This dissertation explores the electrochemical behavior of enzymes and their cofactors at carbon nanotube (CNT) and nitrogen-doped carbon nanotube (N-CNT) electrodes. Two common types of oxidoreductases are considered: flavin adenine dinucleotide (FAD)-dependent oxidases and nicotinamide adenine dinucleotide-dependent (NAD⁺)-dehydrogenases. Chapter 1 presents the oxygen reduction reaction (ORR) at N-CNT electrodes as a way to electrochemically measure enzymatic turnover at the electrode surface. The unique peroxide pathway at N-CNT electrodes, which catalytically disproportionates hydrogen peroxide (H₂O₂) back into oxygen, provides an increased ORR current directly proportional to the rate of enzymatic turnover for H₂O₂ producing enzymes, even in an oxygen saturated solution. Biosensing of L-lactate using the increased ORR current is demonstrated using L-lactate oxidase. Chapter 2 explores the surface bound electrochemical signal of FAD when FAD-dependent enzyme or free FAD is allowed to spontaneously adsorb onto the CNT/N-CNT surface. Specifically, the origin of the enzymatically generated FAD signal and the rate constant of the electron transfer are elucidated. Chapter 3 continues the discussion of the cofactor FAD by demonstrating its use as an informative surface specific redox probe for graphitic carbon surfaces. Primarily, FAD can be used to determine the electroactive surface area and the relative hydrophobicity/hydrophilicity of graphitic surfaces. Chapter 4 changes gears to NAD⁺-dependent dehydrogenases by investigating the electrocatalytic oxidation of NADH at N-CNTs in comparison with conventional carbon electrodes or nondoped CNTs. Biosensing of glucose through the oxidation of NADH is demonstrated using glucose dehydrogenase adsorbed onto the N-CNT surface. Chapter 5 continues the discussion of NAD⁺-dependent dehydrogenases by addressing the reaction kinetics of NADH oxidation at N-CNTs as a tool to measure the enzymatic reduction of NAD⁺.

Carbon nanoparticles (CNPs) have drawn great attention in the last few years owing to their unique properties such as excellent water solubility, chemical stability, inertness, low toxicity, good bio-compatibility, and tunable photo physical properties. Recently, researchers have focused on hetero atom (N, S and B) doped CNPs due to their excellent properties. These properties make the CNPs and doped CNPs as potential candidates for a wide range of applications. For example, metal ion detection in aqueous solution, bio-imaging, bio-sensing, photovoltaic devices, cleavage of deoxyribonucleic acid (DNA), and catalysis. Therefore, CNPs are alternative to inorganic semiconductor nanoparticles. However, CNPs with diameter less than 10 nm have been prepared using various approaches including top down and bottom methods. Cutting the bulk carbon from high dimensional to zero dimensional by using either physical or chemical process are classified as top down method. Bottom up method refers the conversion of organic precursor to nano-carbon by using thermal pyrolysis, microwave based hydrothermal method, cage opening of C60 molecules. In the present work, I have dealt with the facile synthesis of CNPs and different hetero atom doped carbon nanoparticles (N-CNPs, B-CNPs, and BN-CNPs) using the hydrothermal method. Based on their intriguing physical and chemical properties, these CNPs/doped-CNPs have been explored for various applications such as (i) metal-free catalysts, (ii) color tunability from red to blue and bio-imaging, (iii) ammonia sensing, (iv) white light generation, and (v) detection of picric acid (PA) in aqueous solution. Finally, I have presented 3D nanodendrites of N-CNPs and Pd NPs and their excellent catalytic mass activity for methanol electro-oxidation and ultra-fast reduction of 4-nitrophenol.

