Orientador: Elizabete Jordão / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-23T06:39:10Z (GMT). No. of bitstreams: 1 Paschoalino_FlaviaCristinaSertori_D.pdf: 2972694 bytes, checksum: 77c5309ec8bdff08525a02274c840aae (MD5) Previous issue date: 2013 / Resumo: Este estudo apresenta a aplicação de três diferentes sistemas fotocatalíticos: (1) reator vítreo com fonte de radiação UV-C (250 W) operando em modo batelada com recirculação, cujo objetivo foi avaliar o desempenho dos fotocatalisadores TiO2, ZnO, CuO ou Ga2O3 em suspensão na degradação de uma solução de fenol a 100 mg L-1. Os resultados mostraram que quando empregado TiO2 P25 foi possível mineralizar 80% do fenol em solução após 150 min, sendo necessários 300 min para obter o mesmo desempenho com ZnO. Os óxidos CuO e Ga2O3 não apresentaram degradação fotocatalítica significativa; (2) reator solar tipo coletor parabólico composto (CPC) operando em modo contínuo ou batelada, com a finalidade de avaliar uma superfície suportada de TiO2 P25 sobre um óxido misto sol-gel TiO2/SiO2 na degradação de antibióticos (levofloxacina, ciprofloxacina, enrofloxacina, trimetoprim) em concentrações comumente encontradas em amostras ambientais. Os compostos ciprofloxacina e enrofloxacina foram rapidamente degradados por fotólise direta enquanto que a levofloxacina e o trimetoprim apresentaram-se mais recalcitrantes, sendo possível atingir valores de degradação próximos a 80% para a levofloxacina e 40% para o trimetoprim; (3) reator construído em Ti com fonte de radiação UV-C (102 W) operando em modo batelada com recirculação, cujo objetivo foi avaliar o desempenho do fotocatalisador TiO2 P25 em suspensão em conjunto com H2O2 na oxidação de uma solução de glicerol 100 mmol L-1 visando a obtenção de substâncias de alto valor agregado. Utilizou-se de um planejamento fatorial para avaliar a influência da concentração inicial do glicerol, do TiO2 e do H2O2. Alcançaram-se valores de degradação máxima do glicerol ao redor de 50%, sendo que o intermediário de degradação identificado de maior valor agregado foi a 1,3-dihidroxiacetona (DHA) com seletividade máxima de 15% / Abstract: This study presents the application of three different photocatalytic systems: (1) glass made reactor using an UV-C source (250 W) operating in batch mode through recirculation with the purpose to evaluate the performance of the photocatalysts TiO2, ZnO, CuO or Ga2O3 in suspension on the degradation of a phenol 100 mg L-1 aqueous solution. Results shown that when using TiO2 P25 it was possible to mineralize 80% of phenol after 150 min reaction. When using ZnO it was necessary 300 min reaction to achieve the same performance. CuO and Ga2O3 did not present significant efficiency; (2) compound parabolic collector (CPC) solar reactor operating in batch or continuous mode with the purpose of evaluate a TiO2 P25 surface supported onto a TiO2/SiO2 layer on the degradation of antibiotics (levofloxacyn, ciprofloxacyn, enrofloxacyn, trimetoprym) under common concentrations of environmental water samples. Ciprofloxacyn and enrofloxacyn were fastly degraded by direct photolysis process while levofloxacyn and trimetoprym presented more recalcitrant. It was possible to reach 80% degradation for levofloxacyn and 40% for trimetoprym; (3) titanium assembled reactor using an UV-C source (102 W) operating in batch mode under recirculation with the purpose of evaluate TiO2 P25 aqueous suspension in conjunction with H2O2 on the generation of substances with high commercial value. It was used a factorial planning to evaluate the influence of glycerol, TiO2 and H2O2 initial concentration. It was possible to obtain glycerol degradation of 50% and the main intermediate identified was 1,3-dihydroxyacetone (DHA) with a maximum selectivity of 15% / Doutorado / Sistemas de Processos Quimicos e Informatica / Doutora em Engenharia Quimica

Orientador: Ítalo Odone Mazali / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T16:18:18Z (GMT). No. of bitstreams: 1 Strauss_Mathias_D.pdf: 3061068 bytes, checksum: 3c7300ded2447af1ac677b59a5b1654c (MD5) Previous issue date: 2012 / Resumo: Materiais baseados no óxido de titânio (TiO2) são bastante explorados no desenvolvimento de tecnologias ambientalmente amigáveis que utilizam a radiação solar para a remediação de poluentes atmosféricos e na água, bem como na geração de energia. Aspectos relacionados aos efeitos da nanoestruturação sobre a atividade fotocatalítica do TiO2 são amplamente discutidos na literatura. Dentro deste contexto, a presente tese teve como objetivos centrais estudar os efeitos da cristalinidade, tamanho de cristalito e dopagem com metais de transição de nanopartículas de TiO2 suportadas em sílicas mesoporosas sobre atividade fotocatalítica. Foram utilizados dois protocolos distintos de síntese: método sol-gel (para estudo do efeito da cristalinidade) e método de ciclos de impregnação-decomposição (para estudo do