Electrosorption involves the application of an electrical potential between carbon electrode pairs submerged in brackish water, effectively “trapping” the ions in an electrical double layer at the solid-liquid interface. Electrosorption has significant applications in environmental engineering, including desalination of water by capacitive deionization (CDI), and in energy storage by supercapacitors. This work combines experimental and modeling studies to investigate the transport and sorption mechanisms of ions in the pores of mesoporous carbon materials that were synthesized at the Oak Ridge National Laboratory (ORNL). The main contribution of this research is examining the effects of operational parameters such as applied potential, solution temperature, ionic concentration, and valence of ions, on the electrosorption behavior of mesoporous carbon materials with the aim to improve the desalination efficiency in the CDI process. It was found that the rates of sorption by mesoporous carbon electrodes and their regeneration increased at a higher temperature and on application of a high-frequency, low-amplitude AC signal. Neutron imaging has been employed as a tool to visually observe and quantify the transport and distribution of ions within the carbon electrodes. The neutron images revealed interesting ion transport phenomena that can aid in the optimization of the CDI process. From the ion concentration profiles inside the electrodes, the effective diffusivities of gadolinium and lithium ions were obtained under various conditions of applied potential. Information on the diffusivity of ions can aid in theoretical modeling of the CDI process as well as guide strategies for the design of advanced electrode materials. In the final part of the study, the extraction of salinity gradient energy or ‘blue energy’ by mixing fluids of different salinities was assessed based on the principle of capacitive double layer expansion. Neutron imaging of blue energy recovery cycles was conducted to observe the ion transport behavior during the various steps of the cycle. The results obtained provide insights into the fundamental ion transport mechanisms during electrosorption by mesoporous carbon materials. This research has important implications for developing advanced system designs for desalination of saline water and energy storage devices.

Made available in DSpace on 2016-06-02T19:56:57Z (GMT). No. of bitstreams: 1 6597.pdf: 4764954 bytes, checksum: 5414abc6292e5e2fc5ec8124840f6a6b (MD5) Previous issue date: 2015-02-20 / Universidade Federal de Sao Carlos / In this work, different commercial carbon materials that could be used as electrodes for capacitive deionization were investigated: carbon cloth, carbon foam, carbon felt, carbon fiber, carbon veil and activated carbon powder (AC). The materials were characterized by scanning electron microscopy (SEM), surface resistivity, wettability and cyclic voltammetry (CV). The performance in terms of electrosorption of NaCl was evaluated for different cell potentials. The AC electrode showed the best capacity of removing ions, and presented good values of charge efficiency (QE) and specific energy consumption (η) and, thusly, it was chosen to be modified using different techniques in an attempt to improve its characteristics aiming better results of electrosorption. Part of the strategies was the addition of carbon black and sodium chloride in order to improve the electrode conductivity and its macroporosity, respectively. A factorial experimental design was used to evaluate the effect of the AC mass, NA, mass of sodium chloride used in the electrode preparation and also the cell potential, on the capacity of removing ions (R), QE and η. The variables that showed the greatest effect on the CDI process was the cell potential and the AC mass (that create different thickness for the electrode). In spite of increasing the electrode conductivity, the NA did not show any improvement on the electrosorption of the electrode. Afterwards, an individual analysis showed that the use of sodium chloride to increase electrode macroporisity improved the capacity of the electrode to remove ions but just for the thickest electrode. However, it was verified that the increase of the thickness did not implied in a linear increase of the ion removal capacity. This behavior may be attributed to the non-uniform distribution of the electric field on the porous film. Thusly, even the thicker electrode showing a better capacity of removing ions, a great part of its mass was not being used for electrosorption. Additionally, the increase of the thickness led to a decrease on desorption. Those results indicate that the electrode thickness must be optimized. Another strategy to improve the electrode wettability and capacitance was the deposition of silica and alumina. It was observed an improvement on the wettability of the electrode, however those electrodes voltammograms showed an increase on the resistivity and as result, besides not presenting any improvement on the capacity of electrosorption, there was still a reduction of the ion removal kinect. Finally, the last strategy used to improve the AC electrode was the addition of the conducting polymer polypyrrole aiming to improve the electrode capacity of removing ions through the pseudo capacitance effect. The addition of polypyrrole increased the total of ions removed from solution, however, in all the cases, the values of QE and η were worse than those observed for the AC