The advancement of quantum dot sensitized solar cell (QDSSC) technology depends on optimizing directional charge transfer between light absorbing quantum dots, TiO2, and a redox mediator. Kinetically, reduction of oxidized quantum dots by the redox mediator should be rapid and faster than the back electron transfer between TiO2 and oxidized quantum dots to maintain photocurrent. Thermodynamically, the reduction potential of the redox mediator should be sufficiently positive to provide high photovoltages. To satisfy both criteria and enhance power conversion efficiencies, we introduced charge transfer spin-crossover MnII/III complexes as promising redox mediator alternatives in QDSSCs. High photovoltages ~ 1 V were achieved by a series of Mn poly(pyrazolyl)borates, with reduction potentials ~0.51 V vs Ag/AgCl. Back electron transfer rates were slower than Co(bpy)3, where bpy = 2,2'-bipyridine. This is indicative of a large barrier to recombination imposed by spin-crossover in these complexes. By capitalizing on these characteristics, efficient MnII/III-based QDSSCs can be achieved with more soluble Mn-complexes. In hybrid bulk heterojunction solar cells (HBHJs), light-absorbing conjugated polymers are interfaced with films of nanostructured TiO2. Photovoltaic action requires photoelectrons in the polymer to transfer into the TiO2, and therefore, polymers are designed with lowest unoccupied molecular orbital levels higher in energy than the conduction band of TiO2 for thermodynamically favorable electron transfer. Currently, the energy level values used to guide solar cell design are referenced from the separated materials, neglecting the fact that upon heterojunction formation material energetics are altered. With spectroelectrochemistry, we discovered that spontaneous charge transfer occurs upon heterojunction formation between poly(3-hexylthiophene) (P3HT) and TiO2. It was determined that deep trap states in TiO2 accept electrons from P3HT and form hole polarons in the polymer. This equilibrium charge separation alters energetics through the formation of interfacial dipoles and results in band bending that inhibits desired photoelectron injection into TiO2, limiting HBHJ solar cell performance. New guidelines for improved photocurrent are proposed by tuning the energetics of the heterojunction to reverse the direction of the interfacial dipole, enhancing photoelectron injection. / Master of Science

Dye-sensitized solar cells (DSCs) convert sunlight to electricity at a low cost. In the DSC, a dye anchored to a mesoporous TiO2 semiconductor is responsible for capturing the sunlight. The resulting excited dye injects an electron into the conduction band of the TiO2 and is in turn regenerated by a redox mediator, normally iodide/triiodide, in a surrounding electrolyte. The success of the iodide/triiodide redox couple is mainly attributed to its slow interception of electrons at the TiO2 surface, which suppresses recombination losses in the DSC. One of the main limitations with the iodide/triiodide redox couple is, however, the large driving force needed for regeneration, which minimizes the open circuit voltage and thus the energy conversion efficiency. In this thesis, alternative redox couples to the iodide/triiodide redox couple have been investigated. These redox couples include the one-electron transition metal complexes, ferrocene and cobalt polypyridine complexes. The use of one-electron redox couples in the DSC has previously been shown to lead to poor photovoltaic performances, because of increased recombination. Cobalt redox couples were here found to give surprisingly high efficiencies in combination with the triphenylamine-based organic dye, D35. The success of the D35 dye, in combination with cobalt redox couples, was mainly attributed to the introduction of steric alkoxy chains on the dye, which supress recombination losses. By introducing steric substituents on the dye, rather than on the redox couple, mass transport limitations could in addition be avoided, which previously has been suggested to limit the performance of cobalt complexes in the DSC. The result of this study formed the basis for the world record efficiency of DSCs of 12.3 % using cobalt redox couples. Interfacial electron-transfer processes in cobalt-based DSCs were investigated to gain information of advantages and limitations using cobalt redox couples in the DSC. The redox potentials of cobalt redox couples are easily tuned by changing the coordination sphere of the complexes, and regeneration and recombination kinetics were systematically investigated by increasing the redox potential of the cobalt complexes. Our hope is that this thesis can be a guideline for future design of new redox systems in DSCs.

No description available.