efeito do tamanho de cristalito e dopagem com metais de transição). As propriedades estruturais, ópticas e eletrônicas das nanopartículas de TiO2 foram caracterizadas principalmente por difratometria de raios X e espectroscopias Raman (aplicada ao Modelo de Confinamento de Fônons) e UV-vis (aplicada ao Modelo de Aproximação da Massa Efetiva). A atividade fotocatalítica dos materiais foi avaliada quanto à fotodescoloração de azul de metileno, fotodegradação de ácido salicílico, fotogeração de radicais hidroxila e/ou fotooxidação de iodeto. Os materiais sintetizados a partir da rota sol-gel seguida por tratamento térmico em diferentes temperaturas permitiram o entendimento dos efeitos da cristalinidade de nanopartículas de TiO2 de tamanho fixo sobre a atividade fotocatalítica. Nanopartículas de baixa cristalinidade apresentaram menor ordem e maior quantidade de defeitos estruturais que atuaram como sítios de aprisionamento e recombinação dos portadores de carga diminuindo a atividade fotocatalítica. Quanto a influência do tamanho de cristalito, o aumento no tamanho diminuiu o valor em energia da banda proibida e aumentou a faixa de absorção do espectro UV-vis dos materiais, o que aumentou a capacidade de fotogeração de radicais OH. Por outro lado, o aumento do tamanho das nanopartículas leva também a uma redução na razão aréa superficial/volume das nanopartículas de TiO2 que trouxe redução na atividade catalítica, frente as reações de fotodescoloração de azul de metileno e fotodegradação de ácido salicílico, deixando clara a dependência com os mecanismos de adsorção e dessorção dos reagentes e produtos na superfície do fotocatalisador. A dopagem das nanopartículas de TiO2 com diferentes metais de transição (Mn, Co, Zn, Ce, Cu, Mo, Ni e Sn) promoveu a redução no valor da banda proibida e aumento na absorção de luz na região do visível. A fotooxidação de I- pelas nanopartículas de TiO2 dopadas mostrou-se fortemente dependente da formação de defeitos pontuais e distorções estruturais que são responsáveis pelo aprisionamento e recombinação dos elétrons e buracos / Abstract: Titanium oxide (TiO2) based material are much explored in the development of environmental friendly technologies that use the solar radiation to mitigate atmospheric and water pollutants, and on energy generation. Aspects related to the nanostructure of the TiO2 over its photocatalytic activity had been widely discussed in the literature. In this context, this thesis has as main objective studing the effects of the cristallinity, cristallite size and transition metals doping of TiO2 nanoparticles supported in mesoporous silicas over the photocatalytic activity. Two distinct synthesis protocols were used: sol-gel method (to study the cristallinity effects) and the impregnation and decomposition cycles method (to study the cristallite size and transition metal doping effects). The structural, optical and electronic properties of the TiO2 nanoparticles were studied using mainly X ray diffractometry, and Raman (applied to the Phonons Confinament Model) and UV-vis (applied to the Effective Mass Approximation Model) spectroscopies. The photocatalytic activity of the materials were tested against the photodecolorization of methylene blue, photodegradation of salycilic acid, photogeneration of OH radicals and/or photooxidation of I-. The material synthesized using the sol-gel route followed by thermal treatment permitted the understanding of the cristallinity effects of size-fixed TiO2 nanoparticles over the photocatalytic activity. Nanoparticles with low cristallinity presented lower structural order and higher number of structural defects that acted as trapping and recombination sites lowering the photocatalytic activity. Regarding the influence of the crystallite size, the increase in size decreased the band gap energy value and enhanced the UV-vis absorption range of the materials, that resulted in an enhanced OH radicals photogeneration capacity. By the other side, the increase in the particle size lead also to a reduction of the surface area/volume ratio of the TiO2 nanoparticles that brought reduction in the catalytic activity at the photodecolorization of methylene blue and photodegradation of salycilic acid reactions, letting clear its dependency with the adsorption and dessorption mechanisms of the reagents and products on the photocatalyst surface. Doping the TiO2 nanoparticles with different transition metals (Mn, Co, Zn, Ce, Cu, Mo, Ni e Sn) resulted in band gap lowering and enhancement of the visible radiation absorption. The photooxidation of I- had shown strong dependence with the generation of punctual defects and structural distortions that are responsible for the electrons and holes trapping and recombination / Doutorado / Quimica Inorganica / Doutor em Ciências

