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Les polydiacétylènes sont des polymères π-conjugués, obtenus par polymérisation topochimique à l'état solide de motifs diacétyléniques, sous l'effet d'un stimulus thermique ou photochimique. Depuis leur découverte en 1969 par Wegner, les polydiacétylènes ont fait l'objet de nombreux travaux de recherche. Ces travaux ont consisté tout d'abord à élucider le mécanisme de polymérisation, puis à étudier les diverses propriétés photophysiques, optiques, et électroniques des polymères. Néanmoins, la plupart des diacétylènes étudiés ne possédaient pas de substituants susceptibles d'être modifiés chimiquement. Le premier chapitre de cette thèse décrit la synthèse de nouvelles molécules diacétyléniques symétriques comportant des groupements azoles, et l'étude de leur polymérisation à l'état solide. La modification de l'organisation des motifs diacétyléniques.par interaction avec des molécules capables de former des liaisons hydrogène, et l'incorporation de ces motifs dans des matériaux hybrides organiques-inorganiques de type,. MOF ont également été examinées.Dans le deuxième chapitre, nous nous sommes intéressés aux composés diacétyléniques dicationiques fonctionnalisés par des groupements triéthylammoniums, imidazoliums et benzimidazoliums. La synthèse de ces composés, leur caractérisation spectroscopique, et cristallographique, ainsi que l'étude de leur réactivité thermique et photochimique ont été réalisées.Dans le troisième chapitre, nous proposons une méthode directe de préparation de carbone dopé à l'azote par pyrolyse des molécules diacétyléniques neutres, ainsi que la synthèse de carbone mésoporeux en présence d'un sel métallique. Un autre aspect de ce chapitre est l'optimisation des teneurs en azote en utilisant comme précurseurs les composés diacétyléniques dicationiques, associés à des anions riches en azote, notamment l'anion dicyanamide [dca] et tricyanométhide [tcm]. / Diacetylenes (DA) are unusual molecules owing to their ability to polymerize in the solid state. Such a polymerization is triggered off thermally or photochemicaly, and leads to the formation of enyne structures. Since their discovery in 1969 by Wegner, polydiacetylenes (PDA) have been the focus of much attention. Initially, many studies were devoted to elucidating the mechanism of polymerization, then assessment of the diverse photophysical, optical, and electronic properties of the polymers became the main goal. Yet, the vast majority of the DA that were studied did not possess substituents that could be modified chemicallyThe first chapter describes the synthesis of new symmetrical diacetylenic molecules functionalized with azole substituents and the study of the polymerization of these compounds in the solid state. Then, we present the modification of the organization of these diacetylenes by the interaction with molecules capable of forming hydrogen bonds, and the use of these molecules as ligands for the synthesis of Metal Organic Frameworks (MOF).The second chapter is devoted to the synthesis, characterization and crystallographic study of ionic diacetylenic compounds bearing triethylammonium, imidazolium and benzimidazolium groups. The photochemical and thermal behaviors of these DA have been tested.In the third chapter, we propose a straightforward route to N-doped graphitic carbon by direct pyrolysis of neutral diacetylenic precursors, and investigate the possibility of forming porous materials by adding a metal salt as a catalyst. Furthermore, another aspect of this chapter was to optimize the nitrogen content of these materials by using dicationic DA with N-rich anions, e.g. dicyanamide [dca] and tricyanomethide [tcm].

Graphitic carbon nitride (g-C3N4) heterojunction composites with the semiconducting metal oxides, CeO2, ZnO and TiO2 are prepared in situ by co-calcination of the precursor materials or by a solvothermal method. The structural, morphological and the optical properties of the prepared materials are studied using various microscopy and spectroscopy techniques. The synthesized composite materials, CeO2/g-C3N4, ZnO/g-C3N4 and TiO2/g-C3N4 are more efficient in the photocatalytic degradation of the water pollutants indigo carmine (IC) and atrazine than the pure metal oxide, g-C3N4, or their physical mixtures. The CeO2/g-C3N4 and ZnO/g-C3N4 composites also exhibit improved degradation efficiencies of atrazine as compared to the individual metal oxide or g-C3N4 materials. The improved photocatalytic activity of the composites are attributed to the effective electron-hole charge separation within composite heterojunction, resulting from the well matched energy levels of the metal oxide and g-C3N4. This strategy could be helpful for the synthesis of other metal oxide and g-C3N4 composites for photocatalytic applications.

