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<p>Electropolishing is a commonly used method of mitigating surface roughness and yielding a polished appearance. One of the first described and most studied of electropolishing systems is the anodization of copper in phosphoric acid. Under normal conditions this reduces copper surface roughness substantially; however deviating from optimal electropolishing conditions can promote the development of semi-ordered surface roughness. Anodizing copper substrates in 98-100% H₃PO₄ solutions generated feature heights ranging from 0.5 - 2µm and surface area increases in excess of 30% were obtained. The samples demonstrated a macroscopic optical dullness characteristic of this type of surface roughening. Investigations as to their applicability in surface enhanced Raman spectroscopy and electron field emission were conducted. And while their formation mechanism is still speculated on, it is believed that oxygen evolution and subsequent bubble formation plays a key role. Electrochemical and microscopic imaging techniques were the primary methodologies used to probe the optical dulling phenomenon. With data obtained from experiments utilizing these techniques and others a qualitative mechanism is proposed.</p> / Master of Science (MSc)

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

京都大学 / 新制・課程博士 / 博士(工学) / 甲第25300号 / 工博第5259号 / 新制||工||2001(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 准教授 松井 敏明 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DGAM

Orientador: Antonio Manoel Mansanares / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin / Made available in DSpace on 2018-09-26T13:53:30Z (GMT). No. of bitstreams: 1 Mesquita_RicksonCoelho_M.pdf: 13672557 bytes, checksum: bbf3df05cb82c513d1c69aa2b28b84da (MD5) Previous issue date: 2005 / Resumo: O nível de iluminação das plantas é determinante da estrutura das folhas, em particular no tocante à quantidade e distribuição dos cloroplastos. O objetivo deste projeto é utilizar a técnica fotoacústica para demonstrar as diferenças fisiológicas entre plantas adaptadas a diferentes condições de irradiância. Plantas de tabaco foram cultivadas em dois níveis distintos de irradiância. Plantas congenéricas, provenientes de habitats diferentes (cerrado e mata atlântica), crescidas sob o mesmo nível de exposição à luz, também foram estudadas. Como a técnica fotoacústica é sensível ao O2 produzido na fotossíntese, a resposta dos sistemas fotossintéticos das plantas de diferentes condições foi avaliada por meio de medidas fotoacústicas de indução fotossintética. A quantidade de energia armazenada também foi determinada nessas plantas. A partir da contribuição da evolução de O2 para o sinal fotoacústico, obtivemos espectros de ação para as diferentes amostras. Os resultados mostraram que plantas adaptadas a ambientes de sol são menos eficientes em armazenar energia para as reações fotoquímicas. As curvas de indução indicaram que essas plantas demoram um tempo maior para atingir um estado estacionário de produção de O2. Experimentos de fotoinibição mostraram que plantas adaptadas a baixas irradiâncias são mais sensíveis ao excesso de luz saturante. Foi observada uma absorção de O2 após a saturação fotossintética em plantas de tabaco de sol, associada a uma provável competição entre fotossíntese e fotorrespiração. Os espectros de ação, obtidos pela primeira vez a partir de medidas fotoacústicas de produção de O2, mostraram uma boa concordância com a literatura (valores obtidos por outras técnicas) / Abstract: Ilumination level of plants during its growth is determinant for structure of leaves, specially refering to quantity and distribution of chloroplasts. The aim of this project is to use the photoacoustic technique to show physiological differences among plants adapted to different light intensity conditions. Tobacco plants were grown up under two distint irradiance levels. Congeneric plants, coming from different habitats (cerrado and florest), grown up under the same light level, were also studied. Since photoacoustic technique is sensitive to O2 produced by photosynthesis, photosynthetic response of plants from different light conditions were studied through PA measurements of photosynthetic induction. The energy storage was also determined in these plants. From the oxygen component of the photoacoustic signal it was possible to obtain action spectra for all the samples. Results showed that plants adapted to sunlight present lower efficiency in storing energy to photochemical reactions. The induction curves indicated these plants also take a longer time to reach a steady state of O2 production, after remaining a period in the dark. Photoinhibition experiments showed that plants grown up under lower light are more susceptible to excess of saturating light. It was also observed O2 uptake after photoinhibition in plants grown under full sunlight, which was associated to a competition between photosynthesis and photorespiration. The action spectra, obtained for the first time with photoacoustic measurements of O2 production, showed a good agreement with literature / Mestrado / Física da Matéria Condensada / Mestre em Física

