Orientador: Dimas Roberto Vollet / Banca: José Ramon Beltran Abrego / Banca: Dario Antonio Donatti / Resumo: O objetivo deste trabalho foi estudar as características estruturais em géis de sílica preparados a partir da hidrólise ácida do tetraetilortosilicato (TEOS) com adições do surfactante aniônico dodecil sulfato de sódio (SDS) e de n-heptano como fase oleosa. Os géis são estudados em estágios que vão do estado saturado (gel úmido) até o estado seco do gel (aerogel) resultante da secagem à pressão ambiente. As caracterizações estruturais das amostras são realizadas através das técnicas de Termogravimetria (TG), densidade aparente, análise de distribuição de tamanho de poros e área superficial por Adsorção de Nitrogênio, e espalhamento de raios-X a baixo ângulo (SAXS). A razão molar água/TEOS e o volume da mistura dos reagentes foram mantidos constantes no processo de hidrólise para todas as adições de n-heptano. Foram obtidos dois grupos de géis úmidos, num primeiro grupo a fase líquida dos géis úmidos foi trocada por água para remoção da microemulsão (amostras Ta) e no outro além da troca por água foi feito troca por uma solução de trimetilclorosilano (TMCS) em álcool isopropílico, para modificação da superfície da sílica (sililação), e finalmente por álcool isopropílico puro (amostras Tm). A estrutura dos géis úmidos pode ser descrita como a de uma estrutura fractal de massa com tamanho característico de cerca de 10 nm e dimensão fractal D em torno de 2.2, composto de partículas primárias de sílica de tamanho característico a1, estimadas como sendo da ordem de 0.7 nm para os géis úmidos Ta e menor do que 0.4 nm para os géis úmidos Tm. Aerogéis foram obtidos por secagem à pressão ambiente a partir dos géis úmidos Tm (aerogéis IPA) e a partir dos géis úmidos Tm com mais uma troca de fase líquida, desta vez por acetona (aerogéis ACE). O processo de secagem estreita o intervalo de comprimentos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: This work aims to study the structural characteristics of silica gels prepared from hydrolysis of tetraethylortosilicate (TEOS) with additions of the anionic surfactant sodium dodecyl sulfate (SDS) and n-heptane as an oily phase. The gels are studied in stages from the saturated state (wet gels) to dried gels (aerogels), resulting from the ambient pressure drying. The samples are characterized by Termogravimetry (TG), apparent density, surface area and porous size distribution by nitrogen adsorption, and small-angle X-ray scattering (SAXS). The water/TEOS molar ratio and the reactant mixture volume were kept constant during the hydrolysis process for all additions of n-heptane. The liquid phase of the wet gels was changed by water (Ta samples), in order to washing for removing the micro-emulsions, followed by changing water by a trimethylchrorosilane (TMCS) solution, in order to modify the silica surface (sililation), and finally changing the TMCS solution by pure isopropyl alcohol (Tm samples). The structure of the wet gels can be described by a mass fractal structure with characteristic size of about 10 nm and fractal dimension of about 2.2, built up by primary silica particles of characteristic size a1, which was found to be about 0.7 nm for the wet gels Ta and smaller than 0.4 nm for the wet gels Tm. Aerogels were obtained by ambient pressure drying from the wet gels Tm (IPA aerogels) and from the wet gels Tm but with once more change of liquid phase, now by acetone (ACE aerogels). The drying process shortens the length scale range of the mass fractal structure of the original wet gels (diminishes and increases a1), without, however, modify substantially the mass fractal dimension D. The mass fractal structure of the original wet gels seems to evolve in the aerogels to a mass and surface fractal structure, when it is observed at high resolution. The values of the specific surface... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2014-06-11T19:25:31Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-09-23Bitstream added on 2014-06-13T20:53:30Z : No. of bitstreams: 1 viceli_mr_me_rcla.pdf: 1171030 bytes, checksum: e09b1414b017e8dddec96fe741c253b7 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo deste trabalho foi estudar as características estruturais em géis de sílica preparados a partir da hidrólise ácida do tetraetilortosilicato (TEOS) com adições do surfactante aniônico dodecil sulfato de sódio (SDS) e de n-heptano como fase oleosa. Os géis são estudados em estágios que vão do estado saturado (gel úmido) até o estado seco do gel (aerogel) resultante da secagem à pressão ambiente. As caracterizações estruturais das amostras são realizadas através das técnicas de Termogravimetria (TG), densidade aparente, análise de distribuição de tamanho de poros e área superficial por Adsorção de Nitrogênio, e espalhamento de raios-X a baixo ângulo (SAXS). A razão molar água/TEOS e o volume da mistura dos reagentes foram mantidos constantes no processo de hidrólise para todas as adições de n-heptano. Foram obtidos dois grupos de géis úmidos, num primeiro grupo a fase líquida dos géis úmidos foi trocada por água para remoção da microemulsão (amostras Ta) e no outro além da troca por água foi feito troca por uma solução de trimetilclorosilano (TMCS) em álcool