Controlled synthesis of functional nanostructures is of paramount interest due to their novel properties and efficient functionalities. The size and morphology of each particle in the nanoscale contribute to their optical and electronic properties. Also, the collective arrangement of these nanostructures in 3D space maximizes active sites available for the cost-effective catalysis. Recent advances in the field show a vast range of nanostructures with unique designs that affect their catalytic properties. In this dissertation, utilizing silver halides as a unique platform to develop high-performance catalysts were discussed with their respective synthesis strategies, structural evolution, and structure-related properties. Initially, we synthesized well-defined silver chlorobromide (AgCl0.5Br0.5) nanostructures investigating the effects of various reaction parameters on the synthesis. Simple reaction parameters were overlooked to gain additional controllability on determining the morphology of the nanocrystals regardless of the composition. Thus, the influence of the size and exposed surface facets was investigated towards photocatalytic activity performing methylene blue degradation on AgCl0.5Br0.5 with different sizes and morphologies, under visible light. Then, the ability to use these AgCl0.5Br0.5 nanocubes were investigated as a reactive and sacrificial template for the synthesis of nanoplates and nanoshells. As an example, fast precipitation reaction between Ag+ and benzenethiol (BT–) results in an uncontrollable growth leading to aggregated structures. The low solubility and the planer surfaces of the silver halide cubes were utilized to reduce the reaction rate and promote the growth of layered AgBT as plates, which can be organized into hollow nanostructures. Time-dependent microscopic and spectroscopic measurements showed the structural evolution and associated kinetics of the conversions. Developing a comprehensive understanding enabled generalizing the procedure to synthesize other silver-based hollow nanostructures. Mechanistic studies showed two different hollowing mechanisms involving, that depends on the anion being exchanged. The degree of nucleation and the crystal structure of silver-sulfur compounds determined the relative diffusion of ions leading to their overall size and morphology. The hollow morphology was shown to have higher stability with a large surface area relative to its aggregated solid counterpart. Next, highly porous Ag nanostructures were synthesized electrochemically, using silver thiolate nanocages. High porosity and their arrangement as plates enhanced available active sites and mass transport for CO2 electroreduction. Furthermore, the strategy was extended to design bimetallic nanostructures with enhanced bimetallic boundaries where selectivity of ethanol formation from CO2 electroreduction can be increased. Overall, the study explores the novel approaches to utilize chemical and physical properties of silver halides for various material designs that determines their enhanced performance. / Chemistry

[EN] This research work constitutes a first approximation to the study of the viability of carbonic fertirrigation in citrus fruits as a CO2 drain potential. To that effect, carbonic fertirrigation experiments were carried out with citrus fruits of the Nadarcott variety from the year 2010 to the year 2015. The study required the monitoring of parameters related to the leaf surface, the phenological state of the trees, the ground, the leaves and the fruits of the tested trees. The analysis of the results obtained showed there were no significant differences in the size and quality of the fruits irrigated with CO2. Differences were neither observed in the trees' vegetative development nor in the advance or delay of the blooming and formation of fruits. The analysis of the grounds revealed that the content in organic matter of the grounds irrigated with CO2 was higher than in the grounds used as reference in at least two tenths of a percentage. Similarly, it was noted that the content in iron in the leaves of the trees irrigated with CO2 was significantly higher than in the trees used as reference. The statistical analysis carried out confirmed