<p>The Arbuscular mycorrhiza (AM) is an endosymbiont of higher plant roots. Most land plants and cultivated crops are concerned to AM symbiosis. This endosymbiosis is based on the mutual exchange of nutrients between plant and fungus. Therefore, AM symbiosis leads to an increased demand for photosynthetic products. The aim of this study was to investigate the pathway used by plants during AM symbiosis to increase photosynthetic performance. Therefore, we have carried out a systematic characterization of photosynthesis in Medicago truncatula (M. truncatula), which is a model legume. We observed colonization by the fungus in roots and that AM symbiosis increases the fresh and dry plant biomass. This could be attributed to an increase in both photosynthetic efficiency and capacity in AM plants. Consistent with these observations, AM symbiosis enhanced phosphorus uptake from the soil into roots, stems and leaves, as based on analyses of phosphorus content. Based on equal chl loading, no differences were found regarding D1, Lhcb1 and Lhcb2 protein content in four plant groups. This indicates similar ratio between chl and PSII proteins. Furthermore, AM symbiosis increases the amount of chlorophyll, steady state oxygen evolution activities, maximum quantum yield (Fv/Fm), and photosynthetic electron transport rate (about 5 fold). Nevertheless, photoprotection was not affected by AM symbiosis. We observed an increase in weight of seed/fruit and weight of seed/plant in AM plants (about 2 fold). Based on these results, we propose that AM symbiosis increases both the efficiency and the capacity of photosynthetic apparatus in the M. truncatula.</p>

