Malgré ses avantages économiques et environnementaux, le procédé de reformage à sec du méthane sur des catalyseurs au nickel supporté se heurte encore à des problèmes de frittage de la phase active (un métal de transition) et de dépôt de carbone, ce qui entraîne une diminution de l'activité catalytique. Cette thèse porte sur l'étude de l'effet de confinement du nickel dans des catalyseurs à base de silice mésoporeuse pour la production de gaz de synthèse par reformage du méthane par le CO2. Dans cette étude, les échantillons ont été caractérisés par physisorption de N2, DRX, MET/MEB, RTP, et, en plus, par Raman, SPX, HTP/SM, ATG/SM pour les catalyseurs après test catalytique. Les résultats montrent qu'un support mésoporeux bien structuré ayant une grande surface spécifique et un grand volume poreux est important pour une meilleure dispersion et stabilisation de la phase active à l'intérieur de la porosité. La silice mésoporeuse de SBA-15 (préparée en grande quantité), composée de grains allongés, semble être appropriée pour atteindre cet objectif. Il est de plus démontré que la formation de petites particules bien confinées à l'intérieur des pores favorise la résistance au dépôt de carbone. Ceci peut être obtenu en imposant un traitement hydrothermal au support, en utilisant la méthode deux solvants pour le dépôt de Ni, en passant à une réduction directe des échantillons non calcinés, en ajoutant du Rh en faibles quantités ou en utilisant du Ce comme promoteur, à condition que le Ni et Ce soient en interaction. / Although economically and environmentally advantageous, the methane dry reforming process using supported nickel based catalysts still faces problems of active phase (a transition metal) sintering and of carbon deposition, which result in catalytic activity loss. This thesis is focused on the study of the confinement effect of nickel in mesoporous silica-based catalysts for syngas production by reforming of methane with CO2. In this study, the samples were characterized by N2 sorption, XRD, TEM/SEM, TPR, in addition to Raman, XPS, TPH/MS, TGA/MS for the spent catalysts. The results indicate that a well-structured mesoporous support with high surface area and large pore volume is important for better dispersion and stabilization of the active phase inside the porosity. The mesoporous SBA-15 silica support (prepared in large quantity), composed of elongated grains, appear to be suitable for the purpose. Moreover, it is demonstrated that the formation of small nickel particles well-confined inside the pores favors carbon resistance. This can be achieved by applying hydrothermal treatment to the support, using two solvents method for Ni deposition, using direct reduction of uncalcined samples, adding Rh in small quantities or promoting with Ce, provided that Ni and Ce are in interaction.

This thesis studies the different ways in which the localized plasmon heating effect of gold nanostructures -activated by plasmon excitation via visible and/or NIR irradiation- can be used to obtain different outcomes following the nanofabrication of applicable devices. Both spatial and temporal control were obtained for each one of the systems developed upon the incorporation of plasmonic gold nanostructures. Spatial control was enabled in hybrid mesoporous drug delivery systems fabricated in this thesis through the localized surface plasmon heating effect that allowed the modification of the dynamics of diffusion of the cargo being delivered, thus giving rise to different rates of release that can be controlled by plasmon excitation. At the same time, the plasmon heating effect proved to be capable of controlling the start of the release by dismantling thermo-responsive gates previously incorporated, thus enabling also a wavelength-controlled feature that enhances the versatility of these systems. Spatial control was also conferred to the photo-patterning applications presented in this dissertation by influencing the degree of motility of gold nanorods (AuNRs) embedded in polymer matrices allowing them to self-assemble when the longitudinal plasmon of the incorporated nanostructures was excited; the patterns generated were quite robust and persisted for extended periods of time. Finally, the feature of spatial heating control was also conferred to catalysis. The Friedel-Crafts alkylation of anisole by benzyl chloride using spherical gold nanoparticles (AuNPs) supported on Nb2O5-based catalysts was performed at bulk temperatures below those necessary for the reaction to occur when using bare or modified Nb2O5; this was the result of the combination of bulk and localized plasmon heating produced -both- via plasmon excitation. This also demonstrates the possibility of using plasmon excitation as an alternative heat source in this type of reactions. By combining the plasmonic properties of metallic nanostructures with those granted by mesoporous materials, polymer matrices and Nb2O5-based materials it was possible to obtain light-activated systems endowed also with temporal control and wavelength control while preserving the original properties of each systems' components. Overall, the content of this thesis describes in detail the practical aspects of combining gold nanostructures with different materials and the rationale behind the development of systems with customized and controllable properties.

