Filmes de óxidos de molibdênio, com ou sem a inclusão de metais, foram eletroquimicamente depositados sobre eletrodos de carbono vítreo em solução de Mo(VI) com pH ajustado em 2,5 ou 3,0. Estes filmes foram caracterizados por Soft X-ray Spectroscopy (SXS), X-ray Diffraction (XRD) e Rutherford Backscattering Spectroscopy (RBS). A coordenação local dos sítios de Mo foram analizadas. As configurações estruturais locais do Mo foram avaliadas quando diferentes números de ciclos de potencial foram empregados na modificação dá superfície do eletrodo. Alguns metais (Pt, Pd, Rh e Cu) foram codepositados com as espécies de Mo e seu efeito nos materiais obtidos foi investigado. O grau de ocupação do orbital 4d do Mo foi examinado como um indicador da existência de interações entre o Mo e o metal codepositado. A incorporação de Pt no filme de óxidos na superfície de um eletrodo de ouro foi caracterizada por espectroscopia PIXE. O eletrodo modificado por óxidos de molibdênio foi estudado em faixas de potencial positivas frente à oxidação de nitrito (NO2-) e de óxido nítrico (NO). A relação entre a porosidade do filme e a presença de água em seus interstícios foi examinada e a capacidade de retenção de NO e NO2 foi também investigada. O eletrodo modificado foi usado como um sensor amperométrico em um sistema de injeção em fluxo (FIA) e o método foi empregado na determinação de nitrito em amostras de lingüiça. A oxidação de H2O2 foi investigada em superfície recoberta por filme de óxidos de Mo com Pt codepositada. O efeito do pH, do potencial e do tempo de pré-redução do filme de Pt e MoOx foi discutida. O comportamento eletroquímico dos filmes codepositados de Rh, Pd, Pt ou Cu e MoOx foi caracterizados comparativamente pela redução do iodato e pela oxidação do nitrito e do etanol nestes substratos. H4MogO26 foi empregado para preparar filmes contendo molibdênio e sua resposta eletroquímica foi comparada com as obtidas com o filme depositado por procedimento usual. O filme de óxidos de molibdênio foi usado com sucesso na imobilização de um complexos de Ru(III) na superfície de carbono vítreo. / Molybdenum oxide films with and without metal inclusion were electrochemically deposited on glassy carbon electrodes from Mo(VI) solutions at pH 2.5 or pH 3.0. These films were characterized by Soft X-ray Spectroscopy (SXS), X-ray Diffraction (XRD) and Rutherford Backscattering Spectroscopy (RBS). The local coordination of Mo sites was analyzed. The Mo local structure configurations were evaluated when different number of potential cycles were employed in the modification of the electrode surface. Some metaIs (Pt, Pd, Rh and Cu) were codeposited with the Mo species and their effect on the obtained material was investigated. The occupancy leveI of the 4d orbital of Mo was examined as an indicator of interactions between Mo and codeposited metals. The incorporation of Pt in the oxide film at a gold electrode surface was characterized by PlXE spectroscopy. The electrode modified by molybdenum oxides was studied at positive potential ranges for the oxidation of nitrite (NO2-) and nitric oxide (NO). The relationship between the porosity of the film and its water content was exarnined and the entrapment of NO and NO2 was also investigated. The modified electrode was used as an amperometric sensor in a flow injection configuration and the method was employed in the deterrnination of nitrite in sausage samples. The oxidation of H2O2 was investigated at surfaces covered by the Mo filrn with codeposited Pt. The effect of pH and potential and time of pre-reduction on the response of the film with Pt was discussed. The electrochemical behaviour of codeposited films of Rh, Pd, Pt or Cu and Mo MoOx was characterized comparatively for the reduction of iodate and the oxidation of nitrite and ethanol. 4MogO26 was also employed to prepare films containing molybdenum and their electrochemical responses were compared with those obtained by using the film electrodeposited by the usual procedure. The molybdenum oxide film was successfully used for the immobilization of Ru(III) complex at glassy carbon surfaces.

<p dir="ltr">Nanoparticles have seen immense development in the past several decades due to their intriguing physicochemical properties. The modern chemist is interested not only in methods of synthesizing nanoparticles with tunable properties but also in the chemistry that nanoparticles can drive. While several methods exist to synthesize nanoparticles, it is often advantageous to put nanoparticles on a variety of conductive substrates for multiple applications (such as energy storage and conversion). Despite enjoying over 200 years of development, the electrodeposition of nanoparticles suffers from a lack of control over nanoparticle size and morphology. Understanding that structure-function studies are imperative to understand the chemistry of nanoparticles, new methods are necessary to electrodeposit a variety of nanoparticles with control over macro-morphology but also microstructure. When a nanodroplet full of a metal salt precursor is incident on the electrode biased sufficiently negative to drive electroplating, nanoparticles form at a shocking rate (on the order of microseconds to milliseconds). We start with the general nuts-and-bolts of the experiment (nanodroplet formation and methods for electrodeposition). The deposition of new nanomaterials often requires one to develop new methods of measurement, and we detail new measurement tools for quantifying nanoparticle porosity and nanopore tortuosity within single nanodroplets. Owing to the small size of the nanodroplets and fast mass transfer, the use of nanodroplets also allows the electrodeposition of high entropy alloy nanoparticles at room temperature. Electrodeposition in aqueous nanodroplets can also be combined with stochastic electrochemistry for a variety of interesting studies. We detail the quantification of the growth kinetics of single nanoparticles in single aqueous nanodroplets. Nanodroplets can also be used as tiny reactors to trap only a few molecules, and the reactivity of those molecules can be electrochemically probed and evaluated with time. Overall, this burgeoning synthetic tool is providing unexpected avenues of tunability of metal nanoparticles on conductive substrates. Moreover, there is little understanding of how ion transfer can affect the fundamental of nanoparticle synthesis with nanodroplet-mediated electrodeposition. This thesis details different experiments performed to study the role of ion transfer during the nucleation and growth of nanoparticles.</p>

Despite the central importance of porous electrodes to any advanced electrochemical system, there is no clear answer to “<i>How to make the best electrode</i>?”. The source of ambiguity lies in the incomplete understanding of convoluted material interactions at smaller – difficult to observe length and timescales. Such mesoscopic interactions, however, abide by the fundamental physical principles such as mass conservation. The porous electrodes are investigated in such a physics-based setting to comprehend the interplay among structural arrangement and off-equilibrium processes. As a result, a synergistic approach exploiting the complementary characteristics of controlled experiments and theoretical analysis emerges to allow mechanistic insights into the associated mesoscopic phenomena. The potential of this philosophy is presented by investigating three distinct electrochemical systems with their unique peculiarities.