these conclusions, noting a 24% increase over the average value in the case of the organic matter in the ground and of a 16% in the case of the iron content in the leaves. Both factors indicate that carbonic fertirrigation does have relevant agronomic repercussions, especially on the organic fraction of the ground and on the iron soluble fraction. Various authors confirm the mobilisation of the iron produced by the decrease in the pH of the irrigation water - this study confirms this fact and strengthens the usage of carbon dioxide as a potential substitute of strong acids normally used for this purpose. The increase in the content of the ground's organic matter is an especially interesting result, as it was not expected, even though some authors have related the decrease of soil respiration to different cultural practices that improve the ground's texture. The interaction between the CO2 of the irrigation water and the content in organic matter in the ground and, therefore, soil respiration must be studied in further detail in a future, with experiences specially aimed at valuing the repercussions of this practice on both parameters. / [ES] Este trabajo de investigación constituye una primera aproximación al estudio de viabilidad de la fertirrigación carbónica en cítricos como potencial sumidero de CO2. A tal efecto, se llevaron a cabos experimentos de fertirrigación carbónica con cítricos de la variedad Nadarcott desde el año 2010 hasta el año 2015. El estudio requirió la monitorización de parámetros relacionados con la superficie foliar, los estados fenológicos de los árboles, el suelo, las hojas y los frutos de los árboles ensayados. El análisis de los resultados obtenidos mostró que no había diferencias significativas en el tamaño y calidad de los frutos regados con CO2. Tampoco se observaron diferencias en el desarrollo vegetativo de los árboles ni en el avance o retraso de la floración y formación de los frutos. Los análisis de los suelos revelaron que el contenido en materia orgánica de los suelos regados con CO2 era más alto que los suelos tomados como referencia en al menos dos décimas porcentuales. De la misma manera, se observó que el contenido en hierro en las hojas de los árboles regados con CO2 era significativamente más alto que en los árboles tomados como referencia. Los análisis estadísticos realizados confirmaron estas conclusiones, observándose un incremento del 24% sobre el valor promedio en el caso de la materia orgánica del suelo y del 16% en el caso del contenido en hierro de las hojas. Ambos factores indican que la fertirrigación carbónica sí que tiene repercusiones agronómicas relevantes, especialmente sobre la fracción orgánica del suelo y sobre la fracción soluble de hierro. Diversos autores confirman la movilización del hierro producido por la disminución del pH del agua de riego; este estudio confirma este hecho y refuerza la utilización del dióxido de carbono como potencial sustituto de los ácidos fuertes normalmente utilizados para este cometido. El aumento en el contenido de materia orgánica del suelo es un resultado especialmente interesante, pues no era esperado pese a que algunos autores han relacionado la disminución de la respiración edáfica con diferentes prácticas culturales que mejoran la textura del suelo. La interacción entre el CO2 del agua de riego y el contenido en materia orgánica del suelo y, por tanto, la respiración edáfica deben de ser estudiados con más detalle, en un futuro con experiencias especialmente dirigidas a valorar las repercusiones de esta práctica sobre ambos parámetros. / [CA] Aquest treball d'investigació constitueix una primera aproximació a l'estudi de la viabilitat de la fertirrigació carbònica en cítrics com a potencial embornal de carboni. Amb aquesta finalitat es dugueren a terme experiments de fertirrigació carbònica amb cítrics de la varietat Nadorcott des de l'any 2010 fins l'any 2015. L'estudi va requerir la monitoratge de paràmetres relacionats amb la superfície foliar, els estat fenològics del arbres, el sòl, les fulles i el fruits dels arbres assatjats. L'anàlisi dels resultats obtinguts mostrà que no hi havia diferències significatives en el tamany i qualitat del fruits regats amb CO2. Tampoc es varen