Orientador: Cláudia Longo / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-21T05:10:58Z (GMT). No. of bitstreams: 1 Oliveira_HaroldoGregoriode_D.pdf: 8058595 bytes, checksum: b4141a5719256524b785c37f949ee3d8 (MD5) Previous issue date: 2012 / Resumo: Eletrodos de filmes porosos contendo TiO2 e WO3 foram preparados sobre vidro revestido com SnO2:F (FTO), a partir de suspensões aquosas de TiO2 Degussa P25®, precursores de WO3, polietileno glicol e aquecimento (450°C, 30 min). As amostras de TiO2 e WO3 apresentaram máximo de absorção respectivamente em 390 e 480 nm; valores intermediários foram observados para as misturas. Os filmes de TiO2, ca. 4,5 mm, consistem de partículas esféricas interconectadas (diâmetro 25 nm) resultando em superfície porosa e excelente cobertura do substrato. A presença de H2WO4 na suspensão de TiO2 resultou no filme TiO2/WO3, com morfologia semelhante porém menos poroso. O eletrodo de WO3 apresentou cobertura não uniforme, com partículas na forma de flocos (0,1-1 mm). A deposição de TiO2 sobre o WO3 resultou no eletrodo de WO3-TiO2, de morfologia similar a do TiO2. As propriedades eletroquímicas foram investigadas em solução aquosa de Na2SO4, na ausência de luz e sob irradiação policromática. Os eletrodos apresentaram comportamento de semicondutor tipo n, com fotopotencial negativo e fotocorrente anódica; a presença do WO3 promoveu um aumento na fotocorrente. Os eletrodos foram utilizados para remediação de solução aquosa do corante rodamina 6G (10 mmol L) nas configurações de fotocatálise heterogênea (FH) e FH eletroquimicamente assistida por polarização a 0,7 V (FHE). Sob irradiação, nas 3 h iniciais, observou-se cinética de pseudo-1a ordem para o descoramento da solução; em FH, os eletrodos de WO3, TiO2 e WO3-TiO2 promoveram respectivamente a remoção de 8, 34 e 38 % do corante (constante de velocidade aparente de 0,37x10; 2,3x10 e 2,8x10 min) e, na ausência de fotocatalisador, apenas 4%. Maior eficiência foi observada em FHE; para o WO3-TiO2, p.ex., houve remoção de 44% do corante (3,2x10 min). Os eletrodos também foram utilizados para tratamento de solução aquosa do hormônio 17 a-etinilestradiol (34 mmol L); após 4 h em condições de FH e FHE, a remediação com TiO2 resultou na degradação de 38 e 48 %, enquanto que o eletrodo de TiO2/WO3 promoveu a degradação de 45 e 54 %. Ambos os eletrodos promoveram mineralização semelhante do hormônio, 15 e 19 %, para as condições de FH e FHE; na ausência de fotocatalisador, observou-se degradação de 10 % (4 % de mineralização). A oxidação fotocatalítica dos poluentes com estes eletrodos foi discutida considerando diagramas de energia; na presença de WO3, além de se obter um maior aproveitamento da radiação visível, a posição favorável das bandas de condução e de valência de ambos os semicondutores promove a separação das cargas fotogeradas, o que minimiza sua recombinação e aumenta a eficiência do processo de oxidação dos compostos orgânicos / Abstract: Porous films electrodes containing TiO2 and WO3 were deposited on SnO2:F (FTO) conducting glass from aqueous suspensions with TiO2 Degussa P25®, WO3 precursors and polyethylene glycol, followed by heating (450°C, 30 min). The maximum absorption was respectively observed at 390 and 480 nm for TiO2 and WO3 samples; intermediate values were obtained for the mixtures. The TiO2 films, ca. 4.5 mm, consisted of interconnected spherical particles (25 nm), resulting in a porous surface and excellent substrate coverage. Adding H2WO4 on the TiO2 suspension resulted in the TiO2/WO3 film, with comparable morphology but less porous. The WO3 electrode exhibited a non-uniform surface coverage with disk shaped particles (0.1-1mm). The morphology of the bilayer WO3-TiO2, obtained from the deposition of a TiO2 film on the top of a WO3 electrode, was similar to that observed for TiO2. The electrochemical properties were investigated in Na2SO4 aqueous solution, in the dark and under polychromatic irradiation. The electrodes exhibited an n-type semiconductor behavior, with negative photopotential and anodic photocurrent; higher photocurrent was observed for electrodes containing WO3. The electrodes were used for remediation of Rhodamine 6G dye aqueous solution (10 mmol L) using the configurations for heterogeneous photocatalysis (HP) and electro assisted-HP by polarization at 0.7 V (EHP). Under irradiation, at the initial 3 h, a pseudo first order kinetics was observed for the dye solution bleaching; in HP configuration, the WO3, TiO2 and WO3-TiO2 electrodes promoted respectively 8, 34 and 38 % of dye removal (apparent rate constants of 0.37x10; 2.3x10 and 2.8x10 min) and, without photocatalysts, only 4 %. Higher efficiency was observed under EHP configuration; for WO3-TiO2, 44 % of dye was removed (3.2x10 min). Also, the electrodes were used for treatment of aqueous solution containing the 17 a-ethynylestradiol hormone (34 mmol L); after 4 h in HP and EHP configurations, the remediation with TiO2 resulted in degradation of 38 and 48 % of the hormone, and the TiO2/WO3 electrode promoted 45 and 54 %. HP and EHP configuration resulted in similar mineralization for both electrodes, 15 and 19 %, respectively; without the photocatalyst, 10 % of degradation was observed (4 % of mineralization). The dye and hormone photocatalytic oxidation by these electrodes was discussed considering energy diagrams; for the electrodes containing WO3, the better harvesting of visible radiation, as well as, the favorable relative position of valence and conduction band of these semiconductors, promotes the separation of photogenerated charges, which minimizes their recombination, improving the efficiency of organic compounds oxidation / Doutorado / Físico-Química / Doutor em Ciências