electrode. Due to the polypyrrole characteristics, the drying temperature used to prepare the electrode was reduced from 130°C to 80°C and when this temperature was reduced, it was verified that this variable had a strong effect on improving the capacity of removing ions and the energy efficiency of the AC electrode. / Neste trabalho foi realizado o estudo de diferentes materiais de carbono disponíveis comercialmente e que poderiam ser utilizados como eletrodos para deionização capacitiva. Dentre eles estão o tecido de carvão ativado, espuma de carbono, feltro de carbono, fibra de carbono, véu de carbono e pó de carvão ativado (CA). Esses materiais foram caracterizados por microscopia eletrônica de varredura, resistividade superficial, molhabilidade e voltametria cíclica. O desempenho dos diferentes eletrodos em termos da eletrossorção de cloreto de sódio foi avaliado para diferentes potenciais de célula. O material que apresentou melhor capacidade de remoção de íons e ao mesmo tempo apresentando bons valores de eficiência de carga (QE) e consumo energético específico (η) foi o eletrodo preparado usando pó carvão ativado. Desta forma, este material foi selecionado para estudos posteriores em que diferentes estratégias de modificação deste eletrodo foram avaliadas para tentar otimizar suas características visando melhores resultados de eletrossorção. Dentre essas estratégias, adicionou-se negro de acetileno e cloreto de sódio na preparação do eletrodo visando melhorar sua condutividade e aumentar sua macroporosidade, respectivamente. Um planejamento fatorial de experimentos foi utilizado a fim de verificar o efeito da massa de CA, negro de acetileno e cloreto de sódio usadas na preparação do eletrodo e também do potencial de célula sobre as variáveis dependentes remoção total de íons (R), QE e η. Observou-se nesta etapa que as variáveis que tiveram o maior efeito no processo de deionização capacitiva foram o potencial de célula e a massa do eletrodo (que por sua vez determina a sua espessura). Constatou-se que a adição de negro de acetileno ao eletrodo, apesar de aumentar a condutividade (como já era esperado), causava uma diminuição da área superficial específica através do entupimento de poros e como consequência, não verificou-se melhoria da eletrossorção, algo que seria esperado pela melhoria da condutividade do eletrodo. Posteriormente, foi realizada uma análise individual do efeito da macroporosidade e da espessura de eletrodo. Os resultados mostraram que o aumento da macroporosidade decorrente do uso de NaCl durante a preparação do eletrodo levou a um aumento da capacidade de eletrossorção somente para o eletrodo mais espesso, porém, na análise da influência do aumento da espessura do eletrodo, verificou-se que não houve um aumento linear na quantidade de íons removidos da solução em função do aumento da espessura, o que pode ser atribuído à nãouniformidade do campo elétrico no filme poroso. Desta forma, apesar do filme mais espesso ter capacidade de remover mais íons, uma grande parte da massa de CA utilizada estava inativa. Adicionalmente, o aumento da espessura levou a uma diminuição da cinética de dessorção. Estes resultados indicam que a espessura do eletrodo deve ser otimizada. Uma outra estratégia analisada para tentar melhorar a molhabilidade e a capacidade de eletrossorção do eletrodo de CA foi a deposição de sílica e alumina. Observouse que houve realmente uma melhoria da molhabilidade, mas por outro lado, os voltamogramas destes eletrodos mostraram um aumento de sua resistividade e como consequência, além de não se verificar uma melhoria na capacidade de eletrossorção, houve ainda uma piora da cinética do processo. Finalmente, a última estratégia utilizada para melhorar o eletrodo de CA foi a adição do polímero condutor polipirrol visando melhorar sua capacidade de remoção de íons através da introdução de pseudocapacitância. A adição de polipirrol causou um leve aumento no total de íons removidos da solução, porém, em todos os casos, os valores de QE e η foram piores do aqueles observados para o eletrodo de CA. Devido às característicos do polipirrol, a temperatura de secagem do eletrodo teve que ser reduzida de 130°C para 80°C e quando se reduziu esta temperatura verificou-se que esta variável desempenhava um papel importante na melhoria da capacidade de remoção de íons e da eficiência energética do eletrodo de CA.

Capacitive deionization based on electrosorption has become a viable process for brackish water desalination. In this study, activated biochar was employed as low-cost and alternative carbon-based electrodes substituting activated carbon with comparable adsorption capacity. Effects of different activation temperatures of the biochar were studied by physical characterization (i.e. SEM, TEM, elemental analysis, and Raman spectroscopy) and electrochemical characterization (i.e. cyclic voltammetry and galvanostatic charge/discharge measurement) based on the electrical double layer theory. The highest specific capacitance obtained (118.50 F g-1) was from activated biochar electrode treated at 800°C. The removal capacity was investigated by AAS and conductivity measurements. Several limitations associated with them were identified to improve the measurements. The removal capacity of biochar electrode is ~ 2 mg g-1 with significant results for both one-sided and two-sided t-test. In summary, activated biochar can be used as a cheap-alternative electrode material for desalination based on capacitive deionization.

