O presente trabalho avaliou o efeito da relação \'C\'/\'N\' na produção biológica de hidrogênio a partir de água residuária sintética a base de sacarose. Reatores de leito fixo e fluxo ascendente, com polietileno de baixa densidade reciclado para adesão da biomassa, foram operados a 25°C e com um tempo de detenção hidráulica (TDH) de 2 horas. Analisaram-se diferentes relações \'C\'/\'N\' (40, 90, 140 e 190), usando a sacarose e a uréia como fontes de carbono e nitrogênio, respectivamente. Os valores médios de produtividade de \'H IND.2\' foram de 0,6 mol-\'H IND.2\'/mol-sac, 1,3 mol-\'H IND.2\'/mol-sac, 2,2 mol-\'H IND.2\'/mol-sac e 1,7 mol-\'H IND.2\'/mol-sac quando operados os reatores com relações \'C\'/\'N\' iguais a 40, 90, 140 e 190, respectivamente. Encontrou-se um valor ótimo para \'C\'/\'N\' de 137, que resultaria em produtividade de \'H IND.2\' de 3,5 mol-\'H IND.2\'/mol-sac, valor igual ao alcançado na relação \'C\'/\'N\' de 140. O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\', com valores médios porcentuais para o \'H IND.2\' de 53%, 49%, 61% e 52% para as relações \'C\'/\'N\' de 40, 90, 140 e 190, respectivamente. Os principais produtos intermediários produzidos durante a produção de \'H IND.2\' foram similares em todas as relações \'C\'/\'N\', sendo principalmente detectados ácido acético, ácido butírico e etanol. Sob excesso de nitrogênio, o crescimento da biomassa foi maior com efeitos negativos sobre a produção de hidrogênio, enquanto carência de nitrogênio permitiu o controle do crescimento da biomassa e resultou em maiores produtividades de hidrogênio. Durante os experimentos observou-se queda na produção do biogás provavelmente por atuação de bactérias hidrogênio-oxidantes. / This study evaluated the effect of the carbon/nitrogen (\'C\'/\'N\') ratio on the hydrogen production from a sucrose-based synthetic wastewater. Up-flow fixed-bed anaerobic reactors with recycled low-density polyethylene for biomass attachment, were operated at 25ºC and with a 2 hours time of hydraulic detention. Several \'C\'/\'N\' relationship were studied (40, 90, 140 and 190), using sucrose and urea as carbon and nitrogen sources, respectively. The average value of the hydrogen productivity were 0,6 mol-\'H IND.2\'/mol-suc, 1,3 mol-\'H IND.2\'/mol-suc, 2,7 mol-\'H IND.2\'/mol-suc e 1,7 mol-\'H IND.2\'/mol-suc they were reached when the reactors were operated with \'C\'/\'N\' of 40, 90, 140 and 190, respectively. It was found an optimal value for \'C\'/\'N\' of 137, which would result in productivity of 3,5 mol-\'H IND.2\'/mol-suc, an amount equal to that achieved in the \'C\'/\'N\' relationship of 140. Biogas produced was composed of \'H IND.2\' and \'CO IND.2\', with average \'H IND.2\' content 53%, 49%, 61% and 52% for \'C\'/\'N\' of 40, 90, 140 e 190, respectively. The mainly intermediary products during \'H IND.2\' fermentation were similar for all the \'C\'/\'N\' ratios, being specially detected acetic acid, butyric acid and ethanol. Under excess of nitrogen the biomass growth is higher with negative effects on hydrogen production while deprivation of nitrogen permits the control of biomass growth and results in higher hydrogen productivity. During the experiments it was been observed decline in the biogas production, probably because of the action of the hydrogen-oxidizing bacteria.

O objetivo deste estudo foi avaliar o efeito da adição de alcalinidade, da concentração da glicose e da taxa de carregamento orgânico na produção de hidrogênio e ácidos orgânicos em reator anaeróbio de leito fluidificado (RALF), contendo argila expandida (2,8 - 3,35 mm) como material suporte para adesão microbiana. Foram utilizados oito reatores idênticos, sendo quatro deles operados sem adição de alcalinidade, e com concentração de glicose de 2000, 4000, 10000 e 25000 mg/L, respectivamente. Outros quatro reatores operados com adição de alcalinidade, e com as mesmas concentrações de glicose cada um. Os reatores foram inoculados com lodo anaeróbio pré-tratado termicamente, operado com tempo de detenção hidráulica (TDH) decrescente de 8 h a 1 h à temperatura controlada de 30°C. Foi constatada produção volumétrica de hidrogênio máxima de 1,58 L/h.L, para o reator operado com 10000 mg/L de glicose com adição de alcalinidade (R10CA) e um rendimento máximo de 2,52 mol \'H IND.2\'/mol glicose, para o reator operado com 4000 mg/L de glicose com adição de alcalinidade (R4CA). O biogás produzido foi composto de \'H IND.2\' e \'CO IND.2\'. Em ambos os reatores, o conteúdo de hidrogênio aumentou com a redução do TDH de 8 h para 1 h, alcançando valor máximo de 77%, para o reator operado com 4000 mg/L sem adição de alcalinidade (R4SA). Os reatores operados com altas concentrações de glicose produção de hidrogênio, o qual predominou o ácido acético e butírico. Neste mesmo reator, o rendimento da produção de hidrogênio foi superior aos outros reatores. As análises de clonagem e sequenciamento do consórcio bacteriano revelaram semelhanças com Clostridium, Klebsiella, Enterobacter e bactérias não cultivadas. / This study evaluated the effect alkalinity addition, glucose concentration and organic loading rate in the hydrogen production and organic acids in an anaerobic fluidized bed reactor (AFBR), containing expanded clay (2.8 - 3,35 mm) as support material for microbial adhesion. We used eight identical reactors, four of them operated without the addition of alkalinity, and concentration of glucose in 2000, 