observar diferències en el desenvolupament vegetatiu dels arbres ni en l'avanç o retard de la floració i formació dels fruits. Les anàlisis dels sòls revelaren que el contingut de matèria orgànica dels sòls regats amb CO2 era més alt que els sòls considerats com a referència en, almenys, dues dècimes percentuals. De la mateixa manera, s'observà que el contingut de ferro en les fulles dels arbres regats amb CO2 era significativament més alt que en els arbres referència. Les anàlisis estadístiques realitzades confirmaren aquestes conclusions, observant-se un increment del 24% sobre el valor mitjà en el cas de la matèria orgànica del sòl i del 16% en el cas del contingut en ferro de les fulles. Tots dos factors indiquen que la fertirrigació carbònica sí que té repercusions agronòmiques rellevants, especialment, sobre la fracció orgànica del sòl i la fracció soluble de ferro. Diferents autors confirmen la mobilització del ferro produit per la disminució del pH de l'agua de reg; aquest estudi confirma aquest fet i reforça l'ús del diòxid de carboni com a potencial subsutitut dels àcids forts normalment gastats per a aquesta tasca. L'augment en el contingut de matèria orgànica del sòl és un resultat especialment interessant, ja que no era esperat, malgrat que alguns autors han relacionat la disminució de la respiració edàfica amb diferents pràctiques culturals que milloren la textura del sòl. La interacció entre el CO2 de l'aigua de reg i el contingut en matèria orgànica del sòl i, per tant, la respiració edàfica han de ser estudiats amb més detall en un futur amb experiències especialment dirigides a valorar les repercussions d'aquesta pràctica sobre tots dos paràmetres. / Tarazona Díez, JV. (2015). ANÁLISIS DEL POTENCIAL DE LA FERTIRRIGACIÓN CARBÓNICA EN CÍTRICOS [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/59405

In view of the challenges of decarbonisation of the cement industry, the use of low-clinker ternary cements especially with calcined clays is becoming increasingly important. The combination of Portland cement clinker (K), ground granulated blast furnace slag (S) and calcined clay (Q) in ternary cements is very promising in terms of cement and concrete properties. In this study the CO2 footprint of such cements as well as the energy required for their production was determined over a wide range of cement compositions systematically for the first time. The results were related to the strength development of the cements and the mineralogical com-position as well as the moisture of the used clays. Compared to an OPC (CEM I 42.5), both the CO2 and energy saving potentials for the production of ternary KSQ cements are between 25 and 55 % respectively, depending on the cement composition.

京都大学 / 新制・課程博士 / 博士(人間・環境学) / 甲第25364号 / 人博第1106号 / 新制||人||259(附属図書館) / 京都大学大学院人間・環境学研究科相関環境学専攻 / (主査)教授 吉田 寿雄, 教授 田部 勢津久, 教授 中村 敏浩, 教授 田中 庸裕 / 学位規則第4条第1項該当 / Doctor of Human and Environmental Studies / Kyoto University / DFAM

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active biomolecules such as DNA bases and neurotransmitters. The results highlight a simplified surface modification procedure for producing efficient and highly selective electrocatalysts. The next four chapters focus on evaluating nitrogen-doped carbon nano-onions (𝑛-CNOs) as electrocatalysts for oxygen reduction and CO2 reduction. 𝑛-CNOs exhibit excellent electrocatalytic performance toward O2 to H2O reduction, which is a pivotal process in fuel cells. 𝑛-CNOs demonstrate excellent resistance against CO poisoning and long-term stability compared to state-of-the-art Pt/C catalysts. In CO2 electrochemical conversion, 𝑛-CNOs demonstrate significant improvement in catalytic performance toward reduction of CO2 to CO with a low overpotential and high selectivity. The outstanding catalytic performance of 𝑛-CNOs originates from the asymmetric charge distribution and creation of catalytic sites during incorporation of nitrogen atoms. High contents of pyridinic and graphitic N are critical for high catalytic performance. This work suggests that carbon-based materials can be outstanding alternatives to traditional metal-based electrocatalysts when their microstructures and surface chemistries are properly tailored.