The chlorate process is very energy intensive and a major part of the production costs are for electrical energy. Since the electricity prices are constantly increasing and may also vary periodically, the chlorate plants may be forced to adjust their production rate to the price at each moment in order to minimise their costs. Variation of current load requires increased knowledge regarding the electrode behaviour in a wide current range. In this thesis, the aim was to study the impact of the electrolyte on the electrode reactions in order to reduce the energy consumption. The work has mainly been experimental and additionally mathematical modelling has been carried out. A wide current range has been investigated in order to increase the understanding of the phenomena and to obtain results useful for low-load operation during the periods of high electricity cost. To operate the anode as energy efficiently as possible, the anode potential should not exceed the critical potential (Ecr), where the slope of the anodic polarisation curve increases, most likely due to ruthenium(VIII)-formation, and where the side reaction of oxygen evolution increases. In this work, the influence of different electrolyte parameters on Ecr has been studied. It was shown that a higher chloride concentration and an increased temperature lowered Ecr, which was expected to increase the risk of exceeding Ecr. However, this was not observed due to a simultaneous favouring of the chloride oxidation. Hence it was concluded that the electrolyte parameters should be optimised so that the lowest possible anode potential is obtained, which would enable higher current densities without exceeding Ecr. A further conclusion is that the increased slope of the polarisation curve at Ecr was possibly related to the lower activity for chloride oxidation on ruthenium oxidised to ruthenium(VIII). At full-load operation, the cathode potential was shown to be rather independent of the electrolyte composition despite a large variation of electrolyte parameters. The cathode composition appears to be more critical than the electrolyte composition when aiming at reducing the energy consumption. A strategy to increase the cathode activity could be to in situ apply a catalytic film onto the electrode surface. Therefore, Y(III) was added to a chloride electrolyte in order to form a yttrium hydroxide film on the alkaline cathode surface during hydrogen evolution. The yttrium-hydroxide film activated reduction of water (hydrogen evolution) and hindered hypochlorite reduction, proton reduction and nitrate reduction. The inhibiting properties are important for the prevention of side reactions, which currently are avoided by reducing Cr(VI) of the electrolyte on the cathode, producing an inhibiting chromium-hydroxide film. The studies on Y(III) increase the expectations for finding alternatives to the toxic Cr(VI). The addition of chromate to the chlorate electrolyte gives a high cathodic current efficiency and chromate has buffering properties in the electrolyte. The role of the buffer has been investigated for the oxygen evolution from water (one possible anodic side reaction), as well as cathodic hydrogen evolution. Models have been developed for these systems to increase the understanding of the interaction between buffer, electrode reactions and mass transport; the results have been verified experimentally. The chromate buffer increased the limiting current significantly for the cathodic H+ reduction and the cathodic overpotential was reduced drastically at currents lower than the limited current. A too low overpotential could result in the cathodic protection being lost. The presence of chromate buffer increased the limiting current for the oxygen evolution from OH-. The modelling of these systems revealed that the homogeneous reactions connected to the electrode reactions were not in equilibrium at the electrode surface. Further, a good resolution of the interface at the electrode surface was crucial since the, for the electrode reactions, important buffering takes place in an nm-thick reaction layer. / Framställning av klorat är mycket energiintensiv och kräver stora mängder elenergi. Stigande elpriser, som dessutom ofta varierar under dygnet eller säsongsvis, gör att man vill reducera onödiga förluster samt ibland försöka anpassa produktionen så att man när elpriset är högt minskar den, för att sedan öka produktionen igen då elpriset sjunker. Denna flexibla drift kräver ny kunskap om hur elektroderna beter sig i ett större strömintervall än vad som tidigare varit av intresse. Målet med detta arbete var att, med fokus på elektrolytens betydelse, identifiera möjliga förbättringar för kloratprocessen och därmed minska energiförbrukningen. Studierna har i huvudsak varit experimentella men även matematisk modellering har använts. Ett brett strömintervall har undersökts för att bättre förstå fenomenen och för att även kunna använda resultaten då höga elpriser gör att man vill köra processen vid lägre laster än normalt. För att driften av anoden ska vara så energieffektiv som möjligt bör anodpotentialen inte överskrida den kritiska potentialen (Ecr), där den anodiska polarisationskurvan får en högre lutning (troligtvis pga Ru(VIII)-bildning) och bireaktionen syrgasutveckling ökar. I detta arbete har påverkan av olika elektrolytparametrar på Ecr undersökts. Det visade sig att en ökad kloridkoncentration och ökad temperatur sänkte Ecr. Trots att detta borde göra att Ecr lättare överskrids, blev inte detta fallet eftersom kloridoxidationen samtidigt gynnades. Slutsatsen blir därför att elektrolytparametrarna bör optimeras så att lägsta möjliga anodpotential uppnås, vilket då även gör att strömtätheten kan ökas utan att Ecr överskrids. Slutsatsen är vidare att polarisationskurvans högre lutning vid Ecr kan ha att göra med att rutenium oxiderat till rutenium(VIII) har lägre aktivitet för kloridoxidation. Vid full last visade sig katodens potential vara relativt oberoende av elektrolytsammansättningen trots att denna varierades kraftigt. Katodens sammansättning verkar vara viktigare att ta hänsyn till än elektrolytens för kunna åstadkomma en större energibesparing. Ett alternativ till att öka katodens aktivitet skulle vara att in-situ belägga elektrodytan med en katalytisk film. Försök gjordes att sätta till Y(III) till kloridelektrolyt för att under vätgasutveckling fälla ut en yttriumhydroxidfilm på den alkaliska katodytan. Yttriumhydroxidfilmen aktiverade vattenreduktion (vätgasutveckling) och inhiberade hypokloritreduktion, protonreduktion och nitratreduktion. De inhiberande egenskaperna är viktiga för att förhindra bireaktioner, vilka idag hindras av att Cr(VI) i elektrolyten reduceras på katoden och bildar en hindrande kromhydroxidfilm. Försöken med Y(III) visar att det finns goda möjligheter att hitta alternativ till det miljöfarliga Cr(VI). Kromattillsatsen i kloratelektrolyt ger förutom ett högt katodiskt strömutbyte även en buffrande effekt till elektrolyten. Effekten av buffert har undersökts för en av de anodiska bireaktionerna, syrgasutveckling ur vatten, samt för vätgasutvecklingen på katoden. Dessa system har modellerats för att bättre förstå samspelet mellan buffert, elektrodreaktioner och materietransport och resultaten har verifierats experimentellt. Kromatbufferten ökade gränsströmmen för katodisk H+-reduktion betydligt och katodöverpotentialen sjönk kraftigt vid lägre strömmar än gränsströmmen. Detta kan vara ett problem om överpotentialen sjunker så lågt att elektroden inte är katodiskt skyddad. För syrgasutvecklingen ökade närvaron av kromatbuffert gränsströmmen för syrgasutveckling ur OH-. Modellering av dessa system visar att de homogena reaktioner som var kopplade till elektrodreaktionerna inte var i jämvikt vid elektrodytan. Vidare visade det sig vara mycket viktigt med en bra upplösning av gränsskiktet vid elektrodytan, då den buffring som är viktig för elektrodreaktionerna sker i ett mycket tunt reaktionsskikt (nanometertjockt). / <p>QC 20100901</p>

