Conjugated polymers are organic polymers that can conduct electricity. They undergo a volume change upon redox reaction and can be used as an active material in some micro- actuator system. Micro-actuators are useful in biomedical and electronic application. We have fabricated a patterned Polypyrrole (PPy) trilayer microactuator device that has individually addressable microactuators (a micro walker) which can operate in air. Furthermore, the PPy trilayer microactuator device is fabricated using standard microfabrication method called photolithography to pattern PPy on PVDF membrane material. An etching process was used to achieve the patterning process. We presented the result of characterization of speed as a function of voltage and thickness of PPy film. Secondly, distance as a function of applied voltage and thirdly, the work density as a function of applied voltage. The procedures for fabrication of PPy microactuator device, using clean room facility is detailed in this thesis.

Dans cette étude, nous avons préparé deux matériaux composites conducteurs par le procédé d’électropolymérisation. Lebut de la première partie de la thèse était l’élaboration de films composites polyaniline /LiMn2O4 pour leur applicationcomme matériau de cathode dans les batteries lithium-ion. Les analyses par diffraction des rayons X, analyse EDX etspectrométrie IRTF ont confirmé l'incorporation de LiMn2O4 dans les films composites. Les analyses électrochimiquesdes films obtenus ont mis en évidence une conductivité plus élevée des films composites comparée à la conductivité desfilms de PANI. La deuxième partie a été consacrée à la préparation de l’oxyde de graphène (OG) à partir de graphiteselon 2 méthodes de synthèse dérivées de la méthode de Hummers. Les résultats obtenus ont montré que le de gréd’oxydation des feuillets n’était pas le seul critère à prendre en compte pour évaluer la stabilité du OG dans l’eau. Lesfeuillets d’OG obtenus ont été incorporés à la polyaniline par électropolymérisation d’une suspension d’OG et d’anilineen milieu neutre. Le milieu électrolytique neutre conduit à des chaînes oligomères de PANI de faible masse molaire avecune proportion significative d’unités aromatiques mono et 1,2-disubstituées dans la structure finale. Différents substratsmétalliques ont été testés et les films ont été en particulier déposés sur fer afin d’évaluer leur protection anticorrosion. / In this study, we prepared two conductive composite materials based on polyaniline (PANI) byelectrodeposition. First, we investigated the development of new polyaniline/LiMn2O4 composite films forapplication as cathode material in lithium-ion batteries. Analysis by X-ray diffraction, EDS analysis and FTIRspectroscopy confirmed the incorporation of LiMn2O4 in composite films. The electrochemical analysis of thefilms obtained showed a higher conductivity of the composite films compared to the conductivity of the filmsof PANI. The second part was devoted to the preparation of oxidized graphene (GO) from graphite by 2methods of synthesis derived from the method of Hummers. The results showed that the degree of oxidation ofthe graphene sheets was not the only criterion in assessing the stability of GO in water. Electropolymerizationof aniline in a neutral electrolyte containing GO sheets was carried out to prepare PANI-GO composite films.The neutral electrolytic medium leads to PANI oligomer chains of low molecular weight with a significantproportion of aromatic mono units and 1,2-di-substituted units in the final structure. The electrodeposition wasperformed on inert and oxidizable metals. The corrosion protection efficiency of PANI/GO composite filmswas studied in HCl corrosion medium.