Ce travail de doctorat a été réalisé dans le cadre d'un accord de cotutelle international entre l'Université de Salento (L3, Italie) et l'Université de Paris 13 (LSPM, France). L'objectif principal était la fabrication de contacts ohmiques sur des surfaces de diamant pour des applications telles que les détecteurs et les dispositifs de l’électronique. Les travaux au L3 ont été consacrés à l'étude du processus de graphitisation du diamant induit par laser afin de produire des électrodes de graphite sur des diamants intrinsèques. L'étude se concentre en particulier sur le développement d’un appareil expérimental pour l’écriture laser sur diamant tant sur les aspects matériel que logiciel, et un protocole a ainsi été développé pour la fabrication de contacts graphitiques segmentés sur de larges surfaces de diamant (cm²). Des travaux approfondis de caractérisation ont démontré la transition de phase diamant-graphite et le comportement ohmique pour les contacts électriques avec une résistivité de l'ordre de 10⁻⁵ Ω.m. Des détecteurs tout-carbone ont ainsi été développés et testés avec des faisceaux électroniques et positroniques de 450 MeV. Ils permettent d’ouvrir des perspectives en tant que cible active pour de nouvelles expériences de physique des hautes énergies (PADME) dans le cadre de l’étude de la matière noire. Le travail au LSPM a été consacré au développement d'un protocole permettant d'obtenir des contacts ohmiques sur des films diamant faiblement dopé au bore et terminé oxygène, élaborés par MPACVD. Les procédés de fabrication de contacts métalliques Ti/Au sur une structure mesa ainsi que l’implantation par des ions He, ont été développés afin d'induire une couche de graphite juste en dessous de la surface de diamant. Les mesures électriques sur des diamants légèrement dopés ([B] = 4 × 10¹⁷ cm⁻³) avec seulement des contacts métalliques ou graphitiques / métalliques ont montré que la présence de la couche graphitique rend les contacts ohmiques et conduisent à une résistance spécifique de contact égale à 3.3 × 10⁻⁴ Ω.cm². / This PhD work has been carried out in international cotutelle agreement between the University of Salento (L3, Italy) and the University of Paris 13 (LSPM, France). The main aim was the manufacturing of ohmic contacts on diamond surface for detector and electronic device applications. The work at L3 was dedicated to the laser-induced diamond graphitization process in order to produce graphitic electrodes on intrinsic diamonds. An experimental set-up dedicated to the laser writing technique on diamond has been developed in both hardware and software aspects and a protocol for the manufacturing of segmented graphitic contacts on diamond surface of large scale (cm²) has been implemented. An extensive characterization work has demonstrated the diamond-graphite phase transition and an ohmic electrical behaviour for the contacts with a resistivity of the order of ≈ 10⁻⁵ Ω.m. Eventually, an all-carbon detector has been developed and tested with 450 MeV electron and positron beams proving to be a good candidate in the role of active target for a new high-energy experiment (PADME) in the framework of the dark matter. The work at LSPM has been dedicated to the development of a protocol allowing reaching ohmic contacts on lightly boron doped diamond with oxygenated surface grown by MPACVD. The fabrication of Ti/Au metallic contact above a mesa structure has relied on a He ion implantation treatment to induce a graphitic layer underneath the diamond surface. The electrical measurements on lightly doped diamonds ([B] = 4 × 10¹⁷ cm⁻³) with metal or graphite / metal contacts have shown that the graphitic layer makes ohmic the contacts leading to a specific contact resistance as low as 3.3 × 10⁻⁴ Ω.cm². / Questo dottorato di ricerca è stato svolto in convenzione di cotutela internazionale tra l’Università del Salento (L3, Italia) e l’Università di Parigi 13 (LSPM, Francia). Il principale obiettivo è stato la fabbricazione di contatti ohmici su superficie di diamante per applicazioni come rivelatori e dispositivi elettronici. Il lavoro a L3 è stato dedicato allo studio del processo di grafitizzazione del diamante indotto da laser al fine di produrre elettrodi grafitici su diamanti intrinseci. In particolare, è stato sviluppato un apparato sperimentale dedicato alla tecnica di scrittura laser su diamante sia nelle componenti hardware che software, ed è stato realizzato un protocollo per la fabbricazione di contatti grafitici segmentati su superfici di diamante di grande scala (cm²). Un ampio lavoro di caratterizzazione ha dimostrato la transizione di fase diamante-grafite e il comportamento ohmico per i contatti elettrici con una resistività dell’ordine di 10⁻⁵ Ω.m. Pertanto, un rivelatore costituito solo di carbonio è stato sviluppato e testato con fasci elettronici e positronici di 450 MeV risultando essere un buon candidato nel ruolo di bersaglio attivo per un nuovo esperimento