4000, 10000 and 25000 mg/L, respectively. Another four reactors operated with the addition of alkalinity, and with the same concentrations of glucose each. The reactors were operated with hydraulic retention times (HRT) ranging from 8 h at 1 h, and temperature of 30°C. It has been found for hydrogen production rate maximum 1.58 L/h.L for the reactor operated with 10000 mg/L glucose with the addition of alkalinity (R10CA) and a maximum yield of 2.52 mol \'H IND.2\'/mol glucose to the reactor operated with 4000 mg/L glucose with the addition of alkalinity (R4CA). The biogas produced was composed of \'H IND.2\' and \'CO IND.2\'. In both reactors, the hydrogen content increased with the reduction of HRT of 8 h at 1 h, reaching a maximum of 77% for the reactor operated from 4000 mg/L without added alkalinity (R4SA). The reactors operated with high glucose concentrations (10000 mg/L and 25000 mg/L) had higher proportions of solvents such as soluble metabolites. There was a linear correlation between the hydrogen production rate and organic loading rate in all reactors. The yield, the hydrogen production rate and distribution of soluble metabolites in both reactors, were influenced by the glucose concentration. The reactor operated with 4000 mg/L and addition of alkalinity, presented the most favorable distribution of soluble metabolites to hydrogen production, which was predominant acetic and butyric acid. In the same reactor, the hydrogen yield was higher than other reactors. The cloning and sequencing analysis bacterial consortium revealed the presence of Clostridium, Klebsiella, Enterobacter and uncultivated bacteria.

The modernized world is over-consuming low-cost energy sources that strongly contributes to environmental stress. As a consequence, the interest for environmentally friendly alternatives has increased immensely. One such alternative is utilizing the diazotrophic nature of the heterocystous filamentous cyanobacteria Nostoc sp. as feedstock for biodiesel and hydrogen production using pulp and paper wastewater – a phosphorous and nitrogen deficient medium. In this work, biodiesel and hydrogen production was studied with respect to three main aspects: biodiesel quality properties, lipid content and hydrogen production coupled with a preliminary study investigating the luminous effects on the biomass and biodiesel quality properties when exposed to low (50 μEm-2s-1), medium (150 μEm-2s-1) and high light (300 μEm-2s- 1). The preliminary study showed that an increase of light intensity was associated with parabolic results for biomass following the 10-day cultivation period, with the medium light intensity showing an average dried weight of at the most 203% greater than the two other light intensities. When analysing the FAME- composition, similar results were demonstrated for the fatty acid constituents preferred for biofuel applications, C18:1 and C18:2 fatty acids, where the low, medium and high light showed an accumulative 34.65, 43.1 and 31.6 dwt % respectively. The strain could be of interest as feedstock for biodiesel when cultivated in pulp and paper wastewater, due to the positive results pertaining to the lipid content and biodiesel quality properties. Following the 10-day cultivation period the lipid content obtained was 35.9 dwt %. The biodiesel quality properties were tested to assess the strains suitability for biodiesel and were tested to ensure its accordance to the standards on commercial biodiesel quality; European Standard for Biodiesel as heating oil (EN 14213) and European Biodiesel Standard (EN 14214). The critical parameters tested were the regulated (iodine value, cetane number, density, viscosity, pour point, cold filter plugging point, oxidative stability) and unregulated (FAME-composition) fuel properties. Results obtained showed values within the regulated values set by the different standards. However, due to a high saturated fatty acid content, the strain showed inadequate low temperature flow properties (cloud point, pour point and the cold filter plugging point). This study shows that this strain has a low potential for hydrogen production, with a hydrogen production of 0.13 nmol/mg dry wt/h following the 10-day cultivation period. This low hydrogen production could be attributed to the among other things the current growth phase of the cyanobacteria. Chemical analyses were conducted for revealing the total nitrogen, total phosphorus and chemical oxygen demand (COD) content. Following the 10-day cultivation period, the samples showed a 22% decrease in phosphorous concentration, 11% decrease in COD concentration and 51% increase of nitrogen concentration. The probable causes for this increase is the Nostoc’s diazotrophic nature and the ammonium excretion nitrogen fixation entails, as well as the nitrogen release following the final algal growth phase – the death phase. In conclusion, the results showed great potential, however, further studies are recommended investigating the changes that occurs during cultivation period to further assess the strains potential as well as assessing the continuity of the results with a greater initial cellular concentration. Nonetheless, due to the positive results obtained regarding the nutrient uptake, biodiesel and hydrogen production, this study shows potential for further optimization for the use of Nostoc grown in pulp and paper wastewater for wastewater treatment, biodiesel and/or hydrogen production.

