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Tesis por compendio / 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]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/106345 / Compendio

The production of hydrogen fuel via solar water splitting is an important carbon-neutral strategy for the development of renewable resources and has sparked great interest in the scientific community. Hydrogen production efficiencies for supramolecular photocatalysts of the architecture [{(TL)2Ru(BL)}2RhX2]5+ (BL=bridging ligand, TL=terminal ligand, X=halide) are among the highest reported in deoxygenated organic solvents, but do not function in air-saturated aqueous solution due to quenching of the metal-to-ligand charge transfer (MLCT) excited-state under these conditions. Herein, we report the groundbreaking use of polyelectrolytes to increase efficiency of supramolecular photocatalysts in solar hydrogen production schemes under aqueous aerobic conditions. The new photocatalytic system incorporates poly(4-styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)2Ru(dpp)}2RhCl2]5+ (bpy = 2,2'-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine). PSS has a profound impact on photocatalyst efficiency, increasing hydrogen production over three times that of deoxygenated aqueous solutions alone. Hydrogen photocatalysis proceeds even under aerobic conditions for PSS containing solutions, an exciting consequence for solar hydrogen production research. Thermodynamics of binding due to intermolecular interactions between Ru,Rh,Ru photocatalysts and polyelectrolytes was probed using isothermal titration calorimetry (ITC). ITC studies reveal the driving forces of aggregate formation, providing new insight into the intermolecular forces that lead to increased photocatalytic efficiency and stability in the presence of water soluble polymers. Synthesis and characterization of a novel supramolecular photocatalyst having hydrophilic terminal ligands are reported. Addition of sulfonated terminal ligands into a Ru,Rh,Ru photocatalyst has a significant impact on the excited-state properties of the complex. The new complex demonstrates increased solubility and hydrogen production efficiency in aqueous solutions. Hydrogen production is observed even under aerobic conditions for the new complex, a stark contrast to the hydrophobic analog in organic solvents. The synthesis, characterization, and electropolymerization of a chromophore-catalyst assembly having vinyl-substituted terminal ligands to create robust water reduction photocatalysts on wide-bandgap semiconductors is reported. The polymeric photocatalysts are expected to show increased stability over a wide pH range and increased photostability compared to chromophore-catalyst assemblies that employ carboxylic or phosphonic acid groups to adsorb the photoreactive catalyst to the metal oxide surface. / Ph. D. / The production of H₂ fuel from water using sunlight is an important carbon-neutral strategy for the development of renewable resources and has sparked great interest in the scientific community. H₂ production efficiencies for light-activated catalysts of the architecture [{(TL)₂Ru(BL)}₂RhX₂]⁵⁺ (BL=bridging ligand, TL=terminal ligand, X=halide) are among the highest reported in deoxygenated organic solvents, but do not function in air-saturated aqueous solution due to deactivation of the catalyst under these conditions. Herein, we report the groundbreaking use of water soluble polymers to increase efficiency of light activated catalysts in solar H₂ production schemes in air-saturated water. The new photocatalytic system incorporates poly(4-styrenesulfonate) (PSS) into aqueous solutions containing [{(bpy)₂Ru(dpp)}₂RhCl₂]⁵⁺ (bpy = 2,2'-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine). PSS has a profound impact on the efficiency of the light activated catalyst, increasing H₂ production over three times that of deoxygenated aqueous solutions alone. H₂ production proceeds even in air-saturated water for PSS containing solutions, an exciting consequence for solar hydrogen production research. Interactions between Ru,Rh,Ru light activated catalysts and polyelectrolytes were probed using isothermal titration calorimetry (ITC). ITC studies reveal the driving forces of aggregate formation, providing new insight into the intermolecular forces that lead to increased efficiency and stability in the presence of water soluble polymers. Synthesis and characterization of a novel light activated catalyst having hydrophilic terminal ligands are reported. Addition of water soluble terminal ligands into a Ru,Rh,Ru light-activated catalyst has a significant impact on the excited-state properties of the molecule in aqueous solution. The new molecule demonstrates increased solubility and H₂ production efficiency in aqueous solutions. H₂ production is observed even under aerobic conditions for the new molecule, a stark contrast to the hydrophobic analog in organic solvents. The synthesis, characterization, and polymerization of a new light activated catalyst on a metal oxide surface is reported. The polymeric light-activated catalysts are expected to show increased stability over a wide pH range and increased stability compared to light-activated catalysts that employ carboxylic or phosphonic acid groups to adsorb the catalyst to the metal oxide surface.