Considerando aspectos relacionados ao conforto térmico nas edificações e redução da demanda de energia para resfriamento, a utilização de revestimentos frios (que refletem boa parcela da radiação solar recebida e emitem calor) no envelope construtivo pode ser uma alternativa viável para alcançar estas condições. No entanto, a sua durabilidade é o caminho crítico. O presente estudo tem o objetivo de determinar a durabilidade de revestimento multifuncional que reúne as propriedades: fria e autolimpante. Para alcançar esta meta foi formulado um revestimento cimentício monocamada, com e sem a adição de pigmento, ambos com elevada refletância solar e emissividade iniciais. Para manter a refletância ao longo do tempo foi realizada a aplicação de TiO2 anatásio aos revestimentos de duas formas, na primeira as partículas foram adicionadas à matriz cimentícia, enquanto na segunda foram aplicadas superficialmente como pós-tratamento. A exposição à radiação UV proporciona a fotoativação do anatásio que possui capacidade de oxidação da matéria orgânica e alteração do ângulo de contato entre a água e a superfície, facilitando o arraste das sujidades quando esta é molhada tornando-a autolimpante. A manutenção das propriedades frias e a permanência das partículas de TiO2 sobre a superfície foram avaliadas após 6 e 12 meses de exposição natural em estações localizadas nas cidades de Ubatuba, Pirassununga e São Paulo. Após o envelhecimento observou-se a influência determinante das características dos sítios de exposição no comportamento dos materiais. Dentre as formas de aplicação do anatásio verificou-se uma melhora sutil no desempenho dos revestimentos com adição de TiO2 à matriz cimentícia em relação à aplicação superficial do pós-tratamento. O processo de lixiviação observado em ambos os revestimentos expôs as partículas encapsuladas na argamassa com adição de TiO2, enquanto no pós-tratamento houve a remoção da camada superficial de anatásio. Por esse motivo o revestimento com adição apresentou interação com a radiação UV e material a ser degradado por mais tempo. Entretanto os resultados sugeriram que o tempo de exposição foi insuficiente para afirmar este comportamento, pois os resultados são próximos entre si. / Considering aspects related to the indoor thermal comfort in buildings and reducing energy demand for cooling, the use of cool coatings (have high reflectance and emittance of solar radiation) can be a reasonable alternative to achieve these conditions. However, its durability is the critical path. This study aims to measure the durability of multifunctional coating that combines cool and self-cleaning properties. To attain this goal a single-layer cement coating was formulated, with and without pigment added, both with high initial reflectance and emissivity. To maintain these properties over time a coating of TiO2 in crystalline form of anatase was applied to the coating in two ways: in the first way, the particles were mixed to the cementitious layer, and in the second, they were applied superficially as a post-treatment layer. The exposure to UV radiation provides the photoactivation of anatase, activating the oxidation of organic matter and altering the contact angle between water and surface, facilitating the drag of dirt when wet making it self-cleaning. The performance of cool properties and the permanence of TiO2 particles on the surface were evaluated at 6 and 12 months of natural exposure in Ubatuba, Pirassununga and São Paulo. After aging the determinant influence of the sites\' exposure characteristics in the materials performances was observed. A small tendency of improved performance with TiO2 added to the cement layer was verified. In addition, it was noted that these coatings presented higher durability in comparison to the post-treatment layer due to the leaching process, which exposes encapsulated particles in the cementitious mix, providing longer interaction with UV radiation and the organic matter to be degraded. On the other hand leaching caused the partial removal of anatase in the post-treated surfaces. Despite better performance of the TiO2 added coating, the exposure time was insufficient to affirm this behavior because the results are too close to each other.