isopropílico, para modificação da superfície da sílica (sililação), e finalmente por álcool isopropílico puro (amostras Tm). A estrutura dos géis úmidos pode ser descrita como a de uma estrutura fractal de massa com tamanho característico de cerca de 10 nm e dimensão fractal D em torno de 2.2, composto de partículas primárias de sílica de tamanho característico a1, estimadas como sendo da ordem de 0.7 nm para os géis úmidos Ta e menor do que 0.4 nm para os géis úmidos Tm. Aerogéis foram obtidos por secagem à pressão ambiente a partir dos géis úmidos Tm (aerogéis IPA) e a partir dos géis úmidos Tm com mais uma troca de fase líquida, desta vez por acetona (aerogéis ACE). O processo de secagem estreita o intervalo de comprimentos... / This work aims to study the structural characteristics of silica gels prepared from hydrolysis of tetraethylortosilicate (TEOS) with additions of the anionic surfactant sodium dodecyl sulfate (SDS) and n-heptane as an oily phase. The gels are studied in stages from the saturated state (wet gels) to dried gels (aerogels), resulting from the ambient pressure drying. The samples are characterized by Termogravimetry (TG), apparent density, surface area and porous size distribution by nitrogen adsorption, and small-angle X-ray scattering (SAXS). The water/TEOS molar ratio and the reactant mixture volume were kept constant during the hydrolysis process for all additions of n-heptane. The liquid phase of the wet gels was changed by water (Ta samples), in order to washing for removing the micro-emulsions, followed by changing water by a trimethylchrorosilane (TMCS) solution, in order to modify the silica surface (sililation), and finally changing the TMCS solution by pure isopropyl alcohol (Tm samples). The structure of the wet gels can be described by a mass fractal structure with characteristic size of about 10 nm and fractal dimension of about 2.2, built up by primary silica particles of characteristic size a1, which was found to be about 0.7 nm for the wet gels Ta and smaller than 0.4 nm for the wet gels Tm. Aerogels were obtained by ambient pressure drying from the wet gels Tm (IPA aerogels) and from the wet gels Tm but with once more change of liquid phase, now by acetone (ACE aerogels). The drying process shortens the length scale range of the mass fractal structure of the original wet gels (diminishes and increases a1), without, however, modify substantially the mass fractal dimension D. The mass fractal structure of the original wet gels seems to evolve in the aerogels to a mass and surface fractal structure, when it is observed at high resolution. The values of the specific surface... (Complete abstract click electronic access below)

Hydrogen storage is a developing technology that can be used as an energy vector for sustainable energy applications such as fuel cells for transport applications or for supplying power to the grid in moments of high demand. However, before hydrogen can be used as a practical energy vector, hydrogen storage issues, such as low gravimetric storage density, need to be addressed. One possible solution could be using nanoporous materials to physically adsorb hydrogen at low temperatures and moderate pressures. Hydrogen adsorption excess isotherms in solid-state porous materials can be obtained experimentally. However, the total amount stored in them, a quantity of more practical interest, cannot be measured by experimental techniques. Therefore, a model developed at the University of Bath is used to predict the total amount of hydrogen contained in nanoporous materials from their experimentally derived excess isotherm data. According to inelastic neutron scattering experiments (TOSCA, ISIS, RAL, Oxfordshire), solid-like hydrogen is likely to exist within the pores. The model is applied in this work in order to search for relationships between intrinsic properties of the materials (BET surface area, pore volume and pore size) and the predicted total hydrogen capacity of the materials. The model assumes adsorbed hydrogen at a constant density within the pore (defined as the absolute), also taking bulk hydrogen in the pore (amount that is not considered to be adsorbed by the adsorbent), into account. Several MOF datasets have been used to search for these relations, since they are the materials that have the highest hydrogen uptake in solid-state adsorption. Different MOFs and MOF families have been tested in order to widen the range of the correlations. Also, different strategies, such as fixing the pore volume when applying the fittings, relying on experimental data, or using high pressure hydrogen isotherm data to increase the robustness of the model have been researched. These MOFs have been either synthesized and characterized at the University of Bath or their datasets obtained from literature. Some of these MOFs with zeolitic structure exhibited unreported flexibility, being their structures further characterized. Changes on accessible pore size for hydrogen storage were also investigated using C60 in IRMOF-1. The final aim of this work is to find possible correlations between BET surface area, pore volume and pore size to find out what the values of these parameters have to be in a specific material to fulfil the DOE hydrogen storage requirements.