Conselho Nacional de Desenvolvimento CientÃfico 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 desses compostos ainda à uma das maiores dificuldades enfrentadas pelas estaÃÃes de tratamento de efluentes das indÃstrias desse segmento. Dentre os mÃtodos de descoloraÃÃo, o tratamento anaerÃbio tem merecido bastante destaque por ser economicamente atraente. Nesta pesquisa, foram realizados dois experimentos acerca da remoÃÃo de cor de corantes de efluentes tÃxteis. O primeiro objetivou, inicialmente, avaliar e comparar a remoÃÃo de cor de efluente tÃxtil sintÃtico, contendo o corante azo Congo Red (CR), em sistemas anaerÃbios de um estÃgio, composto por um Ãnico reator UASB (R1), e de dois estÃgios (R2), composto por um reator UASB acidogÃnico (R2,A) seguido de um outro metanogÃnico (R2,M). Os reatores foram submetidos a diferentes condiÃÃes operacionais, variando-se as concentraÃÃes iniciais do corante e do substrato doador de elÃtrons (etanol) assim como o tempo de detenÃÃo hidrÃulica (TDH) dos reatores. Constatou-se que, com o aumento gradual da concentraÃÃo de CR de 0,3 para 1,2 mM, a eficiÃncia mÃdia total de remoÃÃo de cor do R1 diminuiu de 97,8 para 95,1%, enquanto a do R2 nÃo apresentou variaÃÃo relevante, sendo o R2,A responsÃvel por grande parte da descoloraÃÃo total alcanÃada (98,5%). Em relaÃÃo à concentraÃÃo inicial de etanol, observou-se queda de menos de 2% na eficiÃncia mÃdia do R1 contra quase 6% na do R2 ao se reduzir a concentraÃÃo do substrato de 1,0 para apenas 0,2 g DQO/L. E, ao se reduzir o TDH total dos sistemas de 24 para 12 horas, as eficiÃncias mÃdias de R1 e R2 passaram de, aproximadamente, 98% para 96,6 e 97,7%, respectivamente. Posteriormente, esses mesmos sistemas ainda foram alimentados com efluente tÃxtil real, e, apesar de ambos terem apresentado eficiÃncias de remoÃÃo de cor menores do que as obtidas com o CR, o R1 atingiu um valor mÃdio 7% maior do que o do R2. O segundo experimento buscou avaliar e comparar a remoÃÃo de cor de efluente tÃxtil real em sistemas anaerÃbios de um estÃgio (TDH = 12 h) suplementados ou nÃo com doador de elÃtrons (etanol) e mediador redox (AQDS). NÃo se observou nenhuma diferenÃa entre os valores mÃdios de eficiÃncia de descoloraÃÃo obtidos pelo reator suplementado com AQDS (R3) e pelo reator livre desse composto (R4). Entretanto, na ausÃncia de etanol, embora ambos os reatores tenham apresentado menores valores de eficiÃncia de remoÃÃo de cor, o R3 obteve uma eficiÃncia mÃdia 5% maior do que a do R4. Concluiu-se que os sistemas anaerÃbios empregados foram capazes de remover a cor de corantes de efluentes sintÃtico e real sob diferentes condiÃÃes operacionais. O impacto do mediador redox nÃo foi evidente no tratamento do efluente real a um TDH de 12 horas, e a ausÃncia de doador de elÃtrons adicional reduziu a eficiÃncia de remoÃÃo de cor dos reatores / The release of textile effluents into superficial water bodies represents a serious environmental problem and a public health concern because lots of dyes from wastewater and their breakdown products are potentially toxic and carcinogenic. Colour removal of dyes is still a challenge for textile industry wastewater treatment plants. Amongst the decolourisation methods, the anaerobic treatment has called attention for being economically attractive. This work reports two textile wastewater colour removal experiments. The first one aimed, primarily, to assess and compare colour removal of synthetic textile effluent, which contained the azo dye Congo Red (CR), in an one-stage anaerobic system, consisted of only a UASB reactor (R1), and in a two-stage anaerobic system (R2), consisted of an acidogenic (R2,A) followed by a methanogenic reactor (R2,M). The reactors were run under different operational conditions by varying the initial dye and electron donor (ethanol) concentrations as well as the hydraulic retention time (HRT) of the reactors. It was observed that, with gradual increase of CR concentration from 0.3 to 1.2 mM, R1 total average colour removal efficiency decreased from 97.8 to 95.1%, while R2 did not present remarkable variation, and R2,A was responsible for the major part of total decolourisation reached (98.5%). Concerning the initial ethanol concentration, a less than 2% drop was observed at R1 average efficiency against an almost 6% one at R2 by reducing the substrate concentration from 1.0 to only 0.2 g COD/L. And, by reducing the systems total HRT from 24 for 12 hours, the R1 and R2 average efficiencies changed from, approximately, 98% to 