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Esta tese apresenta um estudo detalhado das propriedades eletroquímicas dos nanocompósitos de V2O5.nH2O e poli(pirrol) sobre a superfície de eletrodos. Demonstramos aqui que pelo controle de parâmetros de síntese é possível alterar a composição das interfaces eletroquímicas dos eletrodos modificados, fazendo com que o poli(pirrol) esteja por cima, por baixo ou dentro do V2O5 que recobre os eletrodos. Esta diferenciação estrutural tem repercussão nas propriedades eletroquímicas e espectroscópicas dos eletrodos modificados. Desenvolvemos além disto um método para gerar matrizes de V2O5.nH2O, assim como nanocompósitos com poli(pirrol) que possuam anisotropia elétrica tridimensional, propriedade útil em eletrônica. Na última parte do trabalho, poli(pirrol) foi inserido em matrizes de intercalação do tipo BV (V2O5.nH2O estabilizado com esmectita) gerando materiais estáveis em meio aquoso e adequados modificadores de eletrodos, viabilizando a exploração das propriedades dos compósitos de V2O5/poli(pirrol) em água. / This thesis focuses on the electrochemical properties of V2O5.nH2O and its poly(pyrrole) nanocomposites over electrodes. We demonstrate that it is possible, by controlling synthetic procedures, to change the composition of the modified electrodes interfaces, leaving poly(pyrrole) over, under or inside the V2O5 films covering the electrodes. This structural differenciation repercutes on the electrochemical and spectroscopic properties of the modified electrodes. We have developed also a method to generate V2O5.nH2O matrices as well as their nanocomposites with poly(pyrrole) showing tridimensional electrical anisotropy, a useful property in electronics. Additionally, poly(pyrrole) has been inserted into BV (smectite stabilized V2O5.nH2O) matrices, generating stable materials in aqueous medium, conveying to this, the properties of V2O5/poly(pyrrole) nanocomposites modified electrodes.

Esta tese apresenta um estudo detalhado das propriedades eletroquímicas dos nanocompósitos de V2O5.nH2O e poli(pirrol) sobre a superfície de eletrodos. Demonstramos aqui que pelo controle de parâmetros de síntese é possível alterar a composição das interfaces eletroquímicas dos eletrodos modificados, fazendo com que o poli(pirrol) esteja por cima, por baixo ou dentro do V2O5 que recobre os eletrodos. Esta diferenciação estrutural tem repercussão nas propriedades eletroquímicas e espectroscópicas dos eletrodos modificados. Desenvolvemos além disto um método para gerar matrizes de V2O5.nH2O, assim como nanocompósitos com poli(pirrol) que possuam anisotropia elétrica tridimensional, propriedade útil em eletrônica. Na última parte do trabalho, poli(pirrol) foi inserido em matrizes de intercalação do tipo BV (V2O5.nH2O estabilizado com esmectita) gerando materiais estáveis em meio aquoso e adequados modificadores de eletrodos, viabilizando a exploração das propriedades dos compósitos de V2O5/poli(pirrol) em água. / This thesis focuses on the electrochemical properties of V2O5.nH2O and its poly(pyrrole) nanocomposites over electrodes. We demonstrate that it is possible, by controlling synthetic procedures, to change the composition of the modified electrodes interfaces, leaving poly(pyrrole) over, under or inside the V2O5 films covering the electrodes. This structural differenciation repercutes on the electrochemical and spectroscopic properties of the modified electrodes. We have developed also a method to generate V2O5.nH2O matrices as well as their nanocomposites with poly(pyrrole) showing tridimensional electrical anisotropy, a useful property in electronics. Additionally, poly(pyrrole) has been inserted into BV (smectite stabilized V2O5.nH2O) matrices, generating stable materials in aqueous medium, conveying to this, the properties of V2O5/poly(pyrrole) nanocomposites modified electrodes.