<p>The main conclusion of this dissertation is that global H2 production within young ocean crust (<10 Mya) is higher than currently recognized, in part because current estimates of H2 production accompanying the serpentinization of peridotite may be too low (Chapter 2) and in part because a number of abiogenic H2-producing processes have heretofore gone unquantified (Chapter 3). The importance of free H2 to a range of geochemical processes makes the quantitative understanding of H2 production advanced in this dissertation pertinent to an array of open research questions across the geosciences (e.g. the origin and evolution of life and the oxidation of the Earth’s atmosphere and oceans).</p><p>The first component of this dissertation (Chapter 2) examines H2 produced within young ocean crust [e.g. near the mid-ocean ridge (MOR)] by serpentinization. In the presence of water, olivine-rich rocks (peridotites) undergo serpentinization (hydration) at temperatures of up to ~500°C but only produce H2 at temperatures up to ~350°C. A simple analytical model is presented that mechanistically ties the process to seafloor spreading and explicitly accounts for the importance of temperature in H2 formation. The model suggests that H2 production increases with the rate of seafloor spreading and the net thickness of serpentinized peridotite (S-P) in a column of lithosphere. The model is applied globally to the MOR using conservative estimates for the net thickness of lithospheric S-P, our least certain model input. Despite the large uncertainties surrounding the amount of serpentinized peridotite within oceanic crust, conservative model parameters suggest a magnitude of H2 production (~1012 moles H2/y) that is larger than the most widely cited previous estimates (~1011 although previous estimates range from 1010-1012 moles H2/y). Certain model relationships are also consistent with what has been established through field studies, for example that the highest H2 fluxes (moles H2/km2 seafloor) are produced near slower-spreading ridges (<20 mm/y). Other modeled relationships are new and represent testable predictions. Principal among these is that about half of the H2 produced globally is produced off-axis beneath faster-spreading seafloor (>20 mm/y), a region where only one measurement of H2 has been made thus far and is ripe for future investigation.</p><p>In the second part of this dissertation (Chapter 3), I construct the first budget for free H2 in young ocean crust that quantifies and compares all currently recognized H2 sources and H2 sinks. First global estimates of budget components are proposed in instances where previous estimate(s) could not be located provided that the literature on that specific budget component was not too sparse to do so. Results suggest that the nine known H2 sources, listed in order of quantitative importance, are: Crystallization (6x1012 moles H2/y or 61% of total H2 production), serpentinization (2x1012 moles H2/y or 21%), magmatic degassing (7x1011 moles H2/y or 7%), lava-seawater interaction (5x1011 moles H2/y or 5%), low-temperature alteration of basalt (5x1011 moles H2/y or 5%), high-temperature alteration of basalt (3x1010 moles H2/y or <1%), catalysis (3x108 moles H2/y or <<1%), radiolysis (2x108 moles H2/y or <<1%), and pyrite formation (3x106 moles H2/y or <<1%). Next we consider two well-known H2 sinks, H2 lost to the ocean and H2 occluded within rock minerals, and our analysis suggests that both are of similar size (both are 6x1011 moles H2/y). Budgeting results suggest a large difference between H2 sources (total production = 1x1013 moles H2/y) and H2 sinks (total losses = 1x1011 moles H2/y). Assuming this large difference represents H2 consumed by microbes (total consumption = 9x1011 moles H2/y), we explore rates of primary production by the chemosynthetic, sub-seafloor biosphere. Although the numbers presented require further examination and future modifications, the analysis suggests that the sub-seafloor H2 budget is similar to the sub-seafloor CH4 budget in the sense that globally significant quantities of both of these reduced gases are produced beneath the seafloor but never escape the seafloor due to microbial consumption.</p><p>The third and final component of this dissertation (Chapter 4) explores the self-organization of barchan sand dune fields. In nature, barchan dunes typically exist as members of larger dune fields that display striking, enigmatic structures that cannot be readily explained by examining the dynamics at the scale of single dunes, or by appealing to patterns in external forcing. To explore the possibility that observed structures emerge spontaneously as a collective result of many dunes interacting with each other, we built a numerical model that treats barchans as discrete entities that interact with one another according to simplified rules derived from theoretical and numerical work, and from field observations: Dunes exchange sand through the fluxes that leak from the downwind side of each dune and are captured on their upstream