Submitted by AMANDA PASQUOTO PERISSINOTTO null (amandap@rc.unesp.br) on 2016-02-17T12:33:22Z No. of bitstreams: 2 DissertaçãoAmandaok.pdf: 4083559 bytes, checksum: 7362f582721fdb5515688043eff181ca (MD5) DissertaçãoAmandaok.pdf: 4083559 bytes, checksum: 7362f582721fdb5515688043eff181ca (MD5) / Approved for entry into archive by Juliano Benedito Ferreira (julianoferreira@reitoria.unesp.br) on 2016-02-17T13:06:09Z (GMT) No. of bitstreams: 1 perissinotto_ap_me_rcla.pdf: 4083559 bytes, checksum: 7362f582721fdb5515688043eff181ca (MD5) / Made available in DSpace on 2016-02-17T13:06:09Z (GMT). No. of bitstreams: 1 perissinotto_ap_me_rcla.pdf: 4083559 bytes, checksum: 7362f582721fdb5515688043eff181ca (MD5) Previous issue date: 2016-02-16 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O objetivo deste trabalho foi estudar as características estruturais em géis úmidos de sílica preparados a partir da hidrólise ácida de Tetraetilortosilicato (TEOS) com adições do surfactante aniônico Dodecil Sulfato de Sódio (SDS). O surfactante foi removido após a gelificação. Os géis úmidos exibem uma estrutura fractal de massa com dimensão fractal de massa D (típicamente em torno de 2,25) numa escala de comprimentos que se estende desde o tamanho característico ξ (geralmente em torno de 10 nm) do domínio do fractal de massa até um tamanho característico a0 (típicamente entre 0,3 - 0,4 nm) da partícula primária que constituí o domínio fractal. ξ aumenta enquanto que D e a0 diminuem ligeiramente com o aumento da quantidade de SDS. Aerogéis SCD com superfície específica típica de 1000 m2 /g e massa específica aparente de 0,20 g/cm3 foram obtidos por secagem supercrítica (SCD) dos géis úmidos depois da lavagem com etanol. O volume de poros e o tamanho médio de poros aumentaram com o aumento da quantidade de SDS. Os aerogéis SCD preservaram a maior parte das características do fractal de massa dos géis úmidos originais em larga escala de comprimento e exibiram num nível de resolução em torno de 0,7 nm uma mudança („crossover‟) para uma estrutura de fractal de massa e superfície, com dimensão aparente de fractal de massa Dm ~ 2,4 e dimensão de fractal de superfície Ds ~ 2,6, conforme concluído a partir dos dados de espalhamento de raios-X à baixo angulo (SAXS) e adsorção de Nitrogênio. Aerogéis hidrofóbicos secos a pressão ambiente (APD) apresentaram superfície específica típica de 800 m2 /g e massa específica aparente de 0,20 g/cm3 e foram obtidos após sililação dos precursores géis úmidos com uma mistura de Hexametildisiloxano (HMDSO) e Trimetilclorosilano (TMCS). O volume de poros e o tamanho médio de poros dos aerogéis APD aumentaram com o aumento da quantidade de SDS. Os aerogéis APD preservaram a maior parte das características do fractal de massa do precursor gel úmido em larga escala de comprimento. O raio de giração dos clusters dos aerogéis APD (tipicamente 17 nm) aumentou com o aumento da quantidade de SDS, enquanto que o raio da partícula primária de sílica (tipicamente 2,0 nm) aumentou com a primeira adição de SDS (em relação à amostra sem SDS) e depois diminuiu regularmente com o aumento da quantidade de SDS. A partícula primária apresentou ainda alguma heterogeneidade interna e uma interface do contorno difuso com espessura em torno de 0,7 nm, de acordo com o modelo de gradiente linear para o contorno difuso. / This work aims to study the structural characteristics of silica wet gels prepared from hydrolysis of Tetraethoxysilane (TEOS) with additions of the anionic surfactant Sodium Dodecyl-Sulfate (SDS). The surfactant was removed after gelation. Wet gels exhibited massfractal structure with mass-fractal dimension D (typically around 2.25) in a length scale extending from a characteristic size ξ (typically