The fundamental understanding of the dynamic characteristics of metal dissolution and redeposition behavior at the electrode-electrolyte interface is essential, which provides the basis for the development of advanced energy and conversion devices (such as electrochromic devices, electrocatalysts, and batteries) with superior electrochemical performances. We firstly demonstrate the feasibility of resynthesizing the electrode surface chemistry and tuning the electrochemical reactions at the solid-liquid interface by selectively changing the electrolyte composition and electrochemical cycling conditions. Amorphous TiO2 surface layers can be formed on WO3 electrodes by adding exotic Ti cations to the electrolyte, and slow electrochemical cycling. The dissolution and redeposition of electrodes and surface coatings are intertwined, helping to establish a dissolution-redeposition equilibrium at the interface, which can inhibit metal dissolution, stabilize electrode morphology, and promote electrochemical performance. Since the diffusion layer generated by the dissolution of transition metals is ubiquitous at the electrochemical solid-liquid interface, by combining in situ three-electrode electrochemical reaction cell with advanced spatially resolved synchrotron X-ray fluorescence microscopy and micro-X-ray absorption spectroscopy, we then successfully demonstrate the formation and chemical identification of the diffusion layer. By studying the evolution of diffusion layers(tens of micrometers thick) when using WO3 electrodes in acidic electrolytes, we find that with increasing distance of the dissolved species from the electrode surface, the oxidation state remains largely unchanged, but the local electronic environment of the dissolved W species becomes more distorted. We subsequently report a systematic experimental approach by collecting a series of twodimensional fluorescence images at the electrodes to study electrode dissolution and redeposition under different electrochemical conditions. The results show that (1) metal dissolution and redeposition behaviors greatly evolve under different electrode polarization and electrolyte compositions; (2) metal dissolution and redeposition behaviors are independent of bulk electrolyte pH but depend on interfacial pH; and (3) the accumulation of interfacial dissolved species promotes the formation of polytungstate interfacial networks, which ultimately manifest as temporal heterogeneity of redeposition. Lastly, we provide an in-depth study of the underlying mechanism of electrochemicalcycling induced crystallization at the electrode-electrolyte interface through a combination of advanced synchrotron radiation characterization techniques and an in situ electrochemical reaction setup. We have discovered that (1) foreign cations from the electrolyte engender both tensile and compressive strains inside the crystal; (2) repeated electrode dissolution and redeposition promote crystal growth through a non-classical crystallization pathway of particle attachment, but the initial growth of crystals is inhibited by internal strains; and (3) as the strain accumulates, the crystal rotates or moves, which is the fundamental reason for the dynamic structure evolution of the crystal during electrochemical cycling. To our knowledge, this is the first study of electrochemical-cycling-induced crystallization and its strain evolution. These new findings reveal a previously unknown relationship between crystal growth and its internal strain at the electrode-electrolyte interface. / Doctor of Philosophy / Energy drives the entire economy and human civilization. Energy is needed in every aspect of everyday life, and energy is an essential raw material for making and delivering all the products and services that modern society needs, even though it is invisible to us. Since 2000, the global energy demand has increased tenfold and economic growth has spawned a large number of new energy industries, but billions of people are still in urgent need of clean water, sanitation, nutrition, and medical care. Energy is a key factor in meeting these basic requirements for all of humanity. The increasing global energy demand and the increasing impact of climate change have put enormous pressure on the energy market. Therefore, it is necessary to accelerate the relevant actions of energy transition in the world. Among them, the research and innovation of electrochemical energy storage and conversion technology is a major direction. The electrochemical energy storage and conversion technology heavily relies on the various electrochemical reactions in practical devices such as rechargeable batteries, water electrocatalysts, and energy-saving electrochromic smart windows. Within numerous electrochemical reactions under the application, the solid (electrode)-liquid (electrolyte) interface dominates the most important electrochemical reactions. How to understand thephysicochemical reactions at the interface under electrochemical conditions is of great significance. As a major component of research innovations, this research contributes to the design of rational electrode materials, electrolyte compositions, and more efficient and durable electrochemical performance. From a fundamental perspective, my research enriches the understanding of solid-liquid interface reactions under electrochemical conditions, pointing out that electrode dissolution and redeposition and dynamic structural evolution of solid-liquid interfaces are important for further optimizing electrode material design and improving electrochemical performance.