La synthèse de particules d'oxydes mixtes en solution aqueuse est souvent difficile à contrôler en raison de la réactivité potentiellement différente des espèces qui coprécipitent. L’objectif de la thèse est de tenter de comprendre et piloter la synthèse dans le cas du système de particules d’oxydes mixtes de titane et d'étain, choisi en raison de l'existence d'une solution solide sur toute la gamme de composition et de la possibilité de recourir à une précipitation homogène plus simple à modéliser que le mélange réactif. Les synthèses sont réalisées par thermohydrolyse avec chauffage micro-ondes de solutions acides, fournissant des particules directement cristallisées avec des temps de réaction réduits. Les résultats des synthèses, à savoir le rendement et la composition du solide, sont modélisés par un calcul de sursaturation nécessitant la connaissance de la spéciation des solutions préparées. Cette dernière est calculée par la détermination à la température de thermohydrolyse des constantes d’équilibres en solution à partir de données bibliographiques et de mesures de solubilité à basse température d'une part et d'autre part de modélisation de la dépendance thermique des grandeurs thermodynamiques. Enfin, des nanocomposites Anatase-Rutile ont été obtenus par coprécipitation de titane avec de petites quantité d’étain et les propriétés photocatalytiques de ces nanoparticules ont été testées. / The synthesis of mixed oxide particles in aqueous solution is often difficult to control because of the potentially different reactivity of coprecipitating species. The aim of the thesis is to try to understand and control the synthesis in the case of mixed titanium oxide particles and tin system, chosen because of the existence of a solid solution over the entire range composition and the possibility of using a simpler homogeneous precipitation to model the reactant mixture. The syntheses are carried out by thermal hydrolysis of acidic solutions with microwave heating, providing particles directly crystallized with reduced reaction times. The results of the synthesis, namely the yield and composition of the solid, are modeled by a calculation of the supersaturation requiring knowledge of the speciation of the prepared solutions. This is calculated by determining the temperature of thermal hydrolysis in solution equilibrium constants from bibliographic data and low-temperature solubility measurements on the one hand and on the other hand, modeling of the temperature dependence of the thermodynamic. Finally, Anatase-Rutile nanocomposites were obtained by coprecipitation of titanium with small amounts of tin and the photocatalytic properties of these nanoparticles were tested

Ce travail se résume en deux objectifs principaux. Le premier concerne l'élaboration de matériaux nanohybrides de dioxyde de titane (sous forme sphérique ou tubulaire) décoré par des allotropes de carbone (fullerène fonctionnalisé ou graphène). Le deuxième objectif consiste à l'évaluation de ces différents nanomatériaux dans la photodégradation de l'acide formique (AF) sous irradiation UV. Un effet bénéfique des allotropes de carbone sur l'activité photocatalytique des nanohybrides a été observé suite à l'augmentation de la durée de vie des paires électron-trou photogénérées. Dans un premier temps, la méthode d'élaboration et la teneur en fullerène fonctionnalisé ont été optimisées conduisant ainsi à l'élaboration de nanomatériaux révélant des propriétés photocatalytiques améliorées par rapport au TiO2 nanotube seul. Une corrélation entre les propriétés texturales, les propriétés photoélectriques et la constante de vitesse de dégradation de l'AF a été établie afin d'élucider les causes de l'amélioration de l'activité photocatalytique. Dans un second temps, une étude détaillée portant sur l'élaboration d'une nouvelle génération de nanocomposites combinant nanotubes de TiO2 et oxyde de graphène (OG) a été menée. Le degré de réduction de l'oxyde de graphène influence fortement l'activité photocatalytique. Ainsi, l'addition d'OG ou OG réduit aux nanotubes de TiO2 influence positivement les performances intrinsèques en photodégradation de l'acide formique en facilitant le transfert de photoélectrons de la bande de conduction du TiO2 vers l'oxyde de graphène. Finalement, l'étude des matériaux composites combinant l'oxyde de graphène et diverses compositions anatase/rutile a permis de mettre en évidence une synergie entre le OG et les deux phases TiO2 / Two main objectives were achieved in the present work. The first objective concerns the elaboration of nanohybrid materials formed by combining titanium dioxide (in spherical or tubular form) with carbon allotropes (functionalized fullerene or graphene). The second objective consists in evaluating these different nanomaterials in the photodegradation of formic acid (FA) under UV irradiation. A beneficial effect of the different carbon allotropes on the photocatalytic activity of the resulting nanohybrids was observed and ascribed to an increased lifetime of photogenerated electron-hole pairs. In a first step, the elaboration method of functionalized fullerenes and their content were optimized leading to the development of nanomaterials showing improved photocatalytic properties compared to TiO2 nanotube alone. Textural properties, photoelectric properties and the FA degradation rate constant were correlated in order to determine the reasons for the photocatalytic activity improvement. In a second step, a detailed study about the development of a new generation of nanocomposites combining TiO2 nanotubes and graphene oxide (GO) was carried out. The degree of reduction of GO strongly influences the photocatalytic activity. Thus, the addition of reduced GO or GO to TiO2 nanotubes improves the intrinsic photodegradation performance of formic acid by facilitating the transfer of photoelectrons from the conduction band of TiO2 to graphene oxide. Finally, composite materials combining graphene oxide and various anatase/rutile compositions were analyzed showing a synergy between GO and the two TiO2 phases