Dans ce travail, les propriétés des oxydes de titane mésoporeux organisés ont été étudiées en détail. La synthèse de ces matériaux a été mise au point auparavant au laboratoire à l’aide d’une méthode combinant le mécanisme transcriptif à partir des cristaux liquides du copolymère bloc P123 et la méthode EISA. Tout d’abord, une optimisation des conditions d’élimination du tensioactif a été effectuée en testant des méthodes d’extraction à partir de solvant et des méthodes thermiques. L’élimination du P123 par l’eau suivie d’un rinçage à l’acétone est efficace, simple et rapide et en même temps favorise la formation de la phase anatase du TiO2. Par contre, les propriétés photocatalytiques de ces TiO2 extraits à l’eau sont médiocres et ne sont améliorées qu’après calcination. En combinant une extraction du P123 à l’eau avec une calcination les oxydes de titane mésoporeux possédent une meilleure activité photocatalytique que celle de l’anatase commercial. Dans un second temps l’incorporation du zinc et du tungstène dans les TiO2 mésoporeux organisés a été investie dans le but d’améliorer leur activité photocatalytique. L’introduction de faibles quantités de zinc (<10% mol) augmente la surface spécifique ; au-delà la mésostructuration est perdue. L’incorporation du tungstène dans le TiO2 mésoporeux n’a pas d’influence sur l’organisation des mésopores, mais des agrégats de WO3 orthorhombique coexistent avec le réseau mésoporeux de TiO2 anatase. Même si la présence d’oxyde de zinc ou de tungstène dans la matrice TiO2 mésoporeux diminue bien l’énergie bandgap, l’activité photocatalytique ne s’en trouve pas améliorée. D’autre part, la synthèse de matériaux à porosité bimodale, en utilisant deux systèmes mixtes de tensioactifs hydrogéné/fluoré, CTABr/RF8(EO)9 et P123/ RF8(EO)9, a été explorée. Sur la base des diagrammes de phase de ces deux systèmes dans l’eau, les solutions micellaires et les cristaux liquides ont été investis pour préparer des silices mésoporeuses en utilisant les deux mécanismes CTM et LCT. Quand le CTABr est présent une seule taille de pores dans le domaine mésoporeux est observée, toutefois il est possible qu’une bimodalité de type micro-mésopores existe. Par contre, l’utilisation de la phase hexagonale du système P123/RF8(EO)9 permet d’obtenir des matériaux à deux tailles de pores distincts dans le domaine mésoporeux. / In this work we will study in detail the properties of the mesoporous TiO2 materials, for which the preparation was developed previously via a method combining Liquid Crystal Templating (LCT) and EISA mechanisms, using P123 as template. We have tested, in the first time, extraction and thermal methods efficiency to eliminate surfactant in order to optimize the P123 elimination step. Removal of P123 using water followed by washing with acetone is effective, easy and promotes the formation of the anatase phase of TiO2. Otherwise, the photocatalytic properties of the obtained TiO2 are not important and can be improved after calcination. Combining extraction using water and calcination give rise to mesoporous TiO2 with better photocatalytic activity than that of commercial anatase. The incorporation of zinc and tungsten in the mesoporous well-ordered TiO2 has been investigated in the third time, in order to improve their photocatalytic activity. The introduction of small amounts of zinc (<10 mol%) increases the surface area; beyond this amount the mesostructure is lost. The incorporation of tungsten in the mesoporous TiO2 does not affect the mesopores organization, and orthorhombic WO3 aggregates are formed beside the mesoporous network of anatase TiO2. Although, the presence of zinc or tungsten oxides in the matrix decreases the bandgap of mesoporous TiO2, the photocatalytic activity is not improved. In the third time, the synthesis of bimodal porosity materials, using a mixed surfactant systems hydrogenated/fluorinated, CTABr/RF8(EO)9 and P123/RF8(EO)9, was explored. Based on the phase diagrams of these two systems in water, micellar solutions and liquid crystals have been investigated to prepare mesoporous silicas using two mechanisms CTM and LCT. When CTABr is present, pores of one size in the mesoporous range are observed, however, it is possible that bimodal type micro-mesopores exist. The use of the hexagonal liquid crystal phase of P123/RF8(EO)9 provides two separate pore sizes materials in the mesoporous range.