sides; when dunes become sufficiently large, small dunes are born on their downwind sides (“calving”); and when dunes collide directly enough, they merge. Results show that these relatively simple interactions provide potential explanations for a range of field-scale phenomena including isolated patches of dunes and heterogeneous arrangements of similarly sized dunes in denser fields. The results also suggest that (1) dune field characteristics depend on the sand flux fed into the upwind boundary, although (2) moving downwind, the system approaches a common attracting state in which the memory of the upwind conditions vanishes. This work supports the hypothesis that calving exerts a first order control on field-scale phenomena; it prevents individual dunes from growing without bound, as single-dune analyses suggest, and allows the formation of roughly realistic, persistent dune field patterns.</p> / Dissertation

Thermochemical water splitting cycles have been conceptualized and researched for over half a century, yet to this day none are commercially viable. The heavily studied Sulfur-Iodine cycle has been stalled in the early development stage due to a difficult HI-H₂O separation step and material compatibility issues. In an effort to avoid the azeotropic HI-H₂O mixture, an imidazolium-based ionic liquid was used as a reaction medium instead of water. Ionic liquids were selected based on their high solubility for SO₂, I₂, and tunable miscibility with water. The initial low temperature step of the Sulfur-Iodine cycle was successfully carried out in ionic liquid reaction medium. Kinetics of the reaction were investigated by I₂ colorimetry. The reaction also evolved H₂S gas, which led to the conceptual idea of a new Sulfur-Sulfur thermochemical cycle, shown below: / 4I₂(l)+4SO₂(l)+8H₂O(l)↔4H₂SO₄(l)+ 8HI(l) / 8HI(l)+H₂SO₄(l)↔ H₂S(g)+4H₂O(l)+4I₂(l) / 3H₂SO₄(g)↔ 3H₂O(g)+3SO₂(g)+1½O₂(g) / H₂S(g)+2H₂O(g)↔ SO₂(g)+3H₂(g) / The critical step in the Sulfur-Sulfur cycle is the steam reformation of H₂S. This highly endothermic step is shown to successfully occur at temperatures in excess of 800˚C in the presence of a molybdenum catalyst. A parametric study varying the H₂O:H₂S ratio, temperature, and residence time in a simple tubular quartz reactor was carried out and Arrhenius parameters were estimated. All reactive steps of the Sulfur-Sulfur cycle have been either demonstrated previously or demonstrated in this work. A theoretical heat-to-hydrogen thermal efficiency is estimated to be 55% at a hot temperature of 1100 K and 59% at 2000 K. As a highly efficient, all-fluid based thermochemical cycle, the Sulfur-Sulfur cycle has great potential for feasible process implementation for the transformation of high quality heat to chemical energy. / Graduation date: 2012

L’azote est l’élément le plus abondant dans l’atmosphère terrestre avec un pourcentage atteignant 78 %. Composant essentiel pour la biosynthèse des matériels organiques cellulaires, il est inutilisable sous sa forme diatomique (N2) très stable par la plupart des organismes. Seules les bactéries dites diazotrophiques comme Rhodobacter capsulatus sont capables de fixer l’azote moléculaire N2 par le biais de la synthèse d’une enzyme, la nitrogénase. Cette dernière catalyse la réduction du N2 en ammonium (NH4) qui peut alors être assimilé par d’autres organismes. La synthèse et l’activité de la nitrogénase consomment beaucoup d’énergie ce qui implique une régulation rigoureuse et son inhibition tant qu’une quantité suffisante d’ammonium est disponible. Parmi les protéines impliquées dans cette régulation, la protéine d’intérêt AmtB est un transporteur membranaire responsable de la perception et le transport de l’ammonium. Chez R. capsulatus, il a été démontré que suite à l’addition de l’ammonium, l’AmtB inhibe de façon réversible (switch off/switch on) l’activité de la nitrogénase en séquestrant la protéine PII GlnK accompagnée de l’ajout d’un groupement ADP ribose sur la sous unités Fe de l’enzyme par DraT. De plus, la formation de ce complexe à lui seul ne serait pas suffisant pour cette inactivation, ce qui suggère la séquestration d’une troisième protéine, DraG, afin d’inhiber son action qui consiste à enlever l’ADP ribose de la nitrogénase et donc sa réactivation. Afin de mieux comprendre le fonctionnement de l’AmtB dans la régulation et le transport de l’ammonium à un niveau moléculaire et par la même occasion la fixation de l’azote, le premier volet de ce mémoire a été d’introduire une mutation ponctuelle par mutagénèse dirigée au niveau du résidu conservé W237 de l’AmtB. La production d’hydrogène est un autre aspect longtemps étudié chez R. capsulatus. Cette bactérie est capable de produire de l’hydrogène à partir de composés organiques par photofermentation suite à l’intervention exclusive de la nitrogénase. Plusieurs études ont été entreprises afin d’améliorer la production d’hydrogène. Certaines d’entre elles se sont intéressées à déterminer les conditions optimales qui confèrent une production maximale de gaz tandis que d’autres