O desenvolvimento de novos materiais para a aplicação em eletroanalítica, uma atividade extremamente atraente, visa produzir compostos com condutividade elétrica alta, estabilidade mecânica e química e grandes áreas superficiais. Assim, nesta tese foram desenvolvidos Carbonos Mesoporosos Ordenados, um tipo de material carbônico recentemente explorado para diversas aplicações devido às suas propriedades específicas e facilmente manipuláveis. A produção inicia-se com a síntese da sílica mesoporosa utilizada como template, seguida pela impregnação por molhamento incipiente utilizando moléculas que são concomitantemente, fontes de carbono e de um heteroátomo (S, N ou O). Após a polimerização e carbonização em atmosfera não-oxidante, removeu-se o template de sílica, obtendo-se um material altamente organizado de estrutura mesoporosa, caracterizado pelas análises de BET, MET e DRX em ângulos baixos. Os materiais sintetizados apresentaram área superficial grande e acessível, indicadas pelas as análises de BET, o que ofereceu uma alta eficiência de pré-concentração de analitos. A fim de garantir um carbono com características grafíticas e boa condutividade, partiu-se de fontes carbônicas aromáticas e utilizou-se o óxido de ferro como catalisador da polimerização. Com isso, obteve-se materiais com carácter grafítico, mostrado pelas análises de DRX e Raman, com excelentes propriedades elétricas e transferência eletrônica mais rápida, mostrado pelas análises eletroquímicas (VC e EIE) garantindo um material com excelente atividade eletrocatalítica. Os três diferentes tipos de dopagem geraram três materiais distintos, que diferem não apenas na composição química, mas também nas propriedades físicas, elétricas e em sua resposta eletroanalítica. Os materiais sintetizados foram aplicados na detecção do cloranfenicol, um antibiótico com propriedades antibacterianas e farmacocinéticas excelentes, porém proibido em produtos destinados ao consumo humano. A metodologia desenvolvida apresentou boa sensibilidade e limites de detecção e quantificação, além da capacidade de analisar diretamente leite em pó, sem a necessidade de etapas trabalhosas de preparo de amostra. / The development of new materials for electroanalitycal application aims to produce materials with high electric conductivity, mechanical and chemical stability, and high surface areas. So, in this thesis, it was developed Ordered Mesoporous Carbon, a carbonic material recently explored in several applications due its specific plasticity properties. The production starts with the mesoporous silica synthesis. It is used as template, followed by the incipient wetness impregnation using molecules that are both a carbon source and heteroatom precursor (S, N or O). After the polymerization and the non-oxidant atmosphere carbonization, the template was removed, what yielded a highy ordered mesoporous structure, demonstrated by BET, TEM and low-angle XRD analysis. The synthetized materials showed high and accessible surface area, demonstrated by BET, which allowed high pre-concentration efficiency with a fast diffusion process. In order to get a graphitic carbon with good conductivity, it was used aromatic carbon precursors and iron as polymerization catalyst. Consequently, a material with graphitic character was getting, as we can see at XRD and Raman, with excellent electric properties and faster electronic transference, showed by electrochemical analysis (CV and EIS), leading to a material with excellent electrocatalytic activity. The three different doping types leading to three distinct materials, which differ not only at chemical composition, but also at physical, electrics and electroanalytical properties. The materials was applied at chloramphenicol detection, an antibiotic with excellent antibacterial and pharmacokinetics properties. However, it is forbidden in edible products. The developed methodology has good sensibility, and limits of detection and quantification. In addition, was possible to analyze powder milk directly, without any other timing consuming procedure of sample preparing.