about 10 nm) of the mass-fractal domains to a characteristic size a0 (typically between 0.3 - 0.4 nm) of the primary particles building up the fractal domains. ξ increased while D and a0 diminished slightly as the SDS quantity increased. Aerogels with typical specific surface of 1000 m 2 /g and density of 0.20 g/cm3 were obtained by supercritical drying (SCD) of the wet gels after washing with ethanol and n-hexane. The pore volume and the mean pore size increased with the increase of the SDS quantity. The aerogels presented most of the mass-fractal characteristics of the original wet gels at large length scales and exhibited at a higher resolution level at about 0.7 nm a crossover to a masssurface fractal structure, with apparent mass-fractal dimension Dm ~ 2.4 and surface-fractal dimension Ds ~ 2.6, as inferred from small-angle X-ray scattering (SAXS) and Nitrogen adsorption data. Hydrophobic ambient pressure drying (APD) aerogels with typical specific surface of 800 m2 /g and bulk density of 0.20 g/cm3 were obtained after silylation of the precursor wet gels with a mixture of Hexamethyldisiloxane (HMDSO) and Trimethylchlorosilane (TMCS). The pore volume and the mean pore size of the APD aerogels increased with increasing the SDS quantity. APD aerogels presented most of the mass-fractal characteristics of the precursor wet gels at large length scales. The radius of gyration of the clusters of the APD aerogels (typically 17 nm) increased with increasing the SDS quantity, while the radius of the silica primary particles (typically 2.0 nm) increased at first with the addition of SDS (with respect to the sample without SDS) and decreased regularly afterward with increasing the SDS quantity. The primary particles presented yet some internal inhomogeneity and a diffuse-boundary interface with thickness of about 0.7 nm, according to a linear-gradient model for the diffuse boundary.

Submitted by Bruna Patrocinio Lima null (brunapatrocinio@globo.com) on 2017-05-12T15:11:12Z No. of bitstreams: 1 Bruna_ dissertação final.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-12T16:51:27Z (GMT) No. of bitstreams: 1 lima_bp_me_rcla.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5) / Made available in DSpace on 2017-05-12T16:51:27Z (GMT). No. of bitstreams: 1 lima_bp_me_rcla.pdf: 13918588 bytes, checksum: 30ea5c3dcd5492e9be4f34c07ae6e137 (MD5) Previous issue date: 2017-03-15 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O Processo Sol-Gel tem sido utilizado para a preparação de materiais vítreos ou vítreo-cerâmicos a partir das reações de hidrólise e policondensação de alcoóxidos metálicos. A reação global do processo envolve a reação de hidrólise e policondensação dos siloxanos, seguido de gelificação, envelhecimento e secagem dos géis. Para preservar as propriedades estruturais dos géis úmidos, a secagem pode ser realizada por processos hipercríticos, ou pela introdução de agentes hidrofóbicos, ou até mesmo por sublimação dos solventes remanescentes das reações de hidrólise e policondensação. Quando a secagem é realizada por processo hipercrítico, o material obtido é conhecido como Aerogel. O método consiste em fazer a troca dos solventes remanescentes das reações de hidrólise e policondensação por um solvente que possa ser extraído por processo hipercrítico. No nosso caso, as amostras híbridas de sílica foram preparadas via Processo Sol-Gel utilizando os alcoóxidos 3-Glicidoxipropiltrimetoxisilano e Tetraethoxisilano na relação molar de 4:1. A hidrólise do sistema foi promovida em meio ácido pela adição de 3 diferentes ácidos Clorídrico, ou Nítrico, ou Bromídrico. Após o término da reação de hidrólise, as soluções, que recebem o nome de Sol, foram acondicionadas em recipientes e mantidas em