Des films du type polyoxométallates-porphyrines ont été synthetisés et sont basés sur des interactions du types covalentes ou électrostatiques. Les films polyoxométallates–porphyrines sont obtenus par électro-oxydation de l’octaéthylporphyrine de zinc (ZnOEP) ou la 5,15-ditolylporphyrine (H2T2P) en présence de différents types of polyoxométallates (POMs) portant deux groupes pyridyles pendants (py-POM-py) Trois type de systèmes py-POM-py ont été utilises : i) un Lindqvist polyoxovanadate fonctionalisé via deux groupes tris-alkoxo , ii) un derive organosilyl fonctionalisé du type Keggin ou Dawson, et iii) des briques du type Dawson [P2W15V3O62]9− fonctionalisée avec des groupements organiques bis-pyridine de géométrie variée via un greffage diolamide). Tous ces films ont été testé pour la génération de photocourant et la photocatalyse de la réduction de métaux (Ag et Pt). Des films électrostatiques POM-porphyrin ont été également préparés par incorporation de polyanion du type Preyssler [NaP5W30O110]14- sur les films de porphyrine polycationic (poly-ZnOEP) électropolymérisés avec des espaceurs viologènes ou bis-viologènes. [NaP5W30O110]14- agit comme relais d’électron entre une porphyrine excitée ZnOEP* et le viologène (ou le bis-viologène) retardant la recombinaison de charge ce qui permet une augmentation du photocourant. Enfin, des nanoparticules POM@NPs (Pt, Au, Ag) ont été introduites en surface de copolymère polycationique à base de bis-porphyrine par métathèse afin d’augmenter l’efficacité de la génération de photocourant. La résonance de plasmon de surface localisée qui se produit à la surface des nanoparticules d'argent a sensiblement améliorée l'excitation électronique de porphyrine. / Polyoxometalates-porphyrin hybrid films were synthesized based on covalent or electrostatic interactions. Copolymeric polyoxometalate–porphyrin films were obtained by the electro-oxidation of zinc octaethylporphyrin (ZnOEP) or 5,15-ditolyl porphyrin (H2T2P) in the presence of a different type of polyoxometalates (POMs) bearing two pyridyl groups (py-POM-py). Three type of py-POM-py have been used: i) a tris-alkoxo functionalized Lindqvist polyoxovanadate, ii) an organosilyl functionalized Keggin-type [PW11Si2O40C26H16N2]3- and Dawson-type [P2W17Si2O62C26H16N2]6-, and iii) a bis-pyridine-substituted organo-polyoxometallic bricks using [P2W15V3O62]9− diolamide-grafting method with various geometries of the pendant group. All are applied for photocurrent generation and photocatalytical recovery of metals (Ag and Pt). Electrostatic POM-porphyrin films were also prepared by incorporated Preyssler type polyanion [NaP5W30O110]14- onto the electropolymerized polycationic porphyrin (poly-ZnOEP) with viologen or bis-viologen as spacers. [NaP5W30O110]14- as an efficient electron shuttle between the excited ZnOEP and viologen (or bis-viologen) which effectively retarded the fast charge pair recombination and enhanced the photocurrent magnitude. Later, we introduced nanoparticles POM@MNPs to a bis-porphyrin copolymer through metathesis reaction to further improve the efficiency of the photocurrent generation in which the localized surface plasmon resonance that occurs at the surface of silver nanoparticles has substantially enhanced the electronic excitation of surface-anchored porphyrin.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / In this work, the synthesis of the oxide zinc aluminate spinel (ZnAl2O4) was realized by the metal-chitosan complexation method in different calcinations temperatures with the purpose of studying their influence in the physical properties of the material. The powders obtained were characterized by X-ray diffraction (XRD), infrared spectroscopy (FTIR), nitrogen adsorption-dessorption by the Brunauer-Emmett-Teller (BET) method, scanning electron microscopy (SEM) and differential thermal analysis (DTA). This material was used as catalyst and its activity was investigated in the photodegradation reaction of an organic textile dye under ultraviolet irradiation. In order to do this research, aqueous solutions of the dye were used in different initial concentrations and different amounts of catalyst. In the photocatalytic tests, parameters like the influence of the dye s calcinations temperature, the influence of the dye s initial concentration and the effect of the catalyst concentration. The rates constants of photocatalytic reactions were determined. The summary of the results demonstrated the obtainment of mesoporous particles with high surface area. The photocatalytic tests indicated that the material prepared in this work shows