O desenvolvimento de novos materiais para a aplicação em eletroanalítica, uma atividade extremamente atraente, visa produzir compostos com condutividade elétrica alta, estabilidade mecânica e química e grandes áreas superficiais. Assim, nesta tese foram desenvolvidos Carbonos Mesoporosos Ordenados, um tipo de material carbônico recentemente explorado para diversas aplicações devido às suas propriedades específicas e facilmente manipuláveis. A produção inicia-se com a síntese da sílica mesoporosa utilizada como template, seguida pela impregnação por molhamento incipiente utilizando moléculas que são concomitantemente, fontes de carbono e de um heteroátomo (S, N ou O). Após a polimerização e carbonização em atmosfera não-oxidante, removeu-se o template de sílica, obtendo-se um material altamente organizado de estrutura mesoporosa, caracterizado pelas análises de BET, MET e DRX em ângulos baixos. Os materiais sintetizados apresentaram área superficial grande e acessível, indicadas pelas as análises de BET, o que ofereceu uma alta eficiência de pré-concentração de analitos. A fim de garantir um carbono com características grafíticas e boa condutividade, partiu-se de fontes carbônicas aromáticas e utilizou-se o óxido de ferro como catalisador da polimerização. Com isso, obteve-se materiais com carácter grafítico, mostrado pelas análises de DRX e Raman, com excelentes propriedades elétricas e transferência eletrônica mais rápida, mostrado pelas análises eletroquímicas (VC e EIE) garantindo um material com excelente atividade eletrocatalítica. Os três diferentes tipos de dopagem geraram três materiais distintos, que diferem não apenas na composição química, mas também nas propriedades físicas, elétricas e em sua resposta eletroanalítica. Os materiais sintetizados foram aplicados na detecção do cloranfenicol, um antibiótico com propriedades antibacterianas e farmacocinéticas excelentes, porém proibido em produtos destinados ao consumo humano. A metodologia desenvolvida apresentou boa sensibilidade e limites de detecção e quantificação, além da capacidade de analisar diretamente leite em pó, sem a necessidade de etapas trabalhosas de preparo de amostra. / The development of new materials for electroanalitycal application aims to produce materials with high electric conductivity, mechanical and chemical stability, and high surface areas. So, in this thesis, it was developed Ordered Mesoporous Carbon, a carbonic material recently explored in several applications due its specific plasticity properties. The production starts with the mesoporous silica synthesis. It is used as template, followed by the incipient wetness impregnation using molecules that are both a carbon source and heteroatom precursor (S, N or O). After the polymerization and the non-oxidant atmosphere carbonization, the template was removed, what yielded a highy ordered mesoporous structure, demonstrated by BET, TEM and low-angle XRD analysis. The synthetized materials showed high and accessible surface area, demonstrated by BET, which allowed high pre-concentration efficiency with a fast diffusion process. In order to get a graphitic carbon with good conductivity, it was used aromatic carbon precursors and iron as polymerization catalyst. Consequently, a material with graphitic character was getting, as we can see at XRD and Raman, with excellent electric properties and faster electronic transference, showed by electrochemical analysis (CV and EIS), leading to a material with excellent electrocatalytic activity. The three different doping types leading to three distinct materials, which differ not only at chemical composition, but also at physical, electrics and electroanalytical properties. The materials was applied at chloramphenicol detection, an antibiotic with excellent antibacterial and pharmacokinetics properties. However, it is forbidden in edible products. The developed methodology has good sensibility, and limits of detection and quantification. In addition, was possible to analyze powder milk directly, without any other timing consuming procedure of sample preparing.

Carbon nanotubes (CNTs) are a relatively new allotrope of carbon that possess very unique and exciting physical characteristics. However, much is still unknown regarding their physical structure and chemical reactivity. The focus of this dissertation is to utilize the chemical modification of these filamentous carbon structures as a probe to investigate the structure and reactivity of carbon nanotubes. Also discussed is the ability of CNTs, once chemically modified, to interact with specific polymer matrices and how the addition of modified and unmodified CNTs affects the physical properties of these matrices.