di fisica delle alte energie (PADME) nel contesto della materia oscura. Il lavoro a LSPM è stato dedicato allo sviluppo di un protocollo che ha consentito di ottenere contatti ohmici su diamanti leggermente drogati con boro e con superficie terminata con ossigeno, cresciuti mediante MPACVD. I processi di fabbricazione di contatti metallici Ti/Au sopra una struttura mesa sono stati sviluppato così come un trattamento di impiantazione a base di ioni di He al fine di indurre uno strato grafitico appena sotto la superficie del diamante. Le misure elettriche su diamanti leggermente drogati ([B] = 4 × 10¹⁷ cm⁻³) con contatti o solo metallici o grafitici / metallici hanno dimostrato che la presenza dello strato grafitico rende i contatti ohmici e comporta una resistenza specifica di contatto pari a 3.3 × 10⁻⁴ Ω.cm².

Carbonation is a natural phenomenon observed in carbon structures, and it is a result of the combined presence of CO2 in the environment and moisture. Carbonation may lower the pH of the concrete to such an extent that the passivation layer of the steel is depleted and the onset of frame corrosion is observed, which is one of the major pathologies in reinforced concrete structures. This study aimed to assess accelerated carbonation in concrete samples prepared with rice husk ash (RHA) with different concentrations of graphitic carbon and different curing periods. Concrete samples were prepared with 5%, 10%, 20% and 30% of RHA as a substitution for high early strength Portland cement (Brazilian grade CPV-ARI), different water/binder ratios (0.35; 0.50; 0.65) and wet cured for 3 and 7 days. In addition, two mixes with 5% and 10% silica fume as substitutions for Portland cement were used for comparison. Accelerated carbonation was performed in 10x10cm test specimens (TS) that were preconditioned as determined by standard RILEM TC 116-PCD. These TSs were stored in a controlled temperature chamber (RH 65 ± 2%, temperature 23 ± 2°C, 3% CO2 b/v), where they were exposed to CO2 for 4, 8, 12 and 16 weeks. The mercury intrusion porosimetry test was performed in 4x8cm TSs, which were tested after 91 days. Overall results show improved accelerated carbonation performance in the samples prepared with rice husk ash with lower concentrations of graphitic carbon, even though figures were similar. Higher concentrations of RHA in the concrete samples resulted in increased carbonation coefficients for all mixes investigated. For samples of the same strength values, a reduction in carbonation coefficients was observed when their compressive strength increased from 40 MPa to 50 MPa, This was seen in all mixes investigated for the curing period used, which shows that the use of longer curing periods improves the service life of structures. / O fenômeno da carbonatação acontece naturalmente em estruturas de concreto, exigindo apenas certa concentração de CO2 no ambiente e determinado teor de umidade. Este fenômeno provoca a redução do pH do concreto a níveis que podem causar a eliminação da película passivadora do aço, podendo ocorrer a instalação do mecanismo de corrosão das armaduras, uma das principais patologias em estruturas de concreto armado. O presente estudo teve por objetivo avaliar a carbonatação acelerada em concretos compostos com cinza de casca de arroz com diferentes teores de carbono grafítico e períodos de cura. Os concretos foram moldados com cinza de casca de arroz com teores de 5%, 10%, 20% e 30% em substituição ao cimento Portland de alta resistência inicial (CPV-ARI), com diferentes relações água/aglomerante (0,35; 0,50; 0,65) e com períodos de cura em câmara úmida de 3 e 7 dias. Duas misturas com 5% e 10% de sílica ativa em substituição ao cimento Portland foram empregadas como parâmetro de comparação. A carbonatação acelerada foi realizada em corpos-de-prova 10x10cm que passaram pelo pré-condicionamento, conforme preconiza a norma RILEM TC 116-PCD, após serem inseridos em uma câmara climatizada com uma umidade de (65 ± 2)%, temperatura de (23 ± 2)°C e uma concentração de CO2 de 3% em volume, por períodos de 4, 8, 12 e 16 semanas de exposição ao CO2. Já o ensaio de porosimetria por intrusão de mercúrio foi realizado em corpos-de-prova medindo 4x8cm, que foram ensaiados aos 91 dias. Os resultados mostram, de maneira geral, um melhor desempenho da cinza de casca de arroz com menor teor de carbono grafítico frente à carbonatação acelerada, apesar da proximidade dos resultados. O aumento do teor substituição, nos concretos com cinza de casca de arroz, provocou um aumento dos coeficientes de carbonatação, para todas as misturas investigadas. Em igualdade de resistência, constata-se que houve uma diminuição dos coeficientes de carbonatação quando a resistência à compressão aumenta de 40 MPa para 50 MPa para todas as misturas analisadas e para o prazo de cura adotado, evidenciando que o prolongamento no período de cura do concreto reflete diretamente no aumento da vida útil da estrutura.