The design, synthesis, characterization and application of carbene-based metallopolymers are described herein. Metallopolymers have found wide applications in the fields of photovoltaics, energy storage and electrochromic windows. The incorporation of N-heterocyclic carbene (NHC) functionalities into a polymerizable scaffold would allow for many different metals to be attached in a facile and high-yielding manner. Such complexes could be functionalized onto surfaces and utilized as either spectroscopic or antimicrobial devices. Early attempts in our lab focused on utilizing bis(thiophene) diimines (instead of NHCs) as scaffolds for metal chelation and polymerization. This approach was unsuccessful due to the lability of the diimine moiety under electrochemical cycling and the thiophene moieties were not able to undergo polymerization. In order to more fully understand the key transformation in synthesizing the thiophene-substituted diimines, a comprehensive investigation of the aldimine coupling transformation was undertaken. A high concentration of substrate and catalyst was determined to be the most important factor in obtaining high yields of the dimerized products. Green solvents such as acetonitrile and hexanes could be used for the dimerization reaction when the cyanide counteranion was changed from sodium to tetrabutylammonium. The steric limitations were systematically identified and a series of possible substrates have been ruled out as viable candidates for dimerization. Applying the experience gleaned from earlier reports, the first example of an NHC polymer was prepared in which the monomer features an NHC functional group orthogonally connected to its main chain. A polymerizable imidazolylidene-AuCl complex containing pendant bithiophene moieties was prepared by a high yielding, multistep procedure. Oxidative electropolymerization of this monomer afforded the desired polymer (Au[NHC]Cl)n, which was characterized on the basis of electrochemical studies as well as by X-ray crystallography, photoelectron and UV-vis spectroscopy. The methodology described above was expanded to develop a series of analogous poly(N-heterocyclic carbene) complexes with appended entities (M = Ir, Au, Ag, or S)and found to be electrochromic. Most of the polymers exhibit an intense absorbance wave at 700 nm under oxidative conditions which is attributable to the formation of polaron excitations along the polymer main chain. The presence of a transition metal significantly increased the electrochromic character of the polycarbene system. The iridium-containing polymer was found to possess significant near-infrared (NIR) absorbance at 1100 nm in which the metal moiety effectively functions as an electron sink. Electrochemical analysis of the polymer thin films revealed that they exhibit highly reversible electrochromic activities. / text

Glucose and other carbohydrates are some of the most abundant renewable energy sources in the world. The oxidation of carbohydrates in a fuel cell allows their chemical energy to be converted directly into electrical energy. Viologen has been indentified and shows promising ability as an electron-transfer catalyst or mediator for carbohydrate oxidation in an alkaline carbohydrate fuel cell. Building on the previous results, the objective of this work was to develop an immobilization chemistry of viologen onto an electrode and to investigate the catalytic activity for carbohydrate oxidation in direct carbohydrate fuel cells.The immobilization was achieved by electropolymerizing a novel viologen monomer onto an electrode surface. The novel viologen monomer, which functions as a monosubstituted viologen, was synthesized and isolated in-house. Gold-plated nickel wire and graphite disks were used as the substrates for the electropolymerization. SEM, EDAX, XPS and water-contact-angle measurement were used to verify the formation of the coating on the gold and graphite surfaces. The catalytic activity of the immobilized viologen on graphite disk surface was examined using a fuel-cell-like device. The test was operated within the desired pH range for an operating fuel cell; it was found that the immobilized viologen polymer has a low catalytic activity toward oxidizing carbohydrates. In addition, the electrochemical properties of the novel viologen monomer were investigated by the method of cyclic voltammetry, as well as for that of two aminoviologens synthesized in-house. Redox potentials, diffusion coefficients, and heterogeneous electron-transfer rate constants were determined.