Les nanotubes de carbone (NTCs) dopés avec différents hétéroéléments tels que l'oxygène et l'azote connaissent un intérêt croissant dans le domaine de la catalyse hétérogène comme leur utilisation en tant que catalyseur sans métaux. L'objectif de cette thèse consiste à la synthèse et la caractérisation de matériaux catalytiques à base de NTC dopés à l'azote supportés sur du carbure de silicium SiC par voie in situ (CVD) et ex-situ méthodes. Une autre approche a été utilisée pour la fonctionnalisation de la surface des nanotubes de carbone et basées sur l'utilisation d'un agent oxydant (HNO3) en phase gazeuse. Ce procédé d'oxydation crée non seulement des défauts sur la surface des nanotubes de carbone mais également décore leur surface avec des groupes fonctionnels oxygénés. Les NTCs dopés à l'oxygène et à l'azote ainsi synthétisés ont été caractérisés par différentes techniques (XPS, MEB, MET, BET, ATG). Ces catalyseurs carbonés présentent des performances remarquables en termes d'activité et de sélectivité en soufre, et une très grande stabilité sous flux en fonction du temps dans la réaction d'oxydation partielle de l'H2S en soufre élémentaire, et ce, même à vitesse spatiale de gaz élevée (WHSV) et faible rapport O2/H2S. L'influence des différentes propriétés physico-chimiques et les défauts présents sur la surface des NTC sur les performances catalytiques ont été étudiée et discutée dans le cadre de ce travail. / Carbon nanotubes (CNTs) containing different doping such as oxygen and nitrogen composites have received more and more scientific attention as metal-free catalyst in the field of heterogeneous catalysis. The aim of this thesis is related to the synthesis and characterization of nitrogen-doped CNTs decorated on SiC support using both in-situ (CVD with NH3) and ex-situ (N@C) methods. Other approach was employed for the surface functionalization of CNTs is based on the use of oxidative agent (HNO3) in gas phase. This oxidation process not only creates defects on the CNTs surface but also decorates their surface with oxygenated functional groups. The as-synthesized oxygen- and nitrogen-doped CNTs are characterized by different techniques (XPS, SEM, TEM, BET, TGA). The carbon based catalysts exhibit outstanding performances in term of activity and sulfur selectivity, and very high stability with time on stream in the partial oxidation of H2S into elemental sulfur even at high gas space velocity (WHSV) and low O2-to-H2S molar ratio. The influence of the physical-chemical properties and defects present on the CNTs surface on the catalytic performance was thoroughly investigated and discussed within the framework of this work.

L'objectif de ce travail est la synthèse et l'étude des propriétés acido-basiques de nanotubes de carbone (CNT) dopés à l’azote pour les utiliser comme catalyseurs ou supports de catalyseurs. Pour ce faire, trois types de nanotubes de carbone dopés à l'azote ont été synthétisés, caractérisés et testés dans la conversion de l'alcool isopropylique. Les nanotubes de carbone dopés diffèrent par le taux d’azote et la présence ou non d'une section non dopée dans leur structure. Pour les matériaux à faible teneur en azote, la réaction conduit à la formation d'acétone indiquant la présence de sites basiques. À plus forte teneur en azote, les catalyseurs dopés conduisent à la formation d'acétone et de propène, mettant en évidence la présence de sites basiques et acides. La caractérisation par XPS nous a permis de proposer que les sites basiques sont constitués de groupes de surface pyridiniques et les sites acides sont des groupements sulfoniques formés au cours de la purification de ces matériaux avec de l'acide sulfurique. Des catalyseurs au ruthénium et au palladium supportés (2%) sur des nanotubes de carbone non dopés et dopés à l'azote (N-CNT), ont été préparés et évalués dans la réaction de décomposition de l'alcool isopropylique comme réaction test. La présence de fonctionnalités azotées (azote pyridinique, pyrrolique et quaternaire) sur le support dopé à l'azote induit une plus grande dispersion du métal. En ce qui concerne les catalyseurs supportés, ceux de palladium étaient plus actifs et plus sélectifs que ceux au ruthénium. De plus, les catalyseurs au Pd sont sélectifs en acétone, tandis que les catalyseurs au Ru conduisent à la déshydratation et la déshydrogénation. Le dopage des nanotubes de carbone par l’azote conduit aussi à l'apparition de propriétés d'oxydo-réduction. Enfin, nous avons montré que des nanotubes de carbone, constitués de deux sections différentes : une partie non dopée hydrophobe reliée à un segment hydrophile, sont amphiphiles. Nous les avons utilisés comme supports tensioactif de catalyseur au palladium. Ces nouveaux catalyseurs à base de Pd supporté ont été testés dans la réaction d'oxydation de plusieurs alcools en utilisant l'oxygène moléculaire en phase liquide. L'oxydation du 2- heptanol produit sélectivement la cétone correspondante, alors que l'oxydation de l'alcool benzylique est très sélective vis-à-vis de l'aldéhyde. Par ailleurs, l'oxydation de l'éthanol produit de l'acide acétique de manière sélective. / The objective of this work is the synthesis and the investigation of the acid and basicproperties of nitrogen doped carbon nanotubes (CNTs) able to be used as catalysts or catalystsupports. For this, three types of purified nitrogen doped CNTs were synthesized,characterized and tested for isopropyl alcohol conversion under nitrogen or air atmosphere,and compared to undoped CNTs. The N-doped CNTs differ from their nitrogen content andfrom the presence or not of undoped section in their structure. The reaction lead to theformation of acetone as the sole product on catalysts presenting no nitrogen or low nitrogencontent (< 2.8% w/w), pointing to the presence of basic sites. At higher nitrogen content, Ndopedcatalysts lead to the formation of acetone and propene, highlighting the presence ofboth basic and acids sites on such material. XPS characterization allow us to propose that thebasic sites consist in pyridinic surface groups and the acidic sites in sulfonic surface groupsformed during the purification of these material with sulfuric acid. Ruthenium and palladiumsupported catalysts (2% w/w) were prepared on nitrogen-doped and non-doped carbonnanotubes (N-CNT), and evaluated for the reaction of decomposition of isopropyl alcohol asprobe reaction. The presence of nitrogen functionalities (pyridinic, pyrrolic and quaternarynitrogen) on the nitrogen doped support induces a higher metal dispersion: 1.8 nm (Pd/NCNT)< 4.9 nm (Pd/CNT), and 2.4 nm (Ru/N-CNT) < 3.0 nm (Ru/CNT). As far as thesupported catalysts are concerned, the palladium ones were more active and more selectivethan the ruthenium ones. The Pd catalysts were selective towards acetone, whereas Rucatalysts lead to dehydration and dehydrogenation products. The nitrogen doping induces theappearance of redox properties, which appear when oxygen is present in the reaction mixture.Finally, we have shown that unique amphiphilic magnetic hybrid carbon nanotubes thatcontain on the same nanotube two different sections: a hydrophobic undoped part connectedto a hydrophilic N-doped segment are synthesized and used as tensioactive supports forpalladium catalysts. These new Pd-supported catalysts have been used in the alcoholoxidation reaction using molecular oxygen in the liquid phase. The oxidation of 2-heptanolproduces selectively the ketone, the oxidation of benzyl alcohol is very selective towards thealdehyde, and ethanol oxidation produces selectively acetic acid.