Diese Arbeit beinhaltet unsere Studien an selbstorganisierenden Monoschichten (engl. SAM = self- assembled monolayer) einiger aromatischer Thiole auf Gold- und Kupferoberflächen. Die Bildung von Monoschichten von Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin auf Au und Cu wurde untersucht und charakterisiert. Das abschirmende Verhalten und die strukturelle Anordnung dieser Monoschichten wurden mit Hilfe elektrochemischer und spektroskopischer Methoden geprüft und bestimmt. Zyklische Voltammetrie und oberflächenverstärkte Raman Spektroskopie wurden intensiv zur Aufklärung von Elektronentransferreaktionen an diesen mit SAMs modifizierten Oberflächen genutzt. Elektrochemische Studien von Monoschichten aus Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin in 0,1 M wässriger KClO4-Lösung lassen schlussfolgern, dass diese Moleküle schwefelseitig an die Substratoberfläche gebunden sind. In 0,1 M wässriger KClO4-Lösung aufgenommene zyklische Voltammogramme an Gold- und Kupferoberflächen, welche mit oben genannten, aromatischen Thiolen beschichtet wurden, legen nahe, dass Adsorptionsschichten von Thiophenol und 1,4-Dithiobenzol eine stärkere Tendenz zum Abschirmen besitzen als andere. Durch das Einbringen von Kupferproben, welche mit genannten aromatischen Thiolen behandelt wurden, in 0,1 M Silbernitrat-Lösung können sehr leicht Silber-Nanodendritstrukturen erhalten werden. Abscheidezeit und Konzentration der Silbernitrat-Lösung haben einen großen Einfluss auf das Wachstum der Silber-Nanodendritstrukturen auf den modifizierten Kupferproben. Diese Silber-Nanodendritstrukturen besitzen eine hohe katalytische Aktivität hinsichtlich der Oxidation von Hydroquinon. Untersuchungen zur Korrosion an polykristallinem Kupfer, welches mit obigen aromatischen Thiolen modifiziert wurde, in 0,1 M Silbernitrate-Lösung ließen vermuten, dass dieses Kupfersubstrat mehr anodisches Verhalten zeigte als reines Kupfer bei ähnlichen Bedingungen. Zyklische Voltammetrie an wie oben behandeltem Kupfer in 0,1M wässriger KClO4-Lösung zeigte, dass die Geschwindigkeit der Kupferauflösung bei diesen Messungen erhöht war gegenüber anderen, in welchen reines Kupfer bei identischen Bedingungen eingesetzt wurde. / It deals with our studies on self-assembled monolayers of aromatic thiols on gold and copper surfaces. Monolayer formation of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mer¬cap¬to¬pyridine and 2-mercaptopyridine on Au and Cu surfaces was studied and characterized. The blocking behaviour and structural arrange¬ments of these monolayers were evaluated and characterized using electrochemical and spec¬troscopic techniques. Cyclic voltammetry and surface enhanced Raman spectroscopy were extensively used for the study of electron transfer reactions on these SAM modified surfaces. Electrochemical and spectroelectrochemical studies of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mercaptopyridine and 2-mercaptopyridine monolayers in aqueous solution of 0.1 M KClO4 suggest that these molecules adsorbed to substrate. Cyclic voltammetry of gold and copper covered with these aromatic thiolates recorded in aqueous solution of 0.1 M KClO4 suggests that adlayers of thio¬phenol and 1,4-dithiobenzene exhibit more blocking behavior than the other ones. Silver nanodendritic structures are easily produced by placing copper samples modified with these aromatic thiolates into 0.1 M silver nitrate solution. Deposition time and concentration of silver nitrate solution have great influence on growing up silver nanodendritic structures on the surface of modified copper samples. These silver nanodendritic structures exhibit electrocatalytic activity towards the oxidation of hydroquinone. Corrosion investigation of polycrystalline copper modified with these aromatic thiolates in 0.1 M silver nitrate solution suggest that copper substrate might be more anodic compared to bare copper under identical condition. Cyclic voltammetry of copper modified with these aromatic thiolates suggests that the rate of dissolution copper in aqueous solution of 0.1 M KClO4 is higher than bare copper in the same condition.