s’intéressent au fonctionnement de la bactérie elle même. Ainsi, le fait que la bioproduction de H2 par fermentation soit catalysée par la nitrogénase cela implique la régulation de l’activité de cette dernière par différents mécanismes dont le switch off par ADP ribosylation de l’enzyme. De ce fait, un mutant de R. capsulatus dépourvu d’AmtB (DG9) a été étudié dans la deuxième partie de cette thèse en termes d’activité de la nitrogénase, de sa modification par ADP ribosylation avec la détection des deux protéines GlnK et DraG qui interviennent dans cette régulation pour connaitre l’influence de différents acides aminés sur la régulation de la nitrogénase et pour l‘utilisation future de cette souche dans la production d’H2 car R. capsulatus produit de l’hydrogène par photofermentation grâce à cette enzyme. Les résultats obtenus ont révélé une activité de la nitrogénase continue et ininterrompue lorsque l’AmtB est absent avec une activité maximale quand la proline est utilisée comme source d’azote durant la culture bactérienne ce qui implique donc que l’abolition de l’activité de cette protéine entraine une production continue d’H2 chez R. capsulatus lorsque la proline est utilisée comme source d’azote lors de la culture bactérienne. Par ailleurs, avec des Western blots on a pu déterminer l’absence de régulation par ADP ribosylation ainsi que les expressions respectives de GlnK et DraG inchangées entre R. capsulatus sauvage et muté. En conclusion, la nitrogénase n’est pas modifiée et inhibée lorsque l’amtB est muté ce qui fait de la souche R. capsulatus DG9 un candidat idéal pour la production de biohydrogène en particulier lorsque du glucose et de la proline sont respectivement utilisés comme source de carbone et d'azote pour la croissance. / Nitrogen is the most abundant element in the Earth's atmosphere with a percentage of 78 %. This element is essential for the biosynthesis of cellular organic material and is unusable in its stable diatomic form (N2) by most organisms. Only bacteria called diazotrophs such as Rhodobacter capsulatus are able to fix molecular nitrogen N2 through the synthesis of the nitrogenase enzyme. The latter catalyzes the reduction of N2 to NH4 which can then be absorbed by other organisms. The synthesis and activity of nitrogenase consumes a lot of energy and therefore implies a strict regulation and its inhibition when a sufficient amount of ammonium is available. Among the proteins involved in this regulation, is the membrane transporter AmtB which is responsible for the sensing and transportation of ammonia. In R. capsulatus, it was shown that following the addition of ammonium, AmtB reversibly inhibits (switch off / switch on) nitrogenase activity by sequestering the PII protein GlnK accompanied by the addition of an ADP ribose group onto the Fe subunit of the enzyme by DraT. In addition, the formation of this complex alone would not be sufficient for this inactivation, suggesting the sequestration of a third protein, DraG is required to inhibit its action of removing the ADP ribose from the nitrogenase and therefore its reactivation. To better understand the role of the AmtB in the fixation of nitrogen, regulation and transport of ammonium at the molecular level, the first part of this study was to introduce a point mutation by directed mutagenesis in the conserved residue W237 of AmtB . Hydrogen production is another property of R. capsulatus that has been studied for a long time. This bacterium is capable of producing hydrogen from organic compounds following photofermentation and the exclusive enzymatic intervention of nitrogenase. Several studies have been undertaken to improve the production of hydrogen. Some of them were involved in determining the optimum conditions that give maximum gas production while others were interested in improving the growth of the bacterium itself. Thus, since the bio-production of H2 by fermentation is catalyzed by the nitrogenase, it is important to study the regulation of the activity of this enzyme by different mechanisms such as the switch off by ADP ribosylation. Therefore, a mutant of R. capsulatus (DG9) lacking AmtB was studied in the second part of this thesis for its nitrogenase activity, its modification by GlnK-DraG, and to see the effects of different amino acids used in the growth medium on the regulation and therefore the future use of this strain for the production of H2. The results showed a continuous and uninterrupted activity of the nitrogenase when AmtB was absent with a maximum activity when proline was used as a nitrogen source for bacterial growth. In addition, Western blots were used to demonstrate the effect of ADP ribosylation on regulation and that the expression of GlnK and DraG were unchanged between the wild –type and mutant R. capsulatus. In conclusion, nitrogenase is not modified or inhibited when mutated amtB what makes the R. capsulatus strain DG9 an ideal candidate for biohydrogen production especially when glucose and proline are respectively used as source carbon and nitrogen for growth.