Metalopolimeros são considerados excelentes materiais para a construção de eletrodos modificados quimicamente devido ao fato de apresentar propriedades essenciais, como por exemplo, uma alta atividade eletrocatalítica, eletroluminescia, aplicações na área da eletroquímica e eletroanalítica em atividades de eletrocatálise, quimioresistores, fotoeltrocatálise e desenvolvimento de sensores, respectivamente. Alguns complexos de metais de transição contendo Bases de Schiff como ligantes exibem propriedades eletrônicas não convencionais, que têm sido extensivamente estudadas para a aplicação no desenvolvimento de modelos sintéticos aos compostos biológicos como as metaloproteínas e metaloenzimas. O intuito principal desta tese foi o estudo da síntese, otimização e aplicação do nano-metalopolimero à base de poli[Ni(Salpn)] como plataforma sensorial eletroquímica, visando a obtenção de melhoras significativas em determinadas propriedades estruturais, catalíticas, dentre outras. Essas propriedades dependem, não somente do comportamento molecular, mas também, dos efeitos dos possíveis rearranjos estruturais devido às interações intermoleculares. Desta forma, foi construído e estudado o desempenho eletroquímico de uma plataforma sensorial à base de eletrodos constituídos com filmes poliméricos, sendo possível a avaliação de suas aplicações na determinação de substâncias com importância analítica nas áreas clínica, farmacêutica e ambiental. No âmbito que tange a síntese e caracterização do complexo Ni(Salpn), foi possível confirmar por meio de técnicas de caracterização de materiais a eficiência do métodos utilizados. Analogamente, a eletropolimerização foi realizada com sucesso, obtendo nano-filmes com espessura aproximada 110 nm com ótima atividade eletroquímica. A avaliação na aplicação do nano-metalopolímero poli[Ni(Salpn)] apresentou uma excelente resposta frente ao H2O2, possuindo uma rápida resposta, um intervalo linear de 49,9 a 1480 μmol L-1, com limite de detecção de 7,68 μmol L-1 e sensibilidade de 24,05 μÅ mmol-1, viabilizando assim a construção de uma plataforma sensorial viável, rápida, precisa e exata, com a finalidade de resolução de problemas analíticos. / Metalopolymers are considered to be excellent materials for the construction of chemically modified electrodes due to the fact that they present essential properties, such as high electrocatalytic activity, electroluminescence, electrochemical and electroanalytical applications in electrocatalysis, chemoresistors, photoeltrocatalysis and sensor development, respectively. Some transition metal complexes containing Schiff Bases as binders exhibit unconventional electronic properties which have been extensively studied for application in the development of synthetic models for biological compounds such as metalloproteins and metalloenzymes. The most aim of this thesis was to study the synthesis, optimization and application of nano-metallopolymer based on poly [Ni(Salpn)] as an electochemical sensorial platform, aiming at obtaining significant improvements in certain structural, catalytic properties, among others. These properties depend not only on molecular behavior but also on the effects of possible structural rearrangements due to intermolecular interactions. In this way, the electrochemical performance of a sensorial platform based on electrodes made with polymer films was constructed and studied, being possible the evaluation of its applications in the determination of substances with analytical importance in the clinical, pharmaceutical and environmental areas. In terms of the synthesis and characterization of the Ni(Salpn) complex, it was possible to confirm by means of techniques of material characterization the efficiency of the methods used. Analogously, the electropolymerization was performed successfully, obtaining nano-films with a thickness of approximately 110 nm with excellent electrochemical activity. The evaluation in the application of the poly[Ni(Salpn)] nano-metallopolymer showed an excellent response against H2O2, having a fast response, a linear range of 4.99 x 10-5 to 1.48 x 10-3 mol L-1, with detection limit of 7.68 x 10-6 mol L-1 and sensitivity of 24,05 μmol mmol-1, thus making possible the construction of a viable, fast, precise and accurate sensorial platform for the purpose of resolution of analytical problems.