estufa a 40 °C para gelificação e envelhecimento. A troca dos solventes foi realizada por Etanol, seguida de CO2 líquido em autoclave especialmente desenvolvida para o processo e sua extração realizada em temperatura e pressão superiores a 31° C e 74 atm, respectivamente. As características estruturais dos aerogéis de silica foram estudadas através dos métodos de adsorção de nitrogênio e espalhamento de luz visível (λ= 405 nm, 543 nm e 612 nm). A técnica de adsorção de nitrogênio permitiu determinar a distribuição de tamanho dos poros que apresentou um pico relativamente estreito na região de mesoporos , a superfície específica em torno de 600 m²/g, o tamanho médio dos poros em torno de 10 nm e o tamanho médio das partículas em torno de 3 nm. A técnica de espalhamento de luz visível permitiu determinar a dimensão do fractal dentro do intervalo de 1 < D < 3 que caracteriza uma estrutura que pode ser descrita como fractal de massa, o tamanho médio dos poros entre 1000 nm e 4000 nm, e o tamanho médio das partículas entre 300 nm e 800 nm. Os resultados obtidos para o tamanho de poros e tamanho de partícula obtido através das duas técnicas apresentarem grande discrepância, e a razão entre esses parâmetros são equivalentes mesmo quando vistas em diferentes escalas. / The Sol-Gel Process has been used for the preparation of vitreous or vitreous-ceramic materials from the hydrolysis and polycondensation reactions of metal alkoxides. The overall reaction of the process involves the hydrolysis reaction and the polycondensation reaction of the siloxanes, followed by gelling, aging and drying of the gels. To preserve the structural properties of wet gels, the drying can be carried out by hypercritical processes, by the introduction of hydrophobic agents, or even by sublimation of the remaining solvents of the hydrolysis and polycondensation reactions. When the drying is performed by hypercritical process, the material obtained is known as Aerogel. The method consists of making the exchange of remaining solvent hydrolysis and polycondensation reactions by a solvent that can be extracted by hypercritical process. In our case, the hybrid silica samples were prepared by Sol-Gel Process using the alkoxides 3-glycidoxypropyltrimethoxysilane and Tetraethoxisilano in molar ratio of 4:1. Hydrolysis of the system was promoted in acidic medium due to the addition of the 3 different hydrochloric, or nitric, or hydrobromic acids. After completion of the hydrolysis reaction, the solutions, which are called Sol, were packed in containers and kept in an oven at 40° C for gelling and aging. Solvent exchange was carried out by Ethanol, followed by liquid CO2 in an autoclave specially developed for the process and its extraction performed at higher temperature and pressure at 31 ° C and 74 atm, respectively. The structural characteristics of silica aerogels were studied through the methods of nitrogen adsorption and scattering of visible light (λ= 405 nm, 543 nm e 612 nm). The nitrogen adsorption technique made it possible to determine the pore size distribution which presented A relatively narrow peak in the mesoporous region, the specific surface around 600 m²/g, The average size of the pores around 10 nm and the average size of the particle around 3 nm.. The visible light scattering technique allowed to determine the Dimension of the fractal within the range of 1 <D <3 which features a structure that can be described as mass fractal, the average size of the pores between 1000 nm and 4000 nm and the average size of the particle between 300 nm and 800 nm. The results obtained for the size of pore and particle size obtained by the two techniques present greater discrepancy and the ratio between these parameters are equivalent.