The oxygen that we breathe and food that we eat are products of the natural photosynthesis. Molecular oxygen is crucial for life on Earth owing to its role in the glycolysis and citric acid pathways that yield in aerobic organisms the energy-rich ATP molecules. Photosynthetic water oxidation, which produces molecular oxygen from water and sunlight, is performed by higher plants, algae and cyanobacteria. Within the molecular structure of a plant cell, photosynthesis is performed by a specific intracellular organelle – the chloroplast. Chloroplasts contain a membrane system, the thylakoid membrane, which comprises lipids, quinones and a very high content of protein complexes. The unique photosynthetic oxidation of water into molecular oxygen, protons and electrons is performed by the Mn4CaO5 cluster in photosystem II (PSII) complex. Understanding the mechanism of water oxidation by Mn4CaO5 cluster is one of the great challenges in science nowadays. When the mechanism of this process is fully understood, artificial photosynthetic systems can be designed that have high efficiencies of solar energy conversion by imitating the fundamental principle of natural system. These systems can be used in future for generation of fuels from sunlight.   In this thesis, the efficiency of water-splitting process in natural photosynthetic preparations was studied by measuring the flash-induced oxygen evolution pattern (FIOP). The overall aim is to achieve a deeper understanding of oxygen evolving mechanism of the Mn4O5Ca cluster via developing a complete kinetic and energetic model of the light-induced redox reactions within PSII complex. On the way to reach this goal, the hydrogen peroxide that is electrochemically generated on surface of Pt-cathode was discovered. The chemical effect of electrochemically produced H2O2 that can interfere in the oxygen evolution pathway or change the observed FIOP data was demonstrated. Therefore, in order to record the clean FIOP data that are further characterized by global fitting program (GFP), H2O2 has to be abolished by catalase addition and by purging the flow buffer of the Joliot-type electrode with nitrogen gas.      After FIOPs free of H2O2-induced effects were achieved, these clean data were then applied to a global fitting approach (GFP) in order to (i) result a comprehensive figure of all S-state decays whose kinetic rates were simultaneously analyzed in a high reliability and consistency, (ii) the dependence of miss parameter on S-state transitions and the oxidation state of tyrosine D (YD) can be tested, (iii) how dependent of all S-state re-combinations (to S1 state) on the various pH/pD values can be also determined in case of using Cyanidioschyzon merolae (C. merolae) thylakoids. Our data support previous suggestions that the S0 → S1 and S1 → S2 transitions involve low or no misses, while high misses occur in the S2 → S3 transition or the S3 → S0 transition. Moreover, the appearance of very slow S2 decay was clearly observed by using the GFP analysis, while there are no evidences of very slow S3 decay were recorded under all circumstances. The unknown electron donor for the very slow S2 decay which can be one of the substances of PSII-protective branch (i.e. cytochrome b559, carotenoid or ChlZ) will be determined in further researches.

abstract: Membrane proteins are a vital part of cellular structure. They are directly involved in many important cellular functions, such as uptake, signaling, respiration, and photosynthesis, among others. Despite their importance, however, less than 500 unique membrane protein structures have been determined to date. This is due to several difficulties with macromolecular crystallography, primarily the difficulty of growing large, well-ordered protein crystals. Since the first proof of concept for femtosecond nanocrystallography showing that diffraction patterns can be collected on extremely small crystals, thus negating the need to grow larger crystals, there have been many exciting advancements in the field. The technique has been proven to show high spatial resolution, thus making it a viable method for structural biology. However, due to the ultrafast nature of the technique, which allows for a lack of radiation damage in imaging, even more interesting experiments are possible, and the first temporal and spatial images of an undamaged structure could be acquired. This concept was denoted as time-resolved femtosecond nanocrystallography. This dissertation presents on the first time-resolved data set of Photosystem II where structural changes can actually be seen without radiation damage. In order to accomplish this, new crystallization techniques had to be developed so that enough crystals could be made for the liquid jet to deliver a fully hydrated stream of crystals to the high-powered X-ray source. These changes are still in the preliminary stages due to the slightly lower resolution data obtained, but they are still a promising show of the power of this new technique. With further optimization of crystal growth methods and quality, injection technique, and continued development of data analysis software, it is only a matter of time before the ability to make movies of molecules in motion from X-ray diffraction snapshots in time exists. The work presented here is the first step in that process. / Dissertation/Thesis / Doctoral Dissertation Biochemistry 2014

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