Ce travail traite du rôle joué par les fonctions de surface sur le transport et le piégeage de cations alcalins en présence d'eau, dans des SBA-15 fonctionnalisées. Il s'agit aussi d'étudier les effets de confinement sur la thermodynamique de l'eau adsorbée. La première étape a consisté à synthétiser les différentes SBA-15, contenant des groupements fonctionnels acides du type PO(OH)2, SO3H, COOH ainsi que leurs équivalents alcalins contenant du Li, Na, K ou Rb. Les solides obtenus ont été caractérisés à l'état sec par DRX, adsorption-désorption de N2 et par RMN du solide, afin de rendre compte respectivement de l'organisation du réseau poreux, des caractéristiques texturales et de la structure locale des motifs organiques. Puis, nous avons étudié ces solides en présence d'eau adsorbée. Nous avons mis en évidence l'instabilité des solides alcalins contenant des ions Na+, K+ et Rb+. Nous proposons également une étude thermodynamique de la fusion de l'eau confinée par DSC, pour laquelle nous montrons que déplacement de la température de transition solide/liquide de l'eau adsorbée dépend de la taille des pores. Ensuite, nous avons analysé les dynamiques ionique et moléculaire de l'eau confinée par Spectroscopie d'Impédance Complexe (SIC) et par diffusion quasi-élastique des neutrons (QENS). L'étude par SIC nous a permis, pour les solides acides, de révéler une conduction protonique selon un mécanisme de Grötthus, et de montrer une dépendance entre les valeurs de conductivité et le pKa des fonctions acides. Finalement par QENS, nous avons observé deux régimes de mobilité des protons, de part et d'autre de 220K, que nous avons associés à des populations différentes de protons. / This work deals with the role played by the functions of surface transport and trapping of alkali cations in the presence of water in SBA-15 functionalized. It is also to study the effects of confinement on the thermodynamics of the adsorbed water. The first step was to synthesize the different SBA-15 containing acidic functional groups of type PO (OH) 2, SO3H, COOH and alkali equivalents containing Li, Na, K or Rb. The solids obtained were characterized in the dry state by XRD, N2 adsorption-desorption and solid state NMR, respectively, to reflect the organization of the pore network, and textural characteristics of the local structure of organic patterns. Then, we studied the solid presence of adsorbed water. We have highlighted the instability of solids containing alkali ions Na +, K + and Rb +. We also study the thermodynamics of melting of water confined by DSC, for which we show that displacement of the transition temperature of solid / liquid water adsorbed depends on the pore size. Then, we analyzed the ionic and molecular dynamics of water confined by Complex Impedance Spectroscopy (CIS) and by quasi-elastic neutron scattering (QENS). The CIS study allowed us, for strong acids, reveal a proton conduction mechanism in a Grotthus, and show a dependence between conductivity values and the pKa of the acid functions. Finally by QENS, we have observed two regimes of mobility of protons, on both sides of 220K, which we associated with different populations of protons.

Ce travail de thèse s'inscrit dans la problématique de la préparation et l'intégration des matériaux diélectriques poreux à très faible permittivité (ULK) dans les interconnexions des puces microélectroniques. Cette étude porte sur le développement de couches minces hydrophobes ULK à porosité organisée et isolée, préparées par voies sol-gel et PECVD. Elle vise une amélioration des propriétés mécaniques et une diminution de la diffusion de polluants au cœur des films. Des matériaux hydrophobes mésostructurés et ULK (k < 2,2) ont ainsi été obtenus par voie sol-gel, après retrait d'un porogène par traitement thermique, ou pour la première fois sous UV. Les caractéristiques mésostructurales et microstructurales des couches ont été reliées aux caractéristiques de porosité et aux propriétés mécaniques. Les mesures électriques et de perméation de gaz de ces matériaux sont également discutées en vue de leurs applications en tant que matériaux ULK ou comme membranes de séparation de gaz. En PECVD, des matériaux polymère plasma à base de styrène ont été synthétisés et également caractérisés en termes de propriétés mécaniques et de séparation de gaz. / This thesis is dealing with the challenging preparation and integration of porous dielectric materials with ultra low permittivity (ULK) for interconnections in microelectronic devices. This study focuses on synthesis of hydrophobic ULK thin layers with ordered and isolated porosity obtained by sol-gel. An improvement in mechanical properties and a decrease of the impurities migration in the heart of the bulk are expected. Hydrophobic and mesostructured ULK (k < 2.2) materials have been obtained by sol-gel after removal of porogen mesophases by thermal treatment and for the first time under UV irradiation. Mesostructural and microstructural properties of the layers were discussed with regard to the porosity and mechanical properties. The electrical and gas permeation measurements were also discussed in the framework of their possible applications as ULK materials and gas separation membranes, respectively. Using PECVD, styrene-based polymers, have been synthesized and also characterized in terms of mechanical and gas separation properties.