Ces travaux de thèse ont été développés dans un contexte de motivation générale de développement de modes de transport plus électrifiés et plus respectueux de l'environnement, dans le but de réduire considérablement les émissions de gaz à l'effet de serre. Plus particulièrement l'objectif de ce projet de thèse a été d'étudier la faisabilité d'un concept de génération d'hydrogène à bord, par déshydrogénation catalytique partielle (PDh) du carburant, permettent d'obtenir de l'hydrogène pour alimenter une pile à combustibles embarquée en replacement des unités de puissance auxiliaires. Dans un même temps le combustible qui n'est que partiellement déshydrogéné conserve ses propriétés et peut être réinjecté dans le pool de carburant. Cette thèse est divisée en deux grandes parties. Une première partie décrit les travaux de recherche sur la déshydrogénation partielle du kérosène pour la production d'hydrogène à bord d'un avion. Le choix du catalyseur est crucial, il doit permettre de produire de l'hydrogène de haute pureté sans compromettre les propriétés d'origine du kérosène. Des matériaux avancés, composés de métaux imprégnés sur des nouveaux supports ont été développés, caractérisés et évalués en tant que catalyseur dans la réaction de PDh. L'influence de la composition du catalyseur sur son activité, sélectivité et durée de vie ainsi que les mécanismes de désactivation ont été étudiés. Un matériau catalytique optimisé composé d'une phase active de 1% Pt - 1 % Sn (m/m) supporté sur une γ-alumine à porosité contrôlée, a permis une production d'hydrogène de 3500 NL•h-1•kgcat-1, avec une pureté de 97,6% vol. et un temps de vie de 79 h, ce qui correspond à une puissance électrique fournie par une pile à combustible de 3,5 kW.La deuxième partie du manuscrit décrit une étude sur le diesel et l'essence et sur la faisabilité de la génération d'hydrogène par PDh des carburants autres que le kérosène. Les résultats obtenus avec le même matériau sont encourageants et montre une application possible dans des domaines de transports autres que l'aviation. Les résultats les plus significatifs obtenus avec des substituts de gasoil et d'essence sont respectivement des valeurs de productivité d'hydrogène de 3500 et 1800 NL•h-1•kgcat-1 avec des temps de vie de 29 et 376 h et une pureté supérieur à 99 % vol. pour le deux. / This thesis work have been developed in the general context of the development of more electrified and environmentally friendly means of transport, in order to significantly reduce greenhouse gases emissions. More specifically, the objective of this thesis project was to study the feasibility of the concept of on-board hydrogen generation by catalytic partial dehydrogenation (PDh) of fuel. The hydrogen produced serves to power a fuel cell system that replaces vehicles auxiliary power units. At the same time the fuel, that is only partially dehydrogenated, maintains its properties and can be re-injected into the fuel pool.This thesis is divided into two main parts. The first part describes the research on the PDh of kerosene to produce hydrogen on-board an aircraft. The choice of the catalyst is crucial: it should allow to produce high purity hydrogen without compromising the original properties of kerosene. Advanced materials, composed by metals impregnated on different supports, have been developed, characterized and evaluated as a catalysts in the reaction of PDh. The influence of catalyst composition on the activity, selectivity and stability as well as the deactivation mechanisms were studied. One of the optimized catalytic materials, composed of a 1% Pt - Sn 1% (w/w) active phase supported on a γ-alumina with controlled porosity, allowed a hydrogen production of 3500 NL•h-1•kgcat-1, with a purity of 97.6% vol. and a lifetime of 79 h, which corresponds to 3.5 kW of electric power supplied by fuel cells.The second part of the manuscript describes a study on diesel and gasoline and asses the feasibility of hydrogen generation by PDh of fuels different from kerosene. The results obtained with the previously mentioned catalyst are encouraging and show the possibility of applying this concept to other fields of transportation beside the aviation. The most significant results obtained with gasoline and diesel surrogates are respectively a hydrogen productivity value of 3500 et 1800 NL•h-1•kgcat-1 with lifetimes of 29 and 376 h and a purity that exceeds 99% vol. in both cases.