Environmental separation processes such as removal of heavy metals from aqueous solutions, electrosorption in groundwater remediation, and capacitive desalination, as well as energy storage in supercapacitors, are based on the electrical double layer (EDL) formation within nanoporous carbon materials. This research is focused on the nano-scale phenomena of EDL formation inside the confined space of nanopores. The electrosorption behavior of nanoporous carbon materials was characterized by measuring the double-layer capacitance using cyclic voltammetry. The presence of micropores results in the occurrence of EDL overlapping, corresponding to a considerable loss of the double-layer capacitance. Hence, pore size distribution plays an important role in determining the double-layer capacitance. EDL formation has significant influence on ion transport and sorption inside nanopores. The data obtained by simple diffusion and electrochemically-aided diffusion experiments demonstrated the size-exclusion effects on pore accessibility by ions. A larger ion-exclusion volume prevents larger ions from penetrating inside the pores. Batch equilibrium electrosorption experiments using nanoporous carbon materials showed that selective electrosorption, imposed by the difference in the size of hydrated ions, occurs in a competitive environment. Molecular modeling based on Monte Carlo methods was developed to simulate the EDL formation in a slit-type nanopore. Simulation results indicated that the competition in asymmetries of ion charge and size not only determines the screening of surface charge but also affects the electrolyte distribution within charged pores. In a mixture of electrolytes, the charge/size competitive effects can dominate pore accessibility. Multivalent counterions with large size have the energetic advantage of screening surface charge. On the other hand, small monovalent counterions present a ¡§size affinity¡¨ to access the pores. Therefore, electrosorption selectivity of counterions with different properties is a result of a counterbalance between minimization of potential energy and size-exclusion effects. Manipulation of electrosorption selectivity to separate ions could in principle be achieved via tuning the EDL formation inside the pores. The findings of the thesis have several significant implications for the development of advanced techniques for selective separation of ions in environmental systems and energy storage.

The adsorbate formed by adsorption of thiophenol on a polycrystalline gold electrode and brought into contact with aqueous solutions of 1 M HClO4 and 0.1 M KClO4 has been studied using cyclic voltammetry and surface-enhanced Raman spectroscopy. A strong adsorption is deduced from observations made using cyclic voltammetry. From the SER spectra, interactions of thiophenol with the gold surface via a gold–sulfur bond with the aromatic ring pointing away from the surface is concluded for both electrolyte solutions. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Diese Arbeit beinhaltet unsere Studien an selbstorganisierenden Monoschichten (engl. SAM = self- assembled monolayer) einiger aromatischer Thiole auf Gold- und Kupferoberflächen. Die Bildung von Monoschichten von Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin auf Au und Cu wurde untersucht und charakterisiert. Das abschirmende Verhalten und die strukturelle Anordnung dieser Monoschichten wurden mit Hilfe elektrochemischer und spektroskopischer Methoden geprüft und bestimmt. Zyklische Voltammetrie und oberflächenverstärkte Raman Spektroskopie wurden intensiv zur Aufklärung von Elektronentransferreaktionen an diesen mit SAMs modifizierten Oberflächen genutzt. Elektrochemische Studien von Monoschichten aus Thiophenol, 4-Mercaptophenol, 4-Nitrothiophenol, 4-Aminothiophenol, 1,4-Dithiobenzol, 4-Mercaptopyridin und 2-Mercaptopyridin in 0,1 M wässriger KClO4-Lösung lassen schlussfolgern, dass diese Moleküle schwefelseitig an die Substratoberfläche gebunden sind. In 0,1 M wässriger KClO4-Lösung aufgenommene zyklische Voltammogramme an Gold- und Kupferoberflächen, welche mit oben genannten, aromatischen Thiolen beschichtet wurden, legen nahe, dass Adsorptionsschichten von Thiophenol und 1,4-Dithiobenzol eine stärkere Tendenz zum Abschirmen besitzen als andere. Durch das Einbringen von Kupferproben, welche mit genannten aromatischen Thiolen behandelt wurden, in 0,1 M Silbernitrat-Lösung können sehr leicht Silber-Nanodendritstrukturen erhalten werden. Abscheidezeit und Konzentration der Silbernitrat-Lösung haben einen großen Einfluss auf das Wachstum der Silber-Nanodendritstrukturen auf den modifizierten Kupferproben. Diese Silber-Nanodendritstrukturen besitzen eine hohe katalytische Aktivität hinsichtlich der Oxidation von Hydroquinon. Untersuchungen zur Korrosion an polykristallinem Kupfer, welches mit obigen aromatischen Thiolen modifiziert wurde, in 0,1 M Silbernitrate-Lösung ließen vermuten, dass dieses Kupfersubstrat mehr anodisches Verhalten zeigte als reines Kupfer bei ähnlichen Bedingungen. Zyklische Voltammetrie an wie oben behandeltem Kupfer in 0,1M wässriger KClO4-Lösung