Orientador: Claudio Airoldi / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-22T05:32:41Z (GMT). No. of bitstreams: 1 Costa_LuelcSouzada_M.pdf: 4010865 bytes, checksum: 0e6d35c0e46af757fe71fa900c8678f8 (MD5) Previous issue date: 2012 / Resumo: A síntese de sílicas mesoporosas funcionalizadas pela a rota de co-condensação tem despertado a atenção de diversos grupos de pesquisas devido a sua praticidade. Esta síntese consiste na condensação simultânea entre as moléculas dos organossilanos e as moléculas da fonte de silício (TEOS) através do método sol-gel. Isso faz com que a incorporação de grupos orgânicos na estrutura da sílica ocorra de forma direta. No entanto, em muitos casos, os híbridos preparados dessa forma podem apresenta uma má formação estrutural devido a presença dos grupos orgânicos. Nesse trabalho foram sintetizados materiais híbridos com o agente direcionador copolímero tribloco EO20-PO70-EO20 (P123 ¿ Pluronic®). Foram escolhidos grupos organossilanos contendo em suas estruturas sítios básicos Lewis tais como grupos carbonílicos, enxofre e nitrogenados. Os espectros na região do infravermelho juntamente com a análise elementar e ressonância magnética nuclear mostraram concordância que o ancoramento dos grupos orgânicos na matriz inorgânica dos híbridos ocorreu de forma satisfatória. As isotermas de sorção e dessorção de nitrogênio mostraram que todas as isotermas são do tipo IV com histerese do tipo H1 que são característicos de matérias mesoporosos e que os poros dos materiais estão na faixa de mesoporosidade, a área superficial é dependente do tamanho da molécula utilizada na funcionalização. Foram observados os sinais da reflexão típica de materiais do grupo p6mm, denominada 2D-hexagonal, análogas ao material SBA-15. Portanto, todos os híbridos foram sintetizados de forma ordenada como proposto. Os materiais híbridos foram aplicados em sorção de íons metálicos, e na sorção de corantes. Os dados experimentais foram ajustados aos modelos de isoterma de sorção de Langmuir, Freudlich e Sips usando os métodos de regressão não linear. As sílicas apresentaram boa capacidade de sorção tanto para os metais quanto para o corante. Fato esse devido aos sítios básicos de Lewis, de nitrogênio e enxofre presentes e a possibilidade desses grupos serem protonados em solução e estes sítios interagirem com os grupos sulfonados do corante. / Abstract: The synthesis of functionalized mesoporous silicas by a co-condensation route has attracted attention of many research groups due to its practicality. The synthesis consists of the simultaneous condensation among organosilane molecules and the molecules of silicon source by sol-gel method. This makes the incorporation of organic groups in the silica structure occurs directly. However, in many cases, the hybrids may this way prepared has a structural deformation due to the presence of the organic groups. In this work were synthesized hybrid materials with directing agent triblock copolymer EO20-PO70-EO20 (P123 - Pluronic ®).Were chosen organosilanes containing groups in their structures Lewis basic sites such as carbonyl groups, nitrogen and sulfur. Infrared spectra combined with elemental analysis and nuclear magnetic resonance proved that the organic chains were satisfactorily anchored to the inorganic matrices. The nitrogen adsorption-desorption analyses generated isotherms of type IV and hysteresis H1 that are typical of mesoporous materials, where asthe pore size distribution showed that the pores of the silicas are in the mesoporous range. The BET method was applied to acquire the surface areas of the solids, which were found to be dependent on the size of the molecule used for the functionalization processes. SAXS patterns of all samples demonstrated well-resolved peaks characteristic of the typical p6mm space group, called 2D-hexagonal, similar to SBA-15.The hybrid materials were applied to the sorption of metallic ion sand dyes, showing good sorption capacities for both kinds of contaminants. The nitrogen and sulfur Lewis basic sites anchored to the silica inorganic back bone can be protonated to interact with the sulfonated groups of the dyes. The experimental data were fitted to the Langmuir, Freundlich and Sips sorption isotherms using the non-linear regression. / Mestrado / Quimica Inorganica / Mestre em Química