Le monoxyde de carbone déshydrogénase (CODH) catalyse la réduction réversible du dioxyde de carbone par son site actif. En utilisant une méthode électrochimique appelée voltammétrie de film protéique, nous étudions le mécanisme enzymatique de CODH en immobilisant l'enzyme à une surface d'électrode de graphite où le transfert direct d'électrons est possible. Traditionnellement, pour empêcher la déplétion du substrat à l'électrode, les électrochimistes utilisent des électrodes tournantes (RDE). Cependant, comme la CODH est très active, même la RDE ne peut pas empêcher l'épuisement, ce qui masque les caractéristiques cinétiques importantes de l’enzyme. Nous ne pouvons pas résoudre le problème avec RDE, puisque nous l’utilisons déjà à la vitesse maximum. Par conséquent, nous devons concevoir une nouvelle cellule électrochimique. Pour cela, nous avons utilisé des simulations de dynamique des fluides computationnelles pour explorer diverses géométries afin d'en trouver une appropriée. Nous avons commencé par valider notre méthode numérique avec la solution théorique bien définie de la cellule réelle de RDE. Après la bonne validation, nous avons déterminé les vitesses de transport de masse au sein de plusieurs géométries et à basé sur l'optimisation des paramètres géométriques, nous avons atteint notre conception appropriée. Ce nouveau prototype a une électrode graphite uniformément accessible avec un taux de transport trois fois plus rapide que le RDE à des vitesses de solution acceptables. Nous avons construit, mis en place avec succès le système pour caractériser ses performances de transport, et trouvé un excellent accord entre les résultats numériques et expérimentaux / Carbon monoxide dehydrogenase (CODH) catalyzes the reversible reduction of carbon dioxide by its active site. Thus, CODH participates in the first step of fuel production. Using an electrochemical method called protein film voltammetry, we study the enzymatic mechanism of CODH by immobilizing the enzyme at a graphite electrode surface where direct electron transfer is possible. Traditionally, to prevent depletion of the substrate at the electrode, electrochemists use rotating electrodes (RDE). However, since CODH is very active, even RDE cannot prevent depletion, which masks the important kinetic characteristics of the enzyme and complicates the analysis of the enzymatic response.We cannot solve the problem with RDE, since we already use it at maximum speed. Therefore, we must completely change our approach and design a new electrochemical cell. For this, we used computational fluid dynamics (CFD) simulations to explore various geometries to find a suitable one. We began by validating our numerical method with the well-defined theoretical solution of the real cell of RDE. After good validation, we determined the mass transport velocities within several proposed geometries of the flow cell of hydrodynamic channel and jet electrodes. Based on the optimization of geometric parameters, we have achieved our proper design of jet electrode. This new prototype has a uniformly accessible graphite electrode with a transport rate three times faster than the RDE at acceptable solution speeds. We have successfully built and implemented the system to characterize its transport performance. We found an excellent agreement between the numerical and experimental results

Ce mémoire vise à montrer l’intérêt de nanoparticules (NPs) de TiO2 comme plateforme pour immobiliser dans un environnement proche des complexes de coordination pouvant interagir par transfert d’électron photoinduit. Nous nous sommes intéressés à l’étude de nanomatériaux hybrides associant le complexe [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) comme photosensibilisateur aux complexes [Cr(ttpy)2]3+ ou [Mn(ttpy)(CO)3Br] (ttpy = 4'-(p-tolyl)-2,2':6',2''-terpyridine) comme accepteurs d'électrons. Pour immobiliser les différents complexes à la surface du TiO2, une fonction acide phosphonique a été introduite sur une des bipyridines du centre [Ru(bpy)3]2+ et sur la terpyridine des complexes [Cr(ttpy)2]3+. L’étude des processus de transferts de charges photo-induits sous irradiation en lumière visible sur le colloïde TiO2/RuII montre que l'état à charges séparées (e-)TiO2/ RuIII possède une longue durée de vie, ce qui rend possible