zeigte, dass die Geschwindigkeit der Kupferauflösung bei diesen Messungen erhöht war gegenüber anderen, in welchen reines Kupfer bei identischen Bedingungen eingesetzt wurde. / It deals with our studies on self-assembled monolayers of aromatic thiols on gold and copper surfaces. Monolayer formation of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mer¬cap¬to¬pyridine and 2-mercaptopyridine on Au and Cu surfaces was studied and characterized. The blocking behaviour and structural arrange¬ments of these monolayers were evaluated and characterized using electrochemical and spec¬troscopic techniques. Cyclic voltammetry and surface enhanced Raman spectroscopy were extensively used for the study of electron transfer reactions on these SAM modified surfaces. Electrochemical and spectroelectrochemical studies of thiophenol, 4-mercaptophenol, 4-nitrothiophenol, 4-aminothiophenol, 1,4-dithiobenzene, 4-mercaptopyridine and 2-mercaptopyridine monolayers in aqueous solution of 0.1 M KClO4 suggest that these molecules adsorbed to substrate. Cyclic voltammetry of gold and copper covered with these aromatic thiolates recorded in aqueous solution of 0.1 M KClO4 suggests that adlayers of thio¬phenol and 1,4-dithiobenzene exhibit more blocking behavior than the other ones. Silver nanodendritic structures are easily produced by placing copper samples modified with these aromatic thiolates into 0.1 M silver nitrate solution. Deposition time and concentration of silver nitrate solution have great influence on growing up silver nanodendritic structures on the surface of modified copper samples. These silver nanodendritic structures exhibit electrocatalytic activity towards the oxidation of hydroquinone. Corrosion investigation of polycrystalline copper modified with these aromatic thiolates in 0.1 M silver nitrate solution suggest that copper substrate might be more anodic compared to bare copper under identical condition. Cyclic voltammetry of copper modified with these aromatic thiolates suggests that the rate of dissolution copper in aqueous solution of 0.1 M KClO4 is higher than bare copper in the same condition.

Cette thèse a pour objectif de proposer une modélisation performante des supercondensateurs à électrodes à base de carbone activé, composants de puissance présents dans un nombre croissant d’applications de stockage d’énergie. La première étape des travaux a consisté à mettre en évidence les phénomènes physico-chimiques, qu’ils soient électrostatiques ou électrochimiques grâce à des essais de caractérisation spécifiques et de vieillissement. L’analyse des résultats associée à la connaissance des matériaux constitutifs a conduit à attribuer le comportement non linéaire du supercondensateur aux phénomènes d’adsorption-désorption (électrosorption) et de diffusion anomale des espèces adsorbées dans le réseau microporeux de l’électrode. La prise en compte de ces phénomènes et de la capacité de double couche a permis de définir un modèle non linéaire fractionnaire dont les paramètres dépendent des grandeurs physico-chimiques de la cellule. La procédure proposée pour l’identification des paramètres du modèle repose sur la réponse en tension du supercondensateur à des profils de charges-décharges. Malgré la simplicité de l’identification, le modèle traduit fidèlement le comportement du supercondensateur soumis à des profils en courant typiques d’applications véhicules électriques et hybrides. / This work aim is an efficient modelling proposal for supercapacitors made of activated carbon electrodes which are power components used in many energy storage applications. In the first part of this study, the purpose is to evidence physico-chemical phenomena, electrostatic or electrochemical as well, thanks to characterization and aging tests. The results analysis combined with materials knowledge leads to suppose that the supercapacitor non linear behavior is due to adsorption-desorption processes and also to anomalous diffusion of adsorbed species into the electrode microporous network. These mechanisms in addition with the double layer capacitor principle allow us to define a non linear fractional model with parameters that depend on physic0-chemical characteristics of the cell. The proposed identification procedure is based on the voltage response to charges-discharge current profiles. In spite of the simplicity of this identification method, the model matches very well the behavior of the supercapacitor under current profiles that are typical of hybrid and electric vehicle applications.

The adsorbate formed by adsorption of thiophenol on a polycrystalline gold electrode and brought into contact with aqueous solutions of 1 M HClO4 and 0.1 M KClO4 has been studied using cyclic voltammetry and surface-enhanced Raman spectroscopy. A strong adsorption is deduced from observations made using cyclic voltammetry. From the SER spectra, interactions of thiophenol with the gold surface via a gold–sulfur bond with the aromatic ring pointing away from the surface is concluded for both electrolyte solutions. / Dieser Beitrag ist aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.