satisfactory photocatalytic activity for the degradation of the organic pollutant. The initial concentration of the dye as well as the catalyst mass had significant influence in the photocatalytic process. / Neste trabalho foi realizada a síntese do óxido espinélio aluminato de zinco (ZnAl2O4) pelo método de complexação metal-quitosana em diferentes temperaturas de calcinação, a fim de estudar a influência das mesmas sobre as propriedades físicas do material. Os pós obtidos foram caracterizados por difração de raios-X (DRX), espectroscopia no infravermelho (FTIR), adsorção-dessorção de nitrogênio pelo método Brunauer-Emmett-Teller (BET), microscopia eletrônica de varredura (MEV) e análise térmica diferencial (ATD). Este material foi usado como catalisador e sua atividade foi investigada na reação de fotodegradação de um corante orgânico têxtil (Vermelho Procion H-E7B) sob irradiação ultravioleta. Para tal estudo, foram utilizadas soluções aquosas do corante em diferentes concentrações iniciais e diferentes quantidades de catalisador. Nos testes fotocatalíticos foram analisados parâmetros como influência da temperatura de calcinação do catalisador, influência da concentração inicial de corante e efeito da concentração de catalisador. As constantes de velocidade das reações fotocatalíticas foram determinadas. Os resultados da síntese demonstram a obtenção de partículas mesoporosas e com alta área superficial. Os testes fotocatalíticos indicaram que o material preparado neste trabalho apresenta satisfatória atividade fotocatalítica para a degradação do poluente orgânico. A concentração inicial do corante bem como a massa do catalisador influenciaram significativamente no processo fotocatalítico.

Two main subjects are addressed in this study. The ability of a bright red material with metallic behaviour to be used as a visible light photocatalyst for hydrogen evolution and the feasibility of visible light photocatalytic water splitting using Z-schemes constituted from different kinds of photocatalysts and materials used as mediators. Strontium niobate (Sr₁₋ₓNbO₃) is an A-site deficient perovskite with intense red colour. It is an unusual material that displays both metallic type conduction and- as we present- photocatalytic activity. Specifically, photocatalytic visible light hydrogen production with oxalic acid as a sacrificial reagent is achieved from this material even without the need for a co-catalyst or other alteration. This photocatalytic activity is screened with time and related to different parameters that might influence it, like crystal structure, surface area and surface chemistry. The crystal structure of strontium niobate is A site stoichiometry dependant and the materials acquires a cubic symmetry for Sr≤ 0.92 and orthorhombic for 0.92≤ Sr≤ 0.97. The change of crystal structure from cubic to orthorhombic symmetry seems to have a negative effect on the photocatalytic activity, as the NbO₆ octahedra become distorted and unfavourable for d-orbital overlapping. The highest photocatalytic activity is exhibited at the turning point of one structure to the other. Increase in the photocatalytic activity is also exhibited by enlarging the surface area through ball milling, nevertheless, a clear trend for surface area effect on activity is not obtained among samples with different Sr content. Additionally, an enrichment of Sr on the surface of strontium niobate is observed by XPS, which apart from the fact that seems to be a governing factor improving stability it is also considered a key point for the exhibited photocatalytic activity altogether. Full water splitting under visible light from Z-schemes is studied by fabricating three general categories of systems. These three different categories depend on the mediator used to fabricate the Z-schemes and are: redox couple Z-schemes (with Fe⁺³/Fe⁺²), solid mediator Z-schemes (with GO) and no mediator Z-schemes. The materials used as photocatalysts for the fabrication of the Z-schemes are: Sr₀.₉₂NbO₃ for hydrogen production and both WO₃ and BiVO₄ independently for oxygen production. The photocatalytic activity for water splitting is evaluated in production of hydrogen and oxygen with time and the ratio of their production rates is frequently checked to see whether the ideal hydrogen to oxygen 2:1 is achieved. The general idea acquired from the results of all the three types of systems is that, water splitting with Z-schemes is a complicated process and in most cases governed by many subreactions. More specifically, in all cases of redox couple Z-schemes we got hydrogen to oxygen ratio imbalances and with the most prominent one being the lack of hydrogen production. Thankful is the fact that a certain type of system, the one consisting of WO₃ as oxygen photocatalyst and Fe⁺² as initial mediator species gives results very close to the ideal one and with a high degree of reproducibility indicating this way the probable formation of a Z-scheme that has overcome more of the imbalances. In between the two other categories, solid mediator and no mediator Z-schemes, subreactions seem to be the governing factor hence imbalances are always present. A case study in the no mediator Z-schemes on an attempt to investigate sources of imbalances, reveals that a big source of imbalance is most probably from the trapping of protons from WO₃.