Orientador: Nelson Eduardo Durán Caballero / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-27T13:02:52Z (GMT). No. of bitstreams: 1 Bueno_CamilaPedrosoSilveira_M.pdf: 80017692 bytes, checksum: afdb5714b60ba879bf69cbd031077a1d (MD5) Previous issue date: 2015 / Resumo: Um dos principais problemas da quimioterapia, atualmente, é o uso de fármacos extremamente citotóxicos, cuja falta de especificidade acarreta na ação sob todos os tipos de células, incluindo as saudáveis, gerando efeitos colaterais intensos, que prejudicam a terapia em si. Nesse sentido, os nanomateriais oferecem uma opção terapêutica valiosa, pois podem conjugar especificidade e liberação sustentada do fármaco, prevenindo-o de ser degradado prematuramente e permitindo o uso de menores doses. A fim de desenvolver um sistema do tipo drug depot que servisse como plataforma para a liberação sustentada de fármacos, foram produzidas, neste trabalho, formulações baseadas em nanopartículas mesoporosas de sílica e hidrogel de Pluronic F-127, associadas a dois fármacos individualmente: doxorrubicina e sildenafila. As nanopartículas mesoporosas de sílica são boas alternativas para uso médico, pois são biocompatíveis e possuem grande volume de poros, atuando como carreadoras, promovendo a liberação sustentada do fármaco. O Pluronic F-127 atua como agente gelificante e promove uma liberação prolongada das nanopartículas e do fármaco incorporado, uma vez que é um polímero termo-reversível que permite a formação de um hidrogel à temperatura ambiente. A doxorrubicina é um antibiótico antitumoral de largo espectro, amplamente usada no tratamento de diversos cânceres, que atua ligando-se ao DNA e induzindo apoptose celular. Por sua vez, a sildenafila faz parte de uma classe de inibidores da enzima fosfodiesterase-5, cuja expressão aparece aumentada em diversos carcinomas e, por isso, seu papel na progressão tumoral vem sendo amplamente estudado. Após estudar os aspectos físico-químicos envolvendo os componentes dos sistemas, como estabilidade coloidal e interações entre as nanopartículas e biomoléculas presentes no meio biológico, as formulações foram testadas contra câncer de próstata quimicamente induzido em ratos. Os resultados mostram que as nanopartículas possuem um papel determinante no quadro de melhora de tumor, minimizando, também, a toxicidade do antitumoral / Abstract: One of the largest problems of chemotherapy currently is the use of highly cytotoxic drugs with lack of specificity, thus damaging all kinds of tissues, including healthy cells. This leads to aggressive side effects that jeopardize the therapy itself. In this context, nanomaterials emerge as a valuable therapeutic option, as they can provide the specificity to target tumor tissues and a sustained release of the drug, preventing the drugs premature degradation and allowing lower doses. Aiming to develop a drug depot system that would act as platform for the sustained release of drugs, this project proposed to develop formulations based on mesoporous silica nanoparticles and Pluronic F-127 hydrogels, associated with two drugs individually: doxorubicin and sildenafil. The mesoporous silica nanoparticles are good alternatives for biomedical use because of their biocompatible features and their great pore volume, acting as carriers and providing sustained release. Pluronic F-127 acts as the gelling agent and provides a prolonged release of the nanoparticles and the loaded drug, since it is a thermo-reversible polymer that allows the formation of a hydrogel at room temperature. Doxorubicin is an antibiotic and antitumor of large spectra, largely used to treat several types of cancer and acts binding the DNA and inducing cell apoptosis. Sildenafil, in turn, is part of a class of inhibidors of the enzyme phosphodiesterase-5, which expression is increased in many carcinomas and which role in tumor progression has been largely studied. After studying physico-chemical aspects involving the systems produced, such as the colloidal stability, release profile, and the interactions of the nanoparticles with the biomolecules present in biological medium. The formulations were also tested in rats with chemically induced prostate cancer. The results show that the nanoparticles play a determinant role on the improvement of tumor conditions, also reducing doxorubicin's toxicity / Mestrado / Físico-Química / Mestra em Química

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous silica as well as a judicious choice of pH. Modified magnetic mesoporous silica material was also found to have high adsorption capacity for high and low pH aqueous solutions of Uranium (VI). Tuning the loading and release of a small drug molecule (5-FU) onto these iron oxide/ mesoporous silica core-shell materials was also investigated. The polarity of the solvent used to load 5-FU onto the host had an impact not only on the loading but also on the release percentage of 5-FU. The synthesis of a novel core-shell material with a hematite nanofiber core and a SBA type mesoporous silica shell was also explored.