Pure g-C3N4 and MoS2 modified g-C3N4 materials were synthesized using a facile heating method and a low-temperature hydrothermal method, respectively. The obtained samples were characterized by XRD pattern and N2 adsorption-desorption technique at 77K. The adsorption and photocatalytic performance of all obtained samples were investigated by discoloration of direct black 38 dye in the dark and under visible light irradiation. The results showed that all obtained samples exhibited good discoloration efficiency of direct black 38 dye. The two factors including pH values and Mo loading effected mainly on elimination efficiency of direct black 38 dye. MoS2 modified g-C3N4 materials possessed the more enhanced adsorption and photocatalytic performance in comparison to pure g-C3N4 at pH value of 3.5, with adsorbent dosage of 0.1 g/L. Furthermore, it was found that the adsorption process and photo-catalysis simultaneously occurred under visible light irradiation and followed up a pseudo-second-order kinetic reaction of Langmuir - Hinshelwood model. / g-C3N4 và g-C3N4 biến tính bởi MoS2 đã được tổng hợp theo phương pháp nung đơn giản và phương pháp thủy nhiệt ở nhiệt độ thấp tương ứng. Các mẫu tổng hợp đã được đánh giá đặc trưng bởi các phương pháp hiện đại như giản đồ nhiễu xạ tia X, phương pháp hấp phụ-khử hấp phụ N2 ở 77K. Khả năng hấp phụ và quang hóa xúc tác của các vật liệu tổng hợp đã được nghiên cứu bởi quá trình phân hủy màu thuốc nhuộm direct black 38 trong điều kiện bóng tối và chiếu sáng bởi ảnh sáng nhìn thấy của đèn chiếu sáng sợi đốt wolfram (220V-100W). Các kết quả nghiên cứu chỉ ra rằng các mẫu tổng hợp đều có hiệu suất xử lý màu cao đối với thuốc nhuộm direct black 38. Hai yếu tố gồm pH dung dịch và hàm lượng MoS2 ảnh hưởng chính đến hiệu suất xử lý màu direct black 38. g-C3N4 biến tính bởi MoS2 luôn thể hiện hiệu suất hấp phụ và quang hóa cao hơn so với g-C3N4 tinh khiết. Hơn nữa, khi được chiếu sáng bởi ánh sáng nhìn thấy thì quá trình hấp phụ và quá trình quang hóa thuốc nhuộm direct black 38 trên các vật liệu tổng hợp đã xảy ra đồng thời và mô hình Langmuir - Hinshelwood động học bậc 2 đã được đề xuất cho quá trình này.

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The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g –1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route.

The results of this study show that novel mesoporous carbons were obtained as inverse replica of SBA-15, HMS and MCM-41 silica templates, with a large pore diameter (2-4 nm), a BET surface area of 1867, 874 and 910 m2g –1 respectively for CA_SBA-15_LPG_105, CA_HMS_LPG_80 and CA_MCM- 41_LPG_80 with bimodal pore size distribution (PSD) in the mesopores range. The results obtained show that mesoporous carbon with graphitic structures can be synthesized via the LPG route.