abstract: Mixed-ionic electronic conducting (MIEC) oxides have drawn much attention from researchers because of their potential in high temperature separation processes. Among many materials available, perovskite type and fluorite type oxides are the most studied for their excellent oxygen ion transport property. These oxides not only can be oxygen adsorbent or O2-permeable membranes themselves, but also can be incorporated with molten carbonate to form dual-phase membranes for CO2 separation. Oxygen sorption/desorption properties of perovskite oxides with and without oxygen vacancy were investigated first by thermogravimetric analysis (TGA) and fixed-bed experiments. The oxide with unique disorder-order phase transition during desorption exhibited an enhanced oxygen desorption rate during the TGA measurement but not in fixed-bed demonstrations. The difference in oxygen desorption rate is due to much higher oxygen partial pressure surrounding the sorbent during the fixed-bed oxygen desorption process, as revealed by X-ray diffraction (XRD) patterns of rapidly quenched samples. Research on using perovskite oxides as CO2-permeable dual-phase membranes was subsequently conducted. Two CO2-resistant MIEC perovskite ceramics, Pr0.6Sr0.4Co0.2Fe0.8 O3-δ (PSCF) and SrFe0.9Ta0.1O3-δ (SFT) were chosen as support materials for membrane synthesis. PSCF-molten carbonate (MC) and SFT-MC membranes were prepared for CO2-O2 counter-permeation. The geometric factors for the carbonate phase and ceramic phase were used to calculate the effective carbonate and oxygen ionic conductivity in the carbonate and ceramic phase. When tested in CO2-O2 counter-permeation set-up, CO2 flux showed negligible change, but O2 flux decreased by 10-32% compared with single-component permeation. With CO2 counter-permeation, the total oxygen permeation flux is higher than that without counter-permeation. A new concept of CO2-permselective membrane reactor for hydrogen production via steam reforming of methane (SRM) was demonstrated. The results of SRM in the membrane reactor confirm that in-situ CO2 removal effectively promotes water-gas shift conversion and thus enhances hydrogen yield. A modeling study was also conducted to assess the performance of the membrane reactor in high-pressure feed/vacuum sweep conditions, which were not carried out due to limitations in current membrane testing set-up. When 5 atm feed pressure and 10-3 atm sweep pressure were applied, the membrane reactor can produce over 99% hydrogen stream in simulation. / Dissertation/Thesis / Doctoral Dissertation Chemical Engineering 2020

El hidrógeno es un portador de energía que ya ha demostrado su capacidad para reemplazar el petróleo como combustible. Sin embargo, los medios de producción actualmente en uso siguen siendo altamente emisores de gases de efecto invernadero. La foto-electrólisis del agua es un proceso que, a partir de la energía solar, separa los compuestos elementales del agua como el hidrógeno y el oxígeno utilizando un semiconductor con propiedades físicas adecuadas. La hematita (¿-Fe2O3) es un material prometedor para esta aplicación debido a su estabilidad química y su capacidad para absorber una porción significativa de la luz (con una banda prohibida entre 2.0 - 2.2 eV). A pesar de estas propiedades ventajosas, existen limitaciones intrínsecas al uso de óxido de hierro para la descomposición fotoelectroquímica del agua. La primera restricción es la posición de su banda de conducción que es menor que el potencial de reducción de agua. Esta limitación se puede superar mediante la adición en serie de un segundo material, en tándem, que absorberá una parte complementaria del espectro solar y llevar a los electrones a un nivel de energía más alto que el potencial para la liberación de hidrógeno. El segundo obstáculo proviene del desacuerdo entre la corta longitud de difusión de los portadores de carga y la profundidad de penetración larga de la luz. Por lo tanto, es necesario controlar la morfología de los electrodos de hematita en una escala de tamaño similar a la longitud de transporte del orificio. En esta tesis, se introduce un nuevo concepto para mejorar el rendimiento fotoelectroquímico de la hematita. Usando el método hidrotermal depositamos capas delgadas de hematita dopada con Cr en sustratos de vidrio conductivo. También se ha preparado por medios electroquímicos una heterounión del tipo p-CuSCN/n-Fe2O3 depositando secuencialmente una capa de ¿-Fe2O3 y una película de CuSCNsobre sustratos de FTO (SnO2: F).Finalmente, se ha preparado células solares de perovskitas y óxido de hierro. Para ello se depositó una capa delgada, densa y uniformede óxido de hierro (¿-Fe2O3) como capa de transporte de electrones (ETL) en lugar de dióxido de titanio (TiO2) que se utiliza convencionalmente en las células fotovoltaicas perovskitastipoCH3NH3PbI3 (SGP). Este último dispositivo mostró un aumento en la fotocorriente del 20% y un IPCE30 veces mayor que la hematita simple, lo que sugiere una mejor conversión de las longitudes de onda por encima de 500 nm. Palabras clave: Fotoelectroquímica, división de agua, producción de hidrógeno, evolución de oxígeno, semiconductores de óxido de metal, hematita, óxido de hierro, nanoestructuras / Hydrogen is an energy carrier that has already demonstrated its ability to replace oil as a fuel. However, the means of production currently used remain highly emitting greenhouse gases. Photo-electrolysis of water is a process that uses solar energy to separate the elemental compounds of water such as hydrogen and oxygen using a semiconductor with adequate physical properties. Hematite (¿-Fe2O3) is a promising material for this application because of its chemical stability and ability to absorb a significant portion of light (with a band-gap between 2.0 - 2.2 eV). Despite these advantageous properties, there are intrinsic limitations to the use of iron oxide for the photoelectrochemical cracking of