96.6 and 97.7%, respectively. Afterwards, those same systems were fed with real textile wastewater, and, although both have presented lower colour removal efficiencies than the ones achieved with CR, R1 reached a 7% average value higher than R2. The second experiment aimed to assess and compare the real textile wastewater colour removal in one-stage anaerobic systems (HRT = 12 h) supplemented or not with electron donor (ethanol) and redox mediator (AQDS). No difference was observed between decolourisation efficiency average values achieved by the reactor supplemented with AQDS (R3) and by the reactor free of this compound (R4). However, in the absence of ethanol, both reactors have presented lower colour removal efficiency values, the R3 reached a 5% average efficiency higher than R4 one. It can be concluded that the used anaerobic systems achieved good decolourisation efficiencies with both synthetic and real textile wastewaters under the different operational conditions studied. The redox mediator impact was not evident in the treatment of the real effluent at HRT of 12 hours, and the absence of an external electron donor reduced the reactors colour removal efficiency

Les travaux présentés dans cette thèse visent à étudier les interfaces "nanocatalyseur/glucose" et "enzyme/O2" d'une biopile hybride. Dans ce cadre, une nouvelle méthode de synthèse de nanoparticules à base d'or et de platine a été développée. Ces nanomatériaux ont été caractérisés par différentes méthodes physicochimiques pour connaître leur taille, leur morphologie et leur dispersion dans un substrat carboné (Vulcan XC72R). La surface active de chaque électrode a été déterminée par voltammétrie cyclique et par CO stripping. Il a été montré que dans les catalyseurs AuxPty, l'or a un effet promoteur sur le platine vis-à-vis de l'oxydation du glucose. Le catalyseur Au70Pt30 présente la meilleure activité catalytique. L'étude par spectroélectrochimie a permis de déterminer que la B–gluconolactone est le produit primaire de l'oxydation du glucose qui procède à bas potentiel par la déshydrogénation du carbone anomérique sur le platine. La réaction de réduction de O2 a été catalysée par une enzyme, la bilirubine oxydase (BOD). Pour faciliter le transfert électronique, deux médiateurs : ABTS et un complexe d'osmium ont été encapsulés avec l'enzyme dans une matrice de Nafion® pour créer les interfaces : BOD/ABTS/O2 et BOD/Os/O2. L'étude voltammétrique des deux médiateurs en milieu tampon phosphate a révélé deux systèmes quasi-réversibles avec des potentiels apparents proches du potentiel redox du site T1 de la BOD. Bien que difficilement comparables en termes de densité de courant au catalyseur constitué de nanoparticules de platine, les cathodes enzymatiques permettent de catalyser à quatre électrons la réduction de O2 à des potentiels très proches du potentiel de Nernst. / The work developed in this thesis concerns the study of the behavior of redox reactions at the interfaces "nanocatalyst/glucose" and "enzyme/O2" for a hybrid Biofuel Cell. In this framework, a novel synthesis method of based gold and platinum nanoparticles has been achieved. These synthesized nanomaterials were characterized by different physicochemical techniques to determine their size, morphology and their dispersion in Vulcan XC72R used as substrate. The active surface area of each electrode material was determined by cyclic voltammetry and CO stripping. It has been shown that in the bimetallic catalyst gold promotes platinum activity towards the glucose oxidation. The bimetallic composition Au70Pt30 exhibits the better efficiency. The study by spectroelectrochemistry determined that the B-gluconolactone is the primary product of the glucose oxidation which proceeds at low potential by the dehydrogenation of anomeric carbon on platinum. The reduction reaction of O2 was catalyzed by an enzyme, bilirubin oxidase (BOD). Mediated electronic transfer was performed with two redox mediators, ABTS and an Osmium complex (Os). They have been encapsulated with the enzyme in a Nafion® matrix to construct the interfaces: BOD/ABTS/O2 and BOD/Os/O2. The voltammetric study of the mediators in phosphate buffer revealed two quasi-reversible systems with an apparent potential close to the theoretical potential of the T1 BOD center. Although hardly comparable in terms of current density with the Pt nanocatalyst the O2 reduction is a four electron reaction at the cathodes BOD/ABTS and BOD/Os which deliver an electrode potential close to the Nernst one.