Avec les progrès de l'informatique, la quantité de données crée et échangée augmente exponentiellement. Le stockage de l'information doit évoluer pour être plus performant, et les matériaux actuels atteignent leur limite. Une évolution technologique est nécessaire. Une des réponses possibles se trouve dans les polymères de coordinations photo-commutables, dont la propriété de bi-stabilité permettrait d'obtenir des densités de stockage et des vitesses de lecture/écriture jamais atteintes. Afin d'utiliser ces matériaux, leur mise en forme, et particulièrement leur réduction en taille, est nécessaire, mais accomplir cette mise en forme sans affecter la propriété de commutation est ardu. Dans ce travail, nous proposons une mise en forme contrôlée à base de silice mésoporeuse pour obtenir des nanoparticules de composés de coordination possédant des propriétés intéressantes pour des applications. Spécifiquement, Ce travail a pour objectifs de (i) réduire en taille les composés fonctionnels, (ii) étudier la propriété à l'échelle du nanomètre, (iii) utiliser les possibilités de notre voie de synthèse pour comprendre l'effet de la mise en forme et (iv) aller vers de nouvelles propriétés causées par la mise en forme. Nous espérons ainsi poser une base solide pour l'étude de ces composés fonctionnels à l'échelle du nanomètre. / With the raise of information technology, the amount of data created and exchanged increases drastically. Information storage must evolve to be more and more efficient, but the current materials used are reaching their peak. A technological evolution is needed. One of the possible answers is found with the photo-switchable coordination polymers, which property would allow us to attain storage density as well as addressing times never seen before. In order to use these materials, their processing, and especially their size reduction, is the key. However, successfully processing these without impacting the switching property is not an easy task. In this work, we propose a perfectly controlled processing based on mesoporous silica for the synthesis of nanoparticles of potentially applicative coordination compounds. To be specific, our work intends to (i) reduce the size of functional compounds, (ii) study the property at the nanoscale, (iii) use the possibilities of our synthesis to understand the effect of processing on the property and (iv) obtain new properties, caused by the processing. We therefore hope to lay a solid basis for the nanoscale study of these functional compounds.

Nanotechnology as a field has the potential to answer some of the major challenges that mankind faces in regards to environmental sustainability, energy generation and health care. Though, solutions to these concerns can not necessarily rely on our current knowhow. Instead, it is reasonable to expect that humanity must adapt and learn to develop new materials and methods to overcome the adversities that we are facing. This master thesis has involved developing novel materials, serving as a small step in the continuous march towards a bright future where this is possible. More specifically, this work sought to combine mesoporous magnesium carbonate with various metal-organic frameworks to utilize the beneficial aspects from each of these constituents. The ambition was that these could be joined to render combined micro-/mesoporous core-shell structures, with high surface areas and many active sites whilst maintaining a good permeability. Numerous different synthesis routes were developed and explored in the pursuit of viable routes to design novel materials with potential future applications within for instance drug delivery, water harvesting from air and gas adsorption. Coreshell structures of the hydrophilic mesoporous magnesium carbonate covered with the hydrophobic zeolitic imidazole framework ZIF-8 was successfully synthesized for the first time, and practical studies demonstrated a dramatically enhanced water stability, which is perceived to have an impact on further research on these materials. ZIF-67 was also combined with mesoporous magnesium carbonate in a similar manner. Further, Mg-MOF-74 was grown directly from mesoporous magnesium carbonate, where the latter acted as a partially self-sacrificing template, with the aim of rendering a porous hierarchical structure with contributions from the micro- and mesoporous ranges. The outcomes of all these syntheses were characterized using several analyzing methods such as scanning electron microscopy, X-ray diffraction, energy dispersive spectroscopy and nitrogen sorption analysis.