water. The first constraint is the position of its conduction band, which is lower than the water reduction potential. This constraint can be overcome by the addition in series of a second material, in tandem, which will absorb a complementary part of the solar spectrum and bring the electrons to a higher energy level than the potential of hydrogen release. The second obstacle comes from the disagreement between the short diffusion length of the charge carriers and the long light penetration depth. It is therefore necessary to control the morphology of the hematite electrodes on a scale of similar size to the transport length of the hole. In this thesis a new concept is introduced to improve the photoelectrochemical performances. Using the hydrothermal method we deposited thin layers of Cr-doped hematite on conductive glass substrates. We also electrochemically prepared a p-CuSCN / n-Fe2O3 heterojunction by sequentially depositing ¿-Fe2O3 and CuSCN films on FTO (SnO2: F) substrates. Finally, we have used uniform and dense thin layers of iron oxide (¿-Fe2O3) as an electron transport layer (ETL) in place of titanium dioxide (TiO2) conventionally used in photovoltaic cells based on perovskites CH3NH3PbI3 (PSC). This latter concept showed a 20% increase of the photocurrent and an IPCE 30 times greater than the simple hematite, suggesting better conversion of high wavelengths (> 500 nm). Keywords: Photoelectrochemistry, Water Splitting, Hydrogen Production, Oxygen Evolution, MetalOxide Semiconductors, Hematite, Iron Oxide, Nanostructures, Surface. / L'hidrogen és un proveïdor d'energia que ja ha demostrat la seva capacitat per reemplaçar el petroli com a combustible, però els mitjans de producció actuals continuen essent fortament emissors dels gasos responsables d'efecte hivernacle. La fotoelectròlisi de l'aigua és un procés que, a partir de l'energia solar, separa els compostos elementals d'aigua com l'hidrogen i l'oxigen utilitzant un semiconductor amb propietats físiques adequades. La hematita (¿-Fe2O3) és un material prometedor per a aquesta aplicació a causa de la seva estabilitat química i capacitat d'absorbir una porció significativa de la llum (amb un gap entre 2,0 i 2,2 eV). Malgrat aquestes propietats avantatjoses, hi ha limitacions intrínseques per a l'ús d'òxid de ferro per a la descomposició fotoelectroquímica de l'aigua. La primera restricció és la posició de la seva banda de conducció que és inferior al potencial de reducció d'aigua. Aquesta limitació es pot superar mitjançant l'addició en sèrie d'un segon material, en tàndem, que absorbirà una part complementària de l'espectre solar i portar els electrons a un nivell d'energia més alt que el potencial per a l'alliberament d'hidrogen. El segon obstacle prové del desacord entre la curta durada de la difusió dels portadors de càrrega i la llarga profunditat de penetració de la llum. Per tant, és necessari controlar la morfologia dels elèctrodes d'hematita en una escala de mida similar a la longitud del forat del transport. En aquesta tesi, es presenta un nou concepte per millorar el rendiment fotoelectroquímic. Mitjançant el mètode hidrotermal es van dipositar capes primes de hematita Cr-doped sobre substrats de vidre conductor. També s'han preparat electroquímicamentheterounions de tipus p-CuSCN/n-Fe2O3 dipositant seqüencialment una capa de ¿-Fe2O3 i altra de CuSCN sobre substrats FTO (SnO2: F).Finalment, s'han produït cél·lules solars de perovskitesi óxid de ferro. Per això es va depositaruna capa prima,densai uniforme d'òxid de ferro (¿-Fe2O3) com a capa de transport d'electrons (ETL) en lloc de diòxid de titani (TiO2) que s'utilitza convencionalment en les cèl·lules fotovoltaiques de perovskita híbrida del tipus CH3NH3PbI3 (SGP). Aquest últim dispositiu va mostrar un augment del fotocorrent del 20% i una IPCE30 vegades superior a la hematita simple, la qual cosa suggereix una millor conversió a longitud d'ones per sobre de 500 nm. Paraules clau:Fotoelectroquímica, divisió d'aigua, producció d'hidrogen, evolució d'oxigen, semiconductors d'òxids metàl·lics, hematita, òxid de ferro, nanoestructures. / Bouhjar, F. (2018). Preparation et performance d'une cellule photocatalytique à base d'hématite pour la génération d'hydrogène [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/106345 / TESIS

Technologies based on alternative and sustainable energy sources present a vital solution in the present and for the future. These technologies are strongly driven by the increased global energy demand and need to reduce environmental issues created by fossil fuel. Solar energy is an abundant, clean and free-access resource, but it requires harvesting and storage for a sustainable future. Direct conversion and storage of solar energy using heterogeneous photocatalysts have been identified as parts of a promising paradigm for generating green fuels from sunlight and water. This thesis focused on developing semiconductor absorbers in a visible light region for photocatalytic hydrogen production reaction. In addition, theoretical studies are combined with experimental results for a deep understanding of the intrinsic optoelectronic properties of the obtained materials. The study presents a novel family of oxysulfide BiAgOS, produced by applying a full substitution strategy of Cu by Ag in BiCuOS. I was interested to address how the total substitution of Cu by Ag in a BiCuOS system affects its crystal structure, optical and electronic properties using experimental characterizations and theoretical calculations. Single-phase bismuth silver oxysulfide BiAgOS was prepared via a hydrothermal method. Rietveld refinement of the powder confirmed that BiAgOS is an isostructural BiCuOS. The diffraction peak positions of BiAgOS, relative to those of BiCuOS, were shifted toward lower angles, indicating an increase in the cell parameters. BiCuOS and BiAgOS were found to have indirect bandgaps of 1.1 and 1.5 eV, respectively. The