l'utilisation des charges dans des réactions successives d’oxydation ou de réduction. Notamment l’irradiation du colloïde TiO2/RuII en présence de [Cr(ttpy)2]3+ et de triéthanolamine (TEOA) comme donneur d'électron sacrificiel permet la réduction à deux électrons du [Cr(ttpy)2]3+. Par la suite, le complexe [Cr(ttpy)2]3+ est immobilisé sur les NPs de TiO2/RuII pour former un assemblage RuII/TiO2/CrIII au sein duquel les processus de transfert d'électrons photo-induits sont étudiés. De manière à proposer un système pour la réduction photocatalytique du CO2, le complexe [Mn(ttpy)(CO)3Br] a été co-immobilisé avec le [Ru(bpy)3]2+ suivant une approche de chimie sur surface pour former le colloïde RuII/TiO2/MnI. Ce système présente une excellente sélectivité vis-à-vis du HCOOH comme seul produit de la photoréduction du CO2 en présence de 1-benzyl-1,4-dihydronicotinamide (BNAH) comme donneur d'électron sacrificiel. Un système hybride associant le [Ru(bpy)3]2+ portant des fonctions pyrroles et immobilisé sur TiO2 a également été synthétisé et étudié. Sous irradiation lumineuse, le transfert de charges (e-)TiO2/[Ru-pyr]3+ permet d’induire la polymérisation du pyrrole. Le nanocomposite TiO2/poly(Ru-pyr) obtenu et déposé sur une électrode génère, en présence de TEOA, un photocourant anodique stable de plus de 10 μA.cm-2. L’ensemble des résultats montre que les NPs de TiO2 peuvent être un moyen d’assembler des complexes dans un environnement proche en limitant les interactions à l’état fondamental, mais permettant des transferts d’électrons photoinduits entre eux. Suivant les potentiels redox des différents composants, les transferts d’électron ont lieu soit via la nanoparticule soit en surface de celle-ci. / This thesis aims to investigate the possibility of using TiO2 nanoparticles (NPs) as a platform to immobilize proximal coordination complexes that can interact with each other by photoinduced electron transfer. We have studied hybrid nanomaterials combining [Ru(bpy)3]2+ (bpy = 2,2'-bipyridine) as a photosensitizer and [Cr(ttpy)2]3+ or [Mn(ttpy)(CO)3Br (ttpy = 4'-(p-tolyl)-2,2':6',2''-terpyridine) as electron acceptors. To immobilize the various complexes on the surface of TiO2, a phosphonic acid functional group was introduced on one of the bipyridines of the [Ru(bpy)3]2+ center and on the terpyridines of the [Cr(ttpy)2]3+ complex. Under visible light, the TiO2/RuII colloid undergoes a photo-induced charge transfer process leading to a long-lived charge separation state (e )TiO2/RuIII, which makes it possible to be engaged in successive oxidation or reduction reactions. In particular, the visible irradiation of the TiO2/RuII colloid in the presence of [Cr(ttpy)2]3+ and triethanolamine (TEOA) as a sacrificial electron donor allows the two-electron reduction of [Cr(ttpy)2]3+. Subsequently, the [Cr(ttpy)2]3+ complex has been immobilized on the TiO2/RuII NPs to form a RuII/TiO2/CrIII assembly in which the photoinduced electron transfer processes were investigated. In order to propose a system for the photocatalytic reduction of CO2, the [Mn(ttpy)(CO)3Br] and [Ru(bpy)3]2+ complexes were co-immobilized on TiO2 NPs following a chemistry on surface approach to form a RuII/TiO2/MnI triad. Under irradiation at 470 nm, this system exhibits excellent selectivity towards HCOOH as the only product of CO2 photoreduction in DMF/TEOA solvent mixture, in the presence of 1-benzyl-1,4-dihydronicotinamide (BNAH) as a sacrificial electron donor. Another hybrid system linking a [Ru(bpy)3]2+ unit to two pyrrole functions and being immobilized on TiO2 has also been synthesized and studied. Under visible light, the transient (e-)TiO2/[Ru-pyr]3+ species induce the polymerization of pyrrole to form a TiO2/poly(Ru-pyr) nanocomposite. The nanocomposite deposited on an electrode generates, in the presence of TEOA, a stable anodic photocurrent of more than 10 μA.cm-2. All the results show that TiO2 NPs can be used to associate different complexes in a close environment by limiting the interactions in the ground state but allow photoinduced electron transfer processes between them. Depending on the redox potentials of the different components, the electron transfer takes place either through the semiconducting NPs or on the surface.

No description available.

No description available.