Made available in DSpace on 2017-07-24T19:38:03Z (GMT). No. of bitstreams: 1 Engelbert de Souza Folkuenig.pdf: 8804704 bytes, checksum: 956aed781c64725afe3d6dc23b53947c (MD5) Previous issue date: 2010-05-10 / Several electrochemical processes, such as electrocatalysis of organic substrates, make use of mediators. One of the mediators is the most commonly used anion methanesulfonate, CH3SO3, which has several advantages for such use, and chemical stability considered one of them. However, experimental studies indicate the possibility of this compound suffer the adsorption and decomposition on platinum electrodes. To get an understanding at the molecular level these processes, computer simulations were performed with the aid of the semi-empirical PM6. The cluster approach was used in the modeling of platinum surfaces with crystallographic orientations (111) and (100). The symmetries of most stable adsorption calculated for the anion in these areas correspond to the experimental data: C3V symmetry in (111) surface and C1 in (100) surface. To simulate the potential applied to the electrode, external electric fields with a positive sign and perpendicular to the surface of the clusters were applied. Changes in the lengths and angles of bonds adsorbed anion, as well as its values of dipole moment were observed. The infrared spectra of the systems anion-clusters were calculated and the values for the Stark tunning rate (Δstark) of mode δs CH3 were compared with the experimental value. Both for the free anion and for systems where the anion is adsorbed, it was found that the values of Δstark assumed negative values (indicating that the frequency of the vibrational mode δs CH3 diminished with increasing external eletric field), opposite to the experimental positive value (frequency mode δs CH3 increases with the increase in potential). Only with the addition of water molecules in the systems studied, in order to simulate the aqueous solvent is that the values of Δstark started to assume a positive value. The comparison showed the importance of the presence of water molecules in the simulation of an electrochemical system and prompted a detailed analysis of the frontier orbitals involved in this process. It was found that the dipole-dipole coupling between water molecules and the adsorbed anion is responsible for the Stark effect, while the electrostatic interactions between various molecules adsorbed anion affect the intensity of the absorption band mode δs CH3 in the spectra calculated. In (100) surfaces, the joint action of external field and water molecules, lead the anion molecule to adopt the adsorption geometries more inclined to systems without water molecules, indicating that this may be an important factor in explaining the greater reactivity of the anion on the surface. / Vários processos eletroquímicos, como por exemplo a eletrocatálise de substratos orgânicos, fazem uso de mediadores. Um dos mediadores mais utilizados é o ânion metanossulfonato, CH3SO3¯, que apresenta várias vantagens para tal uso, sendo a estabilidade química considerada uma delas. No entanto, estudos experimentais apontam para a possibilidade desse ânion sofrer processos de adsorção e decomposição em eletrodos de platina. Para se obter uma compreensão em nível molecular desses processos, simulações computacionais foram efetuadas com auxílio do método semi-empírico PM6. A aproximação de cluster foi utilizada na modelagem de superfícies de platina com orientações cristalográficas (111) e (100). As simetrias de adsorção mais estáveis calculadas para o ânion nessas superfícies correspondem aos dados experimentais: simetria C3v em superfície (111) e C1 em superfície (100). Para simular o potencial aplicado ao eletrodo, campos elétricos externos de sinal positivo e perpendiculares à superfície dos clusters foram aplicados. Alterações nos comprimentos e ângulos de ligações do ânion adsorvido, bem como em seus valores de momento dipolar foram observados. Os espectros de infravermelho dos sistemas ânion-clusters foram calculados e os valores para a taxa de variação Stark (Δstark) do modo δs CH3 foram comparados com o valor experimental. Tanto para o ânion livre quanto para os sistemas onde o ânion se encontra adsorvido, verificou-se que os valores de Δstark assumiam valores negativos (indicando que a frequência vibracional do modo δs CH3 diminuía com o aumento da intensidade do campo externo), ao contrário do valor experimental, positivo (frequência do modo δs CH3 aumenta com o aumento do potencial). Apenas com a adição de moléculas de água aos sistemas estudados, de modo a simular o solvente aquoso, é que os valores de Δstark passaram a assumir um valor positivo. Essa comparação revelou a importância da presença de moléculas de água na simulação de um sistema eletroquímico e motivou uma análise pormenorizada dos orbitais de fronteira envolvidos nesse processo. Verificou-se que a interação dipolo-dipolo entre as moléculas de água e o ânion adsorvido é o responsável pelo efeito Stark, enquanto as interações eletrostáticas entre várias moléculas do ânion adsorvidas afetam a intensidade da banda de absorção do modo δs CH3 nos espectros calculados. Nas superfícies (100), a ação conjunta do campo externo e das moléculas de água, levam a molécula do ânion a adotar geometrias de adsorção mais inclinadas em relação aos sistemas sem as moléculas de água, indicando que este pode ser um fator importante para explicar a maior reatividade do ânion sobre esse tipo de superfície.