Nitrogen-doped carbon materials have garnered much interest due to their electrocatalytic activity towards important reactions such as the reduction of hydrogen peroxide. N-doped carbon materials are typically prepared and deposited on solid conductive supports, which can sometimes involve time-consuming, complex, and/or costly procedures. Here, nitrogen-doped screen-printed carbon electrodes (N-SPCEs) were fabricated directly from a lab-formulated ink composed of graphite that was modified with surface nitrogen groups by a simple soft nitriding technique. N-SPCEs prepared from inexpensive starting materials (graphite powder and urea) demonstrated good electrocatalytic activity towards hydrogen peroxide reduction. Amperometric detection of H2O2 using N-SPCEs with an applied potential of −0.4 V (vs. Ag/AgCl) exhibited good reproducibility and stability as well as a reasonable limit of detection (2.5 µM) and wide linear range (0.020 to 5.3 mM).

Studies of single, isolated nanoparticles provide better understanding of the structure-function relationship of nanoparticles since they avoid complications like interparticle distance and nanoparticle loading that are typically associated with collections of nanoparticles distributed on electrode supports. However, interpretation of results obtained from single nanoparticle immobilization studies can be difficult to interpret since the underlying nanoelectrode platform can contribute to the measured current, or the immobilization technique can adversely affect electron transfer. Here, we immobilized ligand-free gold nanoparticles on relatively electrocatalytically inert nitrogen-doped carbon ultramicroelectrodes that were prepared via a soft nitriding method. Sizes of the particles were estimated by a recently reported electrochemical method and were found to vary linearly with deposition time. The particles also exhibited electrocatalytic activity toward methanol oxidation. This immobilization strategy shows promise and may be translated to smaller nanoelectrodes in order to study electrocatalytic properties of single nanoparticles.

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