Líquidos Iônicos eletropolimerizáveis são caracterizados como líquidos iônicos que possuem um grupo eletropolimerizável ligado ao cátion ou ânion, a partir da eletropolimerização destes líquidos iônicos ocorre a imobilização dos íons em uma estrutura polimérica. Neste trabalho é apresentado a síntese de um líquido iônico eletropolimerizável onde anilina foi introduzida como grupo eletropolimerizante no cátion metil-imidazólio. Várias metodologias foram testadas para a eletropolimerização deste líquido iônico, envolvendo a utilização de solventes orgânicos e líquidos iônicos como eletrólitos. A copolimerização com anilina mostrou-se eficiente para obtenção de filmes poliméricos com a presença do monômero sintetizado. A influência deste monômero presente no copolímero foi estudada em relação ao comportamento eletroquímico, demonstrando o aumento da eletroatividade do polímero em líquidos iônicos apróticos. Em relação à morfologia, observou-se que a presença do monômero produz filmes mais compactos diferentemente da polianilina que apresenta uma morfologia dendrítica. Os processos eletrocrômicos para o copolímero não sofrem defasagem em relação aos processos eletroquímicos como observados na polianilina. Os processos redox do material foram acompanhados por EQCM-D demonstrando que a compensação de carga ocorre a partir do fluxo de cátions. Assim a presença monômero sintetizado no copolímero afeta o comportamento da polianilina, assim como qualquer substituinte volumoso, porém o copolímero apresenta propriedades intrínsecas de líquidos iônicos, demonstrando a formação de um material multifuncional. / Electropolymerizable lonic liquids have groups that are susceptible to electropolymerization bounded either to the cationic or anionic structure. In such cases, the ionic species can be immobilized into a polymeric matrix. This work presents the synthesis of an electropolymerizable ionic liquid in which aniline was inserted as the eletrocpolymerizable group in methyl-imidazolium. Several methods were tested for the electropolymerization, involving the use of organic solvents or ionic liquids as electrolytes. The copolymerization with aniline units was effective to obtain polyrnenc films in the presence of the synthesized monomer. The influence of the monomer in the copolymer was studied with respect to the electrochemical behavior, showing the increasing of the polymer electroactivity in aprotic ionic liquid electrolyte. The presence of the monomer produces more compact films than polyaniline which presents a dendritic morphology. The spectroeletrochemical processes for the copolymer do not suffer lag in relation to electrochemical processes as observed in polyaniline. The redox processes were monitored by EQCM-D demonstrating that the charge compensation takes place from the flow of cations. The presence of the synthesized monomer in the copolymer affects the behavior of polyaniline, as well as any substituent in the aniline, however the copolymer shows intrinsic properties of ionic liquids, demonstrating the formation of a multifunctional material

Líquidos Iônicos eletropolimerizáveis são caracterizados como líquidos iônicos que possuem um grupo eletropolimerizável ligado ao cátion ou ânion, a partir da eletropolimerização destes líquidos iônicos ocorre a imobilização dos íons em uma estrutura polimérica. Neste trabalho é apresentado a síntese de um líquido iônico eletropolimerizável onde anilina foi introduzida como grupo eletropolimerizante no cátion metil-imidazólio. Várias metodologias foram testadas para a eletropolimerização deste líquido iônico, envolvendo a utilização de solventes orgânicos e líquidos iônicos como eletrólitos. A copolimerização com anilina mostrou-se eficiente para obtenção de filmes poliméricos com a presença do monômero sintetizado. A influência deste monômero presente no copolímero foi estudada em relação ao comportamento eletroquímico, demonstrando o aumento da eletroatividade do polímero em líquidos iônicos apróticos. Em relação à morfologia, observou-se que a presença do monômero produz filmes mais compactos diferentemente da polianilina que apresenta uma morfologia dendrítica. Os processos eletrocrômicos para o copolímero não sofrem defasagem em relação aos processos eletroquímicos como observados na polianilina. Os processos redox do material foram acompanhados por EQCM-D demonstrando que a compensação de carga ocorre a partir do fluxo de cátions. Assim a presença monômero sintetizado no copolímero afeta o comportamento da polianilina, assim como qualquer substituinte volumoso, porém o copolímero apresenta propriedades intrínsecas de líquidos iônicos, demonstrando a formação de um material multifuncional. / Electropolymerizable lonic liquids have groups that are susceptible to electropolymerization bounded either to the cationic or anionic structure. In such cases, the ionic species can be immobilized into a polymeric matrix. This work presents the synthesis of an electropolymerizable ionic liquid in which aniline was inserted as the eletrocpolymerizable group in methyl-imidazolium. Several methods were tested for the electropolymerization, involving the use of organic solvents or ionic liquids as electrolytes. The copolymerization with aniline units was effective