Introduction: Chronic wounds are a great burden to care-givers and patients alike and are the main cause of many preventable amputations. Such wounds are treated with wound dressings but providing a wound environment that is conducive to proper wound healing is not always possible with such dressings. Absorbatox™ is a natural zeolite that has been manipulated to increase its cationic exchange capacity and has its main functionality as a potential wound healing agent in its strong capillary action. This quality enables the zeolite to absorb excess wound exudate and thus prevent wound infection and maceration. Absorbatox™ was characterised to determine its effects on wound healing. Methods: The physical characterisation of two grades of Absorbatox™ - granular and micronised - was conducted using nitrogen adsorption to determine pore size and surface area, and laser particle sizing to determine the particle sizes of the Absorbatox™ particles. Full-thickness wounds of 8 x 8 mm were created on the backs of pigs and treated with Absorbatox™, a positive and a negative control. The wound dimensions were measured and recorded. The wounds were then excised on selected days of each phase of wound healing and fixed in formalin. The wound sections were analysed by mass spectrometry imaging and abundant wound proteins were identified from the tryptic digests using BLAST against the Swiss-Prot database. Results: The surface areas of the micronised and granular Absorbatox™ were 14.43 and 11.23 m2/g, respectively. The micronised Absorbatox™ particle sizes ranged between 0.8 µm to approximately 300 µm with an average pore diameter of 28.2 nm. The granular Absorbatox™ particle sizes ranged between 2 µm and 875 µm with average pore diameters of 43.8 nm. Absorbatox™ showed better wound healing by delaying wound contraction and causing more rapid shallowing of the wound depths compared to the negative control. The difference observed in the wound healing rates of the Absorbatox™-treated and positive control groups were statistically significant and the histological evaluations of the wounds treated with Absorbatox™ showed wound closures that were associated with qualities that more closely resembled normal, healthy tissue than the positive control wounds. The protein activity in the trypsin-digested tissue including within the wound area and the surrounding healthy tissue was successfully imaged using MALDI-MSI. BLAST software was used at an e-value of 30 to identify possible proteins from the tryptic digests and were identified as proteins involved in wound healing. Discussion: Micronised Absorbatox™ treated wounds showed more rapid healing than the other treatments most likely due to the smaller particles and pores which results in strong capillary action to absorb excess exudate. Mass spectrometry imaging allowed monitoring of the protein fluctuations that occur during wound healing. The proteins detected were then identified using BLAST and MASCOT database comparison tools which identified that the abundant proteins detected by mass spectrometry were not those typically observed in wound healing but rather those involved in molecular aspects of wound healing like nerve regeneration, cell proliferation, survival, and migration. / Dissertation (MSc)--University of Pretoria / Pharmacology / unrestricted

No description available.

No description available.

<div> <p>Metal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs.</p><p>The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffrac- tion (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused de-</p><p> </p><p>position modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pres- sure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.</p><div><br></div></div>

Indiana University-Purdue University Indianapolis (IUPUI) / Metal-organic frameworks (MOFs) are a class of compounds consisting of metal ions or clusters coordinated to organic ligands in porous structure forms. MOFs have been proposed in use for gas adsorption, purification, and separation applications. This work combines MOFs with 3D printing technologies, in which 3D printed plastics serve as a mechanical structural support for MOFs powder, in order to realize a component design for gas adsorption. The objective of the thesis is to understand the gas adsorption behavior of MIL-101 (Cr) MOF coated on 3D printed PETG, a glycol modified version of polyethylene terephthalate, through a combined experimental and modeling study. The specific goals are: (1) synthesis of MIL-101 (Cr) MOFs; (2) nitrogen gas adsorption measurements and microstructure and phase characterization of the MOFs; (3) design and 3D printing of porous PETG substrate structures; (4) deposition of MOFs coating on the PETG substrates; and (5) Monte Carlo (MC) modeling of sorption isotherms of nitrogen and carbon dioxide in the MOFs. The results show that pure MIL-101 (Cr) MOFs were successfully synthesized, as confirmed by the scanning electron microscopy (SEM) images and X-ray diffraction (XRD), which are consistent with literature data. The Brunauer-Emmett-Teller (BET) surface area measurement shows that the MOFs samples have a high cover- age of nitrogen. The specific surface area of a typical MIL-101 (Cr) MOFs sample is 2716.83 m2/g. MIL-101 (Cr) also shows good uptake at low pressures in experimental tests for nitrogen adsorption. For the PETG substrate, disk-shape plastic samples with a controlled pore morphology were designed and fabricated using the fused deposition modeling (FDM) process. MOFs were coated on the PETG substrates using a layer-by-layer (LbL) assembly approach, up to 30 layers. The MOFs coating layer thicknesses increase with the number of deposition layers. The computational model illustrates that the MOFs show increased outputs in adsorption of nitrogen as pressure increases, similar to the trend observed in the adsorption experiment. The model also shows promising results for carbon dioxide uptake at low pressures, and hence the developed MOFs based components would serve as a viable candidate in gas adsorption applications.