Replacing conventional generation with renewable generation in power systems is essential for reducing CO2 emissions. It is important to know how effective renewables are in reducing CO2 emissions. Since CO2 reduction cannot be measured directly, different methods have been used to estimate reduction of CO2 emissions. The two most common methods are econometric models and dispatch models. Econometric models apply regression analysis using historical data for CO2 emissions, power production, and electricity demand to estimate CO2 reduction. On the other hand, dispatch models are detailed optimization simulations of power systems where the objective is to calculate the cost-optimal dispatch of the power plants. The dispatch model finds the optimal dispatch for a base case and counterfactual case. In the counterfactual case, the renewable generation in the system is modified. From the difference in CO2 emissions between the two cases, an estimation of CO2 reduction can be made. Recent studies have shown that dispatch models and econometric models can give different estimations of CO2 reduction. However, these studies did not include several factors that can increase CO2 emissions, such as; transmission constraints, security requirements, and non-linear factors. Examples of non-linear factors are; minimum dispatched energy of generating units, start up emissions, minimum up- and downtime for generating units, and energy generated during start-up and shut-down. This thesis examines if there is an agreement between econometric models and dispatch models for estimating CO2 reduction and if the agreement changes when more non-linear factors are considered. To examine these questions a systematic comparison has been done. Two econometric models are constructed, a linear econometric model and a polynomial linear econometric model. The polynomial linear econometric model is constructed to take into account non-linear factors. Eight dispatch models are constructed with increasing modelling complexity. Four model versions do not include any non-linear factors and four include non-linear factors. The results showed that the agreement between econometric and dispatch models is fairly good, except for versions that contain transmission constraints. The simulation is executed in a fictional test system that is not dimensioned for wind power generation at the given buses. Therefore is possible that transmission constraints impacts the reduction of CO2 too heavily. Furthermore, the results show that the non-linear factors contribute to CO2 emission and consequently lower the estimation of CO2 reduction. However, no conclusion can be made if the agreement between econometric and dispatch models divert when more non-linear factors are considered. / Världens utsläpp av CO2 måste minska för att inte jorden ska drabbas av drastiska klimatförändringar som temperaturhöjningar. Idag står elproduktionen för ungefär en fjärdedel av världens utsläpp av CO2. Därmed måste dagens elproduktion och elkraftsystem minska sina utsläpp av CO2 . Ett viktigt verktyg för att kraftsystem ska minska sina utsläpp av CO2 är expansion av förnybar elproduktion. Dock så går det inte att mäta direkt hur mycket CO2-utsläppen minskar vid expansion av förnybar elproduktion. Därför har flera olika estimeringsmetoder utvecklats för att uppskatta CO2-reduktion. De två vanligaste metoderna är ekonometriska modeller och produktionssimuleringsmodeller. Ekonometriska modeller använder sig av regressionsanalys med historiska tidsserier som; CO2 -utsläpp, kraftproduktion och elförbrukning för att uppskata CO2 -minskningen. Produktionssimuleringsmodeller är detaljerade optimeringssimuleringar där avsikten är att beräkna den kostoptimala användningen av kraftverk i ett system. Tidigare studier har visat att ekonometriska modeller och produktionssimuleringsmodeller kan ge olika uppskattningar av CO2 -reduktion. Dock har produktionssimuleringsmodellerna i studierna inte tagit hänsyn till flera faktorer som kan påverka CO2-utsläppen, som t.ex. överföringsbegränsningar, säkerhetsbegräsningar och icke-linjära faktorer. Exempel på icke-linjära faktorer är minimal produktion av energi för varje kraftverk, CO2 -utsläpp vi uppstart, minimal upp- och nertid och produktion vid uppstart och nedstänging för varje generator. Den här uppsatsen undersöker om de två metoderna ekonometriska modeller och produktionssimuleringsmodeller liknade uppskattningar av CO2 -reduktion och hur överrenstämmelsen mellan modellerna påverkas när man beaktar icke-linjära faktorer. För att försöka besvara dessa frågor har en systematisk jämförelse utförts. Två ekonometriska modeller har konstruerats, en linjär och en polynom-linjär ekonometrisk modell. Den polynom-linjära ekonometriska modellen tar i beaktning icke-linjära faktorer. Åtta produktionssimuleringsmodeller har konstruerats och de åtta olika modellerna har formulerats i en ökande ordning av noggrannhet. Fyra av modellerna tar inte hänsyn till några icke-linjära faktorer och fyra av modellerrna tar hänsyn till icke-linjära faktorer.