to obtain polyrnenc films in the presence of the synthesized monomer. The influence of the monomer in the copolymer was studied with respect to the electrochemical behavior, showing the increasing of the polymer electroactivity in aprotic ionic liquid electrolyte. The presence of the monomer produces more compact films than polyaniline which presents a dendritic morphology. The spectroeletrochemical processes for the copolymer do not suffer lag in relation to electrochemical processes as observed in polyaniline. The redox processes were monitored by EQCM-D demonstrating that the charge compensation takes place from the flow of cations. The presence of the synthesized monomer in the copolymer affects the behavior of polyaniline, as well as any substituent in the aniline, however the copolymer shows intrinsic properties of ionic liquids, demonstrating the formation of a multifunctional material

Metalopolimeros são considerados excelentes materiais para a construção de eletrodos modificados quimicamente devido ao fato de apresentar propriedades essenciais, como por exemplo, uma alta atividade eletrocatalítica, eletroluminescia, aplicações na área da eletroquímica e eletroanalítica em atividades de eletrocatálise, quimioresistores, fotoeltrocatálise e desenvolvimento de sensores, respectivamente. Alguns complexos de metais de transição contendo Bases de Schiff como ligantes exibem propriedades eletrônicas não convencionais, que têm sido extensivamente estudadas para a aplicação no desenvolvimento de modelos sintéticos aos compostos biológicos como as metaloproteínas e metaloenzimas. O intuito principal desta tese foi o estudo da síntese, otimização e aplicação do nano-metalopolimero à base de poli[Ni(Salpn)] como plataforma sensorial eletroquímica, visando a obtenção de melhoras significativas em determinadas propriedades estruturais, catalíticas, dentre outras. Essas propriedades dependem, não somente do comportamento molecular, mas também, dos efeitos dos possíveis rearranjos estruturais devido às interações intermoleculares. Desta forma, foi construído e estudado o desempenho eletroquímico de uma plataforma sensorial à base de eletrodos constituídos com filmes poliméricos, sendo possível a avaliação de suas aplicações na determinação de substâncias com importância analítica nas áreas clínica, farmacêutica e ambiental. No âmbito que tange a síntese e caracterização do complexo Ni(Salpn), foi possível confirmar por meio de técnicas de caracterização de materiais a eficiência do métodos utilizados. Analogamente, a eletropolimerização foi realizada com sucesso, obtendo nano-filmes com espessura aproximada 110 nm com ótima atividade eletroquímica. A avaliação na aplicação do nano-metalopolímero poli[Ni(Salpn)] apresentou uma excelente resposta frente ao H2O2, possuindo uma rápida resposta, um intervalo linear de 49,9 a 1480 μmol L-1, com limite de detecção de 7,68 μmol L-1 e sensibilidade de 24,05 μÅ mmol-1, viabilizando assim a construção de uma plataforma sensorial viável, rápida, precisa e exata, com a finalidade de resolução de problemas analíticos. / Metalopolymers are considered to be excellent materials for the construction of chemically modified electrodes due to the fact that they present essential properties, such as high electrocatalytic activity, electroluminescence, electrochemical and electroanalytical applications in electrocatalysis, chemoresistors, photoeltrocatalysis and sensor development, respectively. Some transition metal complexes containing Schiff Bases as binders exhibit unconventional electronic properties which have been extensively studied for application in the development of synthetic models for biological compounds such as metalloproteins and metalloenzymes. The most aim of this thesis was to study the synthesis, optimization and application of nano-metallopolymer based on poly [Ni(Salpn)] as an electochemical sensorial platform, aiming at obtaining significant improvements in certain structural, catalytic properties, among others. These properties depend not only on molecular behavior but also on the effects of possible structural rearrangements due to intermolecular interactions. In this way, the electrochemical performance of a sensorial platform based on electrodes made with polymer films was constructed and studied, being possible the evaluation of its applications in the determination of substances with analytical importance in the clinical, pharmaceutical and environmental areas. In terms of the synthesis and characterization of the Ni(Salpn) complex, it was possible to confirm by means of techniques of material characterization the efficiency of the methods used. Analogously, the electropolymerization was performed successfully, obtaining nano-films with a thickness of approximately 110 nm with excellent electrochemical activity. The evaluation in the application of the poly[Ni(Salpn)] nano-metallopolymer showed an excellent response against H2O2, having a fast response, a linear range of 4.99 x 10-5 to 1.48 x 10-3 mol L-1, with detection limit of 7.68 x 10-6 mol L-1 and sensitivity of 24,05 μmol mmol-1, thus making possible the construction of a viable, fast, precise and accurate sensorial platform for the purpose of resolution of analytical problems.

