cristalinas dos seus precursores na forma isolada, bem como, redu??o da cristalinidade. As curvas TG/DTG sugeriram o aumento da instabilidade t?rmica do PEG nos p?s comp?sitos ? medida que TiO2 ? incorporado ao sistema. A an?lise espectral na regi?o do infravermelho apresentou sobreposi??o de bandas relativas ao pol?mero e ao ?xido met?lico, redu??o da intensidade de estiramentos sim?tricos dos grupos ligantes da cadeia principal polim?rica e deforma??es angulares; foram observadas atrav?s das micrografias de MEV modifica??es morfol?gicas sofridas pelos sistemas comp?sitos com a varia??o da concentra??o do ?xido. As an?lises por imped?ncia eletroqu?mica indicaram que o aumento da condutividade nos comp?sitos ocorre em conson?ncia com a adi??o da concentra??o do ?xido met?lico no sistema comp?sito

No description available.

Thin films are produced from layers of materials ranging from nanometres to micrometres in height. They are increasingly common and are being used in integrated circuit design, optical coatings, protective coatings, and environmental sensing. Thin films can be fabricated using a variety of methods involving chemical reactions or physical transport of matter. Glancing angle deposition (GLAD) thin films are produced using physical vapour deposition techniques under high vacuum conditions where exploitation of the geometric conditions between the source and the substrate causes enhanced atomic self shadowing to produce structured thin films. This work deals with the modification of these films, emph{in situ} by altering growing conditions through substrate temperatures control, or post-deposition through reactive ion etching (RIE). The first part of the thesis deals with the modification of TiO$_2$ GLAD humidity sensors using RIE with CF$_4$. The data presented demonstrates improved response times to step changes in humidity. Characterization revealed response times of better then 50~ms (instrument-limited measurement). An etch recipe for complete removal of TiO$_2$ was also demonstrated with shadow masking to transfer patterns into GLAD films. The subsequent chapter focuses on modification of thin film growth conditions by increasing adatom mobility. A radiative heating system was designed and implemented with the ability to achieve chuck temperatures of 400$^circ$C. Capping layers on top of GLAD films were grown to demonstrate effects of emph{in situ} heating, and a quantitative analysis of crack reduction with increased temperatures is presented. Lithographic pattern transfer onto a capped GLAD film was demonstrated. Opposite to the goal of the preceding chapter, the focus of the final experimental chapter was to limit adatom mobility. A LN$_2$-based cooling system was designed and implemented for the purpose of studying the growth by GLAD of lower melting point materials, which under regular growth conditions do not form well-defined structures. Chuck temperatures of $-60$$^circ$C can be achieved during deposition while still allowing substrate rotation. The growth of helical copper films was used to demonstrate the effects of emph{in situ} substrate cooling. / Micro-Electro-Mechanical Systems (MEMS) and Nanotechnology

The dye-sensitized solar cell (DSC) is a promising efficient low-cost molecular photovoltaic device. One of the key components in DSCs is the dye, as it is responsible for the capture of sunlight. State-of-the-art DSC devices, based on ruthenium dyes, show record efficiencies of 10-12 %. During the last decade, metal-free organic dyes have been extensively explored as sensitizers for DSC application. The use of organic dyes is particularly attractive as it enables easy structural modifications, due to fairly short synthetic routes and reduced material cost. Novel dye should in addition to the light-harvesting properties also be compatible with the DSC components. In this thesis, a series of new organic dyes are investigated, both when integrated in the DSC device and as individual components. The evaluation methods consisted of different electrochemical and photoelectrochemical techniques. Whereas the light-harvesting properties of the dyes were fairly easily improved, the behavior of the dye integrated in the DSC showed less predictable photovoltaic results. The dye series studied in Papers II and IV revealed that their dye energetics limited vital electron-transfer processes, the dye regeneration (Paper II) and injection quantum yield (Paper IV). Further, in Papers III-VI, it was observed that different dye structures seemed to alter the interfacial electron recombination with the electrolyte. In addition to the dye structure sterics, some organic dyes appear to enhance the interfacial recombination, possibly due to specific dye-redox acceptor interaction (Paper V). The impact of dye sterical modifications versus the use of coadsorbent was explored in Paper VI. The dye layer properties in the presence and absence of various coadsorbents were further investigated in Paper VII. The core of this thesis is the identification of the processes and properties limiting the performance of the DSC device, aiming at an overall understanding of the compatibility between the DSC components and novel organic dyes. / QC 20100730

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.