difference in the bandgap results from the difference in the valence band compositions. The hybrid level of the S and Ag orbitals in BiAgOS is located at a more positive potential than that of S and Cu, leading to a widened bandgap. Both materials possess high dielectric constants and low electron and hole effective masses, making them interesting for photoconversion applications. BiAgOS has a potential for photocatalytic hydrogen evolution reaction in the presence of sacrificial reagents; however, it is inactive toward water oxidation. BiCuOS and BiAgOS can be considered interesting starting compositions for the development of new semiconductors for PV or Z-scheme photocatalytic applications. The second study investigates the synthesis and characterization of NaBiS2, this contains Bi3+, which belongs to the p-block electronic configuration Bi3+ 6s26p0, and NaLaS2, which contains La3+ with electronic configuration 6s05d0. Solid-state reactions from oxide precursor starting materials were applied for synthesis the materials. The sulfurization process was conducted by pressurizing a saturated vapor of CS2. The obtained black material of NaBiS2 has an indirect transition with high absorption coefficients in the visible region of the spectrum and the absorption edge is determined at 1.21 eV. However, NaBiS2 did not show photocatalytic activity toward hydrogen production. NaLaS2 is characterized by an indirect transition with a bandgap in the UV region at 3.15 eV and can drive the photocatalytic hydrogen evolution reaction in Na2S/Na2SO3 solution. Utilizing the solid solution NaLa1-xBixS2 strategy, the absorption properties and band edge position for photocatalytic hydrogen evolution reaction were optimized. The results indicated that the bismuth content is critical parameter for maintaining the photocatalytic activity. The incorporation of low Bi content up to 6% in NaLaS2 leads to extending the photon absorption from the UV to the visible region and enhancing the photocatalytic activity of hydrogen production. In contrast, all the solid solutions that have Bi content of more than 12% present absorption edges close to that of pure NaBiS2, and they are inactive for photocatalytic hydrogen production. Combining the experimental measurements with density functional theory calculations, such behavior can be explained by the degree of overlapping of Bi and La states on the conduction band minimum (CBM). Finally, self-assembly of Bi2S3 nanorods were grown on FG or FTO substrates. Bi2S3 thin films were prepared by sulfurization of Bi metal layer using the hydrothermal method. The results show that Bi2S3 has absorption up to 1.3 eV and has a moderate absorption coefficient in the visible region. The ultraviolet photoelectron spectroscopy and photoelectron spectroscopy in air results showed that the conduction band minimum of Bi2S3 is located slightly above the hydrogen redox potential. However, Pt/Bi2S3 did not evolve a detectable amount of hydrogen, suggesting the presence of surface states that can hinder the hydrogen reduction reaction.

L'hydrogène a révélé un grand potentiel en tant que vecteur d'énergie du futur polyvalent et non polluant, offrant une densité d'énergie élevée et une conversion efficace en puissance utilisable. La fermentation noire est l'un des procédés de production biologique les plus prometteurs, mais doit encore surmonter des défis majeurs, notamment des taux de production d'hydrogène faibles (HPR) et des rendements en hydrogène (HY), avant que son application industrielle ne devienne économe en énergie et en coûts. Dans ce travail, nous avons cherché à optimiser la production d’hydrogène par fermentation noire de Thermotoga neapolitana. Les principaux objectifs étaient d'améliorer le HPR et de maintenir une HY élevée en utilisant différentes approches pour contrecarrer les limitations des processus et prévenir les inhibitions les plus pertinentes. En outre, un développement du procédé à flux continu privilégié par l'industrie a été prévu. Une augmentation de la concentration de biomasse initiale de 0,46 à 1,74 g CDW / L dans les essais biologiques en lots a entraîné une augmentation de plus de 2 fois de la HPR jusqu'à 654 (± 30) mL / L / h sans affecter négativement l'HY. Cependant, alors que la productivité volumétrique augmentait, le HPR spécifique (par unité de biomasse) était négativement corrélé avec le HPR et la concentration de biomasse. Par la suite, nous avons étudié la sursaturation en hydrogène de la phase liquide (H2aq) dans des essais biologiques par lots. À 100 tr / min d'agitation, H2aq est sursaturé jusqu'à 3 fois la concentration à l'équilibre. L'augmentation de la vitesse d'agitation diminuait l'accumulation de H2aq jusqu'à atteindre un équilibre entre l'hydrogène en phase gazeuse et liquide en agitation à 500 tr / min à de faibles concentrations cellulaires. Une augmentation de 200 à 600 tr / min a réduit progressivement l'H2aq de 21,9 (± 2,2) à 8,5 (± 0,1) mL / L et a presque doublé le HPR, révélant une corrélation directe entre les deux paramètres. De même, l’ajout de supports K1 et de recirculation de biogaz riche en H2 (GaR) a permis de contrecarrer l’accumulation de H2aq. En accélérant le processus en augmentant la concentration de biomasse dans les réacteurs jusqu'à 0,79 g CDW / L, le GaR s'est révélé plus efficace pour éliminer l'H2aq que l'agitation à 500 tr / min. L'application de GaR à 300 et 500 tr / min a augmenté le HPR d'environ 260% à 850 (± 71) mL H2 / h / L, par rapport à une agitation à 300 tr / min, atteignant une HY de 3,5 mol / mol de glucose. Nous avons démontré qu'un transfert de masse gaz-liquide insuffisant conduit à une accumulation de H2aq qui inhibe le rendement, mais plus encore le taux de fermentation à l'obscurité. Dans la phase finale de ce projet, nous avons réussi à maintenir la production d'hydrogène à débit continu. L'augmentation de la concentration en glucose de l'alimentation, de 11,1 à 41,6 mM, a