Photocatalytic reactions mediated by semiconductors such as ZnS, TiO2, ZnO, etc. can harvest solar energy into chemical bonds, a process with important prebiotic and environmental chemistry applications. The recycling of CO2 into organic molecules (e.g., formate, methane, and methanol) facilitated by irradiated semiconductors such as colloidal ZnS nanoparticles has been demonstrated. ZnS can also drive prebiotic reactions from the reductive tricarboxylic acid (rTCA) cycle such as the reduction of fumarate to succinate. However, the mechanism of photoreduction by ZnS of the previous reaction has not been understood. Thus, this thesis reports the mechanisms for heterogeneous photocatalytic reductions on ZnS for two model reactions in water with sulfide hole scavenger. First the reduction of CO2 is carried out under variable wavelength of irradiation and proposed to proceed thorough five steps resulting in the exclusive formation of formate. Second the reduction of the double bond of fumaric acid to succinic acid is reported in detail and compared to the previous conversion of CO2 to formic acid. Both reactions are carried out under variable wavelength of irradiation and proposed to proceed thorough one electron transfer at a time. In addition, a new method to measure the bandgap of colloidal ZnS suspended in water is established. Furthermore, the time scales of electron transfer and oxidizing hole loss during irradiation of ZnS for both reactions are reported and interpreted in terms of the Butler-Volmer equation. The sunlight promoted production of succinate introduced above, provides a connection of this prebiotic chemistry work to explore if central metabolites of the rTCA cycle can catalyze the synthesis of clay minerals. Clay minerals are strong adsorbents that can retain water and polar organic molecules, which facilitate the polymerization of biomolecules and conversion of fatty acid micelles into vesicles under prebiotic conditions relevant to the early Earth. While typical clay formation requires high temperatures and pressures, this process is hypothesized herein to be accelerated by central metabolites. A series of synthesis are designed to last only 20 hours to study the crystallization of sauconite, an Al- and Zn-rich model clay, at low temperature and ambient pressure in the presence of succinate as a catalyst. Succinate promotes the formation of the trioctahedral 2:1 layer silicate at ≥ 75 °C, 6.5 ≤ pH ≤ 14, [succinate] ≥ 0.01 M. Cryogenic and conventional transmission electron microscopies, X-ray diffraction, diffuse reflectance Fourier transformed infrared spectroscopy, and measurements of total surface area and cation exchange capacity are used to study the time evolution during the synthesis of sauconite. While the studies with ZnS presented above advanced the fundamental understanding of photocatalysis with single semiconductors, the environmental applications of this material appear limited. A common limitation to photocatalysis with single semiconductors is the rapid recombination of photogenerated electron-hole pairs, which reduces significantly the efficiency of the process that in the case of ZnS also suffers from photocorrosion in the presence of air. In order to overcome the fast charge recombination and the limited visible-light absorption of semiconductor photocatalysts, an effective strategy is developed in this work by combining two semiconductors into a nanocomposite. This nanocomposite is solvothermally synthesized creating octahedral cuprous oxide covered with titanium dioxide nanoparticles (Cu2O/TiO2). The nanocomposite exhibits unique surface modifications that provide a heterojunction with a direct Z-scheme for optimal CO2 reduction. The band structure of the nanocomposite is characterized by diffused reflectance UV-visible spectroscopy, X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy. The photoreduction of CO2(g) to CO(g) on the nanocomposite is investigated in the presence water vapor as the hole scavenger that generates the quantifiable hydroxyl radical (). The quantum efficiency of CO production under irradiation at λ ≥ 305 nm with the nanocomposite is 2-times larger than for pure Cu2O. The detection of and XPS analysis contrasting the stability of Cu2O/TiO2 vs Cu2O during irradiation prove that TiO2 prevents the photocorrosion of Cu2O. Overall, the studies of photocatalytic reductions on single component semiconductors reveal new knowledge needed for developing future photocatalytic application for fuel production, wastewater treatment, reducing air pollution, and driving important prebiotic chemistry reactions. Furthermore, the design of a photocatalyst operating under a Z-scheme mechanism provides a new proof of concept for the design of systems that mimic photosynthesis. Finally, this work also demonstrates how molecules obtained by mineral mediated photochemistry can catalyze clay formation; highlighting the important role that photochemistry may have played for the origin of life on the early Earth and other rocky planets.