H ιδέα της παρούσας μεταπτυχιακής ερευνητικής εργασίας βασίζεται στην παραγωγή ηλεκτρικής ενέργειας με φωτοαποικοδόμηση οργανικών ρύπων, μέσω φωτοηλεκτροχημικών κυψελίδων(PECs). Mε τον τρόπο αυτό επιτυγχάνεται η κατανάλωση των οργανικών ουσιών και η μετατροπή της ηλιακής ακτινοβολίας σε ηλεκτρική ενέργεια. Ο σκοπός της εργασίας ήταν η παρασκευή, ο χαρακτηρισμός, η μελέτη φωτοευαίσθητων ηλεκτροκαταλυτών και η μορφοποίηση τους σε ηλεκτρόδια, των οποίων εξετάστηκε και αναλύθηκε η φωτοηλεκτροχημική τους συμπεριφορά. Η φωτοηλεκτροχημική κυψελίδα αποτελείται από τα ηλεκτρόδια ανόδου και καθόδου, τα οποία φέρουν το φωτοκαταλύτη και τον ηλεκτροκαταλύτη αντίστοιχα. Εξαιτίας του n-τύπου ημιαγωγού που φέρει η φωτοάνοδος καθώς και της πρόσπτωσης της ηλεκτρομαγνητικής ακτινοβολίας πάνω στον ημιαγωγό, παρατηρείται η απορρόφηση φωτονίων και ο σχηματισμός ζεύγους ηλεκτρονίων-οπών. Η διαδικασία απορρόφησης ενός φωτονίου,για τη δημιουργία φωτοφορέων,απαιτεί το ποσό ενέργειας του φωτονίου να είναι μεγαλύτερο ή ίσο από/με το ενεργειακό χάσμα του ημιαγωγού. O ρυθμός επανασύνδεσης των φωτοπαραγόμενων ηλεκτρονίων και οπών περιορίζεται, με τη χρήση «θυσιαζόμενων ενώσεων», οι οποίες μπορεί να είναι δέκτες ή δότες ηλεκτρονίων. Με τον τρόπο αυτό προκαλούνται στην επιφάνεια του ημιαγωγού μη αντιστρεπτές αντιδράσεις, όπως οξείδωση των φωτοπαραγόμενων οπών, ώστε οι διαθέσιμοι φορείς φορτίου να ξεκινήσουν τις οξειδοαναγωγικές αντιδράσεις. Παράδειγμα, τέτοιων θυσιαστήριων ενώσεων αποτελεί η μεθανόλη, η οποία χρησιμοποιήθηκε στη συγκεκριμένη ερευνητική εργασία. Ως φωτοκαταλύτες χρησιμοποιήθηκαν η νανοκρυσταλλική τιτανία, TiO2 και ο σύνθετος ημιαγωγός TiO2/CdS, ο οποίος και παρασκευάστηκε με τη μέθοδο SILAR. Συγκεκριμένα το διοξείδιο του τιτανίου είναι η εμπορικά διαθέσιμη Degussa P-25, με αναλογία ανατάση:ρουτηλίου 3:1. Ως ηλεκτροκαταλύτης χρησιμοποιήθηκε ο εμπορικός καταλύτης Pt (30%)/C, πάνω σε αγώγιμο ύφασμα άνθρακα (Carbon Cloth). Η μελέτη των ηλεκτροδίων πραγματοποιήθηκε σε κατάλληλους φωτοηλεκτροχημικούς αντιδραστήρες, που σχεδιάστηκαν και κατασκευάστηκαν από τον κ. Λιανό για το σκοπό αυτό, ενώ έγινε χρήση λαπτήρα προσομοίωσης ορατής και υπεριώδους ακτινοβολίας. Η νανοκρυσταλλική τιτανία (ΤiO2) ως φωτοκαταλύτης, έχει ενεργειακό χάσμα 3,2eV και απορροφά φωτόνια μόνο στο υπεριώδες φάσμα της ηλεκτρομαγνητικής ακτινοβολίας. Για την αντιμετώπιση του ζητήματος αυτού, τοποθετήθηκε ευαισθητοποιητής θειούχου καδμίου (Csd) του οποίου το ενεργειακό χάσμα είναι 2,42eV και ενεργειακά έχει υψηλότερη στάθμη, από το διοξείδιο του τιτανίου, με αποτέλεσμα την αύξηση της απόκρισης στο ορατό φάσμα. Η ορατή ακτινοβολία απορροφάται από τον φωτοευαισθητοποιητή, ο οποίος διεγείρεται και εφόσον το ενεργειακό επίπεδο του διεγερμένου ηλεκτρονίου είναι ηλεκτραρνητικότερο από τη στάθμη αγωγιμότητας του TiO2, μεταπηδά στο TiO2 και συμμετέχει στην φωτοηλεκτροχημική διαδικασία. Η οπή που διαχωρίζεται από το διεγερμένο ηλεκτρόνιο, παραμένει στον φωτοευαισθητοποιητή και συμμετέχει σε αντιδράσεις οξείδωσης. Η ποιότητα και η αποτελεσματικότητα της καθόδου, παίζει εξίσου σπουδαίο ρόλο με εκείνη της ανόδου. Η απόδοση των φωτοηλεκτρικών