entraîné une diminution de l'HY de 3,6 (± 0,1) à 1,4 (± 0,1) mol H2 / mol de glucose. L’HPR a augmenté simultanément jusqu’à environ 55 ml / L / h à 27,8 mM de glucose, tandis qu’une augmentation supplémentaire du glucose dans l’alimentation animale à 41,6 mM n’a pas augmenté les concentrations en HPR et en AA. Pour rechercher si des taux élevés d'AA limitaient le processus, la concentration en AA de l'alimentation a été progressivement augmentée. Cependant, cela n'a révélé aucun effet négatif sur la fermentation à l'obscurité en continu jusqu'à 240 mM de nourriture AA et, tout au long des 110 jours de fermentation en continu, l'HY a augmenté de 47%. La réduction du THS de 24 à 7 h a également entraîné une augmentation du taux de HPR de 82 (± 1) à 192 (± 4) mL / L / h, tout en diminuant le HY. De manière concomitante, le H2aq accumulé est directement corrélé au HPR atteignant 15,6 mL / L pour un THS de 7 h et à une agitation de 500 tr / min. L'application de GaR a efficacement neutralisé la sursaturation en H2aq et a permis d'obtenir le HPR le plus élevé de 277 mL / L à un THS de 5 h / Hydrogen has revealed a great potential as a versatile and non-polluting energy carrier of the future providing a high energy density and an efficiently conversion to usable power. Dark fermentation is one of the most promising biological production processes, but still has to overcome major challenges, most importantly low hydrogen production rates (HPRs) and hydrogen yields (HYs), before its industrial application becomes cost- and energy-efficient.In this work, we aimed to optimize the hydrogen production via dark fermentation by Thermotoga neapolitana. The main objectives were to enhance the HPR and maintaining a high HY using different approaches to counteract process limitations and prevent the most relevant inhibitions. Furthermore, a development of the industrially preferred continuous-flow process was projected. An increase of the initial biomass concentration from 0.46 to 1.74 g CDW/L in batch bioassays resulted in a more than 2-fold enhancement of the HPR up to 654 (±30) mL/L/h without negatively affecting the HY. However, while the volumetric productivity increased the specific HPR (per unit of biomass) was negatively correlated with the HPR and the biomass concentration. Subsequently, we investigated the supersaturation of hydrogen in the liquid phase (H2aq) in batch bioassays. At 100 rpm agitation H2aq supersaturated up to 3 times the equilibrium concentration. Increasing the agitation speed diminished the accumulation of H2aq until an equilibrium between the gas and liquid phase hydrogen was reached with 500 rpm agitation at low cell concentrations. A raise from 200 to 600 rpm gradually reduced H2aq from 21.9 (± 2.2) to 8.5 (± 0.1) mL/L and approximately doubled the HPR, revealing a direct correlation between the two parameters. Similarly, the addition of K1 carrier and H2-rich biogas recirculation (GaR) successfully counteracted the accumulation of H2aq. Accelerating the process by increasing the reactors biomass concentration up to 0.79 g CDW/L, GaR revealed to be more efficient in removing H2aq than 500 rpm agitation. The application of GaR at 300 and 500 rpm enhanced the HPR by approximately 260% up to 850 (± 71) mL H2/h/L, compared to a sole 300 rpm agitation, reaching a HY of 3.5 mol/mol glucose. We demonstrated that an insufficient gas-liquid mass transfer leads to the accumulation of H2aq which inhibits the yield but even more so the rate of dark fermentation. In the final phase of this project we successfully maintained continuous-flow hydrogen production. Increasing the feed glucose concentration from 11.1 to 41.6 mM diminished the HY from 3.6 (± 0.1) to 1.4 (± 0.1) mol H2/mol glucose. The HPR increased concomitantly up to approximately 55 mL/L/h at 27.8 mM of glucose, whereas a further increase of feed glucose to 41.6 mM did not enhance the HPR and the AA concentration. To investigate whether high levels of AA limited the process, the feed AA concentration was gradually increased. However, this revealed no negative effect on continuous dark fermentation up to 240 mM of feed AA and, throughout the 110 days of continuous fermentation, the HY increased by 47%. Decreasing the HRT from 24 to 7 h also led to a HPR enhancement from 82 (± 1) to 192 (± 4) mL/L/h, while decreasing the HY. Concomitantly, the H2aq accumulated, directly correlated to the HPR reaching 15.6 mL/L at an HRT of 7 h and 500 rpm agitation. The application of GaR efficiently counteracted the supersaturation of H2aq and allowed the highest HPR of 277 mL/L at a HRT of 5 h

Awareness of the climate situation and greenhouse gas emissions from fossil fuels has focused attention on hydrogen as a renewable and sustainable energy resource. In this work an economic analysis of hydrogen production by a photovoltaic electrolysis system was conducted. Equations and solution methods from previous works [1, 2] have been used to compile the results. In order to run the electrolysis of water, electricity from the photovoltaic system was used. The photovoltaic electrolysis system for this analysis has been sized with data from previous works [3, 4] to satisfy the hydrogen consumption for a fuel cell bus. Annual savings, payback time and production costs of hydrogen and electricity were compared to analyses conducted by Paolo Laranci [1] and Lucia Bollini Braga [2]. CO2 emissions from steam reforming of natural gas and sugar cane bagasse ethanol have been calculated. In addition ethics for using natural gas and sugar cane bagasse for fuel production was studied to determine the advantages and disadvantages for respective hydrogen production processes. The estimated production cost for photovoltaic electricity calculated in this thesis was higher than the result achieved in Larancis [1] work. In addition the production cost was higher than for electricity from hydropower and photovoltaic-systems in Latin America [2] and also than for the electricity tariff in Brazil [1]. Payback time and annual savings calculated in this thesis was found to be higher than for Larancis photovoltaic system. To reduce the production cost solar cells with higher efficiency should be used, investments costs for the system reduced and governmental subsidies raised. The estimated production cost for photovoltaic electrolysis hydrogen calculated in this thesis was higher compared to Lucia Bollini Braga's. The production cost for hydrogen by steam reforming of natural gas and sugar cane bagasse ethanol was also an economically favorable alternative. For hydrogen produced by photovoltaic electrolysis to be an economically advantageous alternative the electrolysis operating hours should increase likewise the electrolyser efficiency. In addition the investment cost for the electrolyser should decrease. By using photovoltaic electrolysis to produce hydrogen fossil CO2-emissions are eliminated and abundant solar energy can be utilized. Brazil is a country that possesses great natural resources of sugar cane bagasse. Steam reforming of ethanol from sugar cane bagasse could be a future option for producing sustainable, economically favorable and ethically acceptable hydrogen in Brazil. / Medvetenheten om klimatsituationen och utsläppen av växthusgaser från fossila bränslen har riktat uppmärksamheten mot vätgas som är en förnybar och hållbar energiresurs. I detta arbete har en ekonomisk analys för produktion av vätgas genom fotovoltaisk elektrolys av vatten genomförts. Ekvationer och lösningsmetoder från tidigare arbeten [1, 2] har använts för att sammanställa resultat. För att driva elektrolysen av vatten används elektricitet från det fotovoltaiska systemet. Systemet för denna analys har dimensionerats med hjälp av data från tidigare arbeten [3, 4] för att satisfiera konsumtionen av vätgas för en bränslecellsbuss. Årliga besparingar, payback och produktionskostnader för vätgas och elektricitet har jämförts med analyser utförda av Paolo Laranci [1] och Lucia Bollini Braga [2]. Koldioxidutsläpp för ångreformering av naturgas och etanol från sockerrörs bagass har beräknats. Utöver detta har en etikstudie för användning av naturgas och etanol (ur sockerrörs bagass) vid bränsleproduktion gjorts för att avgöra fördelar och nackdelar med respektive system för vätgasproduktion. Den i detta arbete beräknade produktionskostnaden för elektricitet från det fotovoltaiska systemet var högre än resultatet som åstadkoms i Larancis [1] arbete. Vidare var den i detta arbete beräknade produktionskostnaden högre än för elektricitet från vattenkraft och fotovoltaisk energi i Latinamerika [2] samt elpriset i Brasilien[1]. Payback-tiden och de årliga besparingarna visade sig vara högre för det fotovoltaiska systemet beräknat i denna analys än för Larancis system. För att minska produktionskostnaderna bör solceller med högre verkningsgrad användas, investeringskostnader av fotovoltaiska system minskas och statliga subventioner för installationen ökas. Den i detta arbete beräknade produktionskostnaden för vätgas genom fotovoltaisk elektrolys var högre jämfört med Lucia Bollini Bragas system. Produktionskostnaden för vätgas genom ångreformering av naturgas och etanol (ur sockerrörs bagass) var likaså ett mer ekonomiskt gynnsamt alternativ än fotovoltaisk elektrolys. För att vätgas producerat genom fotovoltaiskt elektrolys ska vara ekonomiskt fördelaktigt bör elektrolysens drifttimmar ökas, elektrolysen verkningsgrad öka och investeringskostnader för elektrolysen minska. Genom att använda fotovoltaisk elektrolys för att framställa vätgas elimineras fossila CO2-utsläpp och solenergi som finns i stort överskott kan utnyttjas. Brasilien är ett land som besitter stora naturresurser i form av sockerrör. Ångreformering av etanol från sockerrörs bagass kan vara ett framtida alternativ för att framställa hållbar, ekonomiskt gynnsam och etiskt accepterad vätgas i Brasilien.

Current global demands for energy resources along with continuous global population growth have placed natural environments and societies under great stress to fulfill such a need without disrupting economic and social structures. Policy and decision-making processes hold some of the most important keys to allow safe paths for societies towards energy security and safeguard of the environment. Brazil has played a lead role within renewable energy production and use during the last decades, becoming one of the world’s leading producer of sugarcane based ethanol and adapting policies to support renewable energy generation and use. Although it is true that Brazil has historic experience with managing development of renewables and its further integration into the consumer market, there is still a lot to do to impulse new technologies that could further reduce emissions, increase economic stability and social welfare. Throughout this thesis project a sustainability assessment of hydrogen production technologies in Brazil is conducted through Multi-Criteria Analysis. After defining an initial framework for decision-making, options for hydrogen production were reviewed and selected. Options were evaluated and weighted against selected sustainability indicators that fitted the established framework within a weighting matrix. An overall score was obtained after the assessment, which ranked hydrogen production techniques based on renewable energy sources in first place. Final scoring of options was analyzed and concluded that several approaches could be taken in interpreting results and their further integration into policy making. Concluding that selection of the right approach is dependent on the time scale targeted for implementation amongst other multi-disciplinary factors, the use of MCA as an evaluation tool along with overarching sustainability indicators can aid in narrowing uncertainties and providing a clear understanding of the variables surrounding the problem at hand.