Polymeric membranes typically possess a broad pore-size distribution that leads to much lower selectivity in molecular and ionic separation when compared to membranes made of crystalline porous materials; however, they are highly desirable because of their easy processability and low cost. Recently, a novel type of conjugated microporous polymers (CMPs) has shown uniform pore size and high porosity. However, their brittleness nature has prevented them from preparing robust membranes and using in pressure-driven membrane processes. In this dissertation, we demonstrate the fabrication of robust polycarbazole-type conjugated microporous polymer membranes using an easy to scale-up electropolymerization strategy. The mechanical properties of the CMP membranes were greatly enhanced based on membrane structure optimization and molecular design. The prepared membranes exhibited high uniform sub-nanometer pores and a precisely tunable membrane thickness and properties, yielding high molecular/ionic sieving performance. In addition, using the co-electropolymerization method, the CMP membranes achieve dual softness and functionalization adjustments. The membrane structure comprises rigid monomers to inherit the structural uniformity and flexible and charged monomers to enhance mechanical flexibility and improve ion selectivity by combining the precise size sieving and the Donnan effect. The dual-adjustments result in the further enhancement of the CMP membranes in ionic sieving performance. Inspired by light-gated ion channels in living cells, we further develop a smart artificial light-gated ion channel membrane. The prepared CMP membranes, based on a conjugated microporous polymer (CMP) functionalized with azobenzene and precisely designed on the molecular level, show uniform pore channels and highly sensitive light-switchable response. The photoisomerization results in reversible geometric changes in pore channel size, leading to “on-off-on” light-control over the channels, which results in light-gated ion transport across the smart membrane. The softness adjustment, functionalization adjustment to CMP membranes, and the design of smart CMP membranes provide potential applications for this important category of polymer materials in the membrane field.

In this research, different anionic dopants were investigated for the fabrication of polypyrrole (PPy) electrode materials for electrochemical capacitors (ECs). Anionic dopants from catechol, salicylic acid and chromotropic acid family allowed for the formation of adherent PPy thin film on stainless steels current collectors by electropolymerization. Comparison between galvanostatic and pulse electropolymerization of PPy thin films was made. Pulse electropolymerization was found to provide improved impregnation of Ni plaque current collectors and formation of nanostructured coating. The electrodes prepared by pulse electropolymerization showed higher porosity, lower electrical resistance, higher capacitance and improved cyclic stability. In order to overcome the mass loading limitation for thin film PPy electrodes, chemical polymerization of PPy was investigated. The use of fine particles, prepared by the chemical polymerization method, allows impregnation of Ni foams and fabrication of porous electrodes with high materials loading. Moreover, improved capacitive performance and cyclic stability was obtained for PPy electrodes with high materials loading using new anionic dopants. To further improve the cyclic stability of PPy electrodes, multiwalled carbon nanotubes (MWCNT) were used for the fabrication of PPy-MWCNT composite materials due to their high surface area and excellent conductivity. Different dispersants as well as dispersing methods were studied in order to obtain stable MWCNT suspensions. Among those dispersants, multifunctional anionic dopants were found to benefit the formation of MWCNT suspension as well as the polymerization of PPy. A conceptually new approach has been developed for the fabrication of PPy coated MWCNT based on the use of multifunctional anionic dopants. The use of PPy coated MWCNT allowed excellent electrochemical performance for high active mass loadings, required for commercial EC applications. The electrodes and devices made of PPy coated MWCNT showed high capacitance, good capacitance retention at high charge-discharge rates and good cycling stability. The record high capacitance achieved at high charge-discharge rates is promising for the development of high power ECs. / Thesis / Doctor of Philosophy (PhD)