κυψελίδων ελέγχεται μέσω του συντελεστή πληρότητας (Fill Factor), ο οποίος φαίνεται να παρουσιάζει μεγαλύτερη τιμή όσο αυξάνονται οι επιφάνειες των ηλεκτροδίων της ανόδου και της καθόδου, ενώ βέλτιστη απόδοση της φωτοηλεκτροχημικής κυψελίδας έχει επιτευχθεί με τη χρήση ηλεκτροδίου Carbon Cloth εμπλουτισμένου με νανοσωματίδια Pt (0.5mg Pt/cm2). Οι κυριότερες κατηγορίες των οργανικών ενώσεων που χρησιμοποιούνται ως οργανικοί ρύποι είναι οι αλκοόλες, οι πολυόλες και τα οξέα, ενώ στην παρούσα εργασία πιο αποδοτική φάνηκε να είναι η χρήση της μεθανόλης. / The idea behind this master’s degree thesis is based on the production of electrical energy through photo-degradation of organic emissions using photo-electrochemical cells. This way the consumption of the organic emissions and the conversion of the solar power to electricity are achieved. This thesis was aiming at the production, the characterization and the study of photosensitive electrocatalysts and turning them into electrodes, whose electrochemical behavior was studied and analyzed. The photo-electrochemical fuel cell is composed of the anode and cathode electrodes, who bare the photocatalyst and electrocatalyst respectively. Due to the n-type semiconductor on the photo-anode and its exposure to electromagnetic radiation, consumption of photons is observed and hole-electron pairs are formed. The energy of the incoming photon needs to be higher than the band gap of the semiconductor, for it to be absorbed and carriers to be created. The recombination rate of those carriers is reduced by using sacrificial agents or hole scavengers, which can be donors or acceptors of electrons. This way non- reversible reactions are achieved. Example of those is methanol, which was used in the present thesis. As photo-catalysts nanocrystals of titanium oxide and the composite semiconductor TiO2/CdS were used. The electro-catalyst Pt/C on carbon cloth was utilized. The study of the electrodes was performed used photo-electrochemical reactors designed by Prof. Lianos in combination with lamps simulating the solar spectrum. The nanocrystals of titanium oxide have a band gap of 3.2eV (in the UV region) which is the reason why CdS was deposited on top. The later has a band gap of 2.42eV and so increases the absorption in the visible region of the spectrum. The visible radiation is absorbed by the CdS layer and since the excited electron in more electronegative than the conduction band of the titanium oxide, it lowers its energy by hopping to the titanium oxide layer and participates in the photo-electrochemical procedure. The hole that’s left behind in the CdS layer is participating in the oxidation reactions. The performance of the photoelectrical cells was calculated through the fill factor and has an increasing value for increasing area of the electrodes. The optimum performance of the photoelectrochemical fuel cell was achieved by using a carbon cloth electrode enriched with Pt (0.5mg Pt/cm2). The primary categories of organic compounds used as organic emissions are alcohols, polyols and acids. The optimum performance was achieved by using methanol.