Dissertations / Theses on the topic 'MIL-101'

Orientador: André Luiz Barboza Formiga
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química
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Resumo: O trabalho apresentado explora a modificaçãoo do processo de síntese de uma rede metalorgânica conhecida como MIL-101(Cr), um material formado por clusters trinucleares de crômio(III) unidos por ligantes tereftalato em ponte. A partir do uso de meios reacionais contendo uma mistura de componentes (ligantes ou metais), visou-se a incorporação de diferentes componentes em materiais contendo a mesma estrutura do MIL-101(Cr). Os produtos formados por esta estratégia foram analisados por difração de raios X pelo método de pó, onde se observou que, dependendo da composição do meio reacional, materiais contendo a mesma estrutura do MIL-101(Cr) foram formados. Evidências da incorporação dos diferentes componentes na estrutura dos materiais foram conseguidas pelo uso das espectroscopias nas regiões do infravermelho e ultravioleta e visível. Para os materiais contendo diferentes ligantes, observou-se um grau de incorporação de um dos ligantes substituídos de até aproximadamente 20%, apresentando áreas superficiais da ordem de 2300 mg. Já, para os materiais contendo diferentes metais, obteve-se uma incorporação de Fe(III) de até 17%. Além do mais, neste caso, alguns resultados mostram que há uma homogeneidade da distribuição de ferro nestes materiais. Desta forma, a partir do desenvolvimento deste trabalho, mostrou-se que o método de síntese utilizado foi bastante simples e eficiente para a produção de novos materiais que apresentam a estrutura do MIL-101, mas com superfícies com características e reatividade diferenciadas.
Abstract: This study explores modifications in the process of synthesis of a metal-organic framework known as MIL-101(Cr), formed by chromium(III) trinuclear clusters linked by terephthalate bridges. Through the use of reaction media containing a mixture of components (linkers or metals), we aimed the incorporation of different components in materials presenting MIL-101(Cr) structure. The products obtained from this approach were characterized by powder X-ray diffraction, where we could observe that materials isoreticular to MIL-101(Cr) were formed, depending on the composition of reaction medium. From infrared and ultraviolet and visible spectroscopies, the incorporation of the different components in the structures was confirmed. For the materials containing different linkers, we observed incorporation degrees up to 20% for one of the substituted linkers and these materials presented specific surface areas in the order of 2300 mg. For the systems containing different metals, we obtained incorporation degrees up to 17%. Moreover, some results show that iron centers are homogeneously distributed over the structures. In conclusion, we could show that this synthetic approach was very simple and efficient for the formation of novel materials that are isoreticular to MIL-101(Cr), but presenting surfaces with diverse characteristics and reactivity.
Mestrado
Quimica Inorganica
Mestre em Química

The Metal-Organic Framework (MOF) MIL-101(Cr) has been reported as a good catalyst for cyanosilylation reactions. This process constitutes an important step in the preparation of compounds like -aminoalcohols, -hydroxyacids, -hydroxyketons and -aminoacids, which are very useful in the synthesis of pharmaceuticals and agrochemicals. MIL-101(Cr) is a highly porous solid, with large pores and, therefore, it can be used as heterogeneous catalyst in processes which involve bulky substances, such as the molecules of biological interest. Understanding at the molecular level the performance of this MOF as a catalyst in cyanosilylation of aldehydes is extremely important, because it would allow the identification of the characteristics of this material that make the catalysis possible. Thus, the obtained information could help the design of new MOFs that are more efficient or, different ways to optimize the catalytic activity of MIL-101(Cr). In this work, the catalytic properties of this material are investigated for the cyanosilylation reaction of aldehydes through DFT calculations. Whence, mechanisms of aldehydes conversion in their respective trimethylsilylated cyanohydrins were performed, through the addition of trimethylsilyl cyanide. Five catalyzed mechanisms were studied using models of metallic clusters to describe the catalytic site of MIL-101(Cr) and three non-catalyzed mechanisms were also analyzed, in order to be compared to the catalyzed processes. The results indicate that both, the catalyzed and the non-catalyzed mechanism, occur through concerted processes, in which there is formation of a transition state with a five-membered cycle. Furthermore, the catalytic performance of MIL-101(Cr) probably occurs due to the presence of Lewis acidic sites, which come from coordinatively unsaturated chromium(III) ions in regions of crystal defects, located in the material structure, or in its surface. Thereby, one way of enhancing the catalytic properties of MIL-101(Cr) would be through their preparation by synthetic routes that lead to defects in this solid structure.
A Metal-Organic Framework (MOF) MIL-101(Cr) foi reportada como um bom catalisador para a reação de cianossililação de aldeídos. Esse processo constitui uma etapa importante na preparação de compostos como ß-aminoálcoois, a-hidroxiácidos, a-hidroxi-cetonas e a-aminoácidos, os quais são muito utilizados na preparação de fármacos e agroquímicos. A MIL-101(Cr) é um sólido altamente poroso, de poros largos e, portanto, pode ser utilizada como catalisador heterogêneo em processos que envolvam substâncias volumosas, tais como as moléculas de interesse biológico. O entendimento ao nível molecular da atuação dessa MOF como catalisador na cianossililação de aldeídos é de extrema relevância, pois permitirá a identificação das características desse material que tornam a catálise possível. Assim, as informações obtidas poderão auxiliar na proposta de novas MOFs, mais eficientes ou, de maneiras para otimização do desempenho catalítico da MIL-101(Cr). Por isso, nesta dissertação, a propriedade catalítica desse material é investigada para a reação de cianossililação de aldeídos, utilizando-se a DFT. Assim, foram realizados estudos de mecanismos de conversão de aldeídos em suas respectivas cianoidrinas trimetil-sililadas, através da adição de cianeto de trimetil-silano. Foram estudados cinco mecanismos catalisados, utilizando-se modelos de aglomerados metálicos para a descrição do sítio catalítico da MIL-101(Cr), e três mecanismos não catalisados, com o objetivo de serem comparados aos processos catalisados. Os resultados indicam que ambos os mecanismos, catalisado e não catalisado, ocorrem preferencialmente através de processos concertados, nos quais há formação de um estado de transição que apresenta um ciclo de cinco membros. Além disso, o desempenho catalítico da MIL-101(Cr) deve-se, provavelmente, aos sítios ácidos de Lewis, que ocorrem devido à presença de íons de cromo(III) coordenativamente insaturados, localizados em regiões de defeitos da estrutura cristalina do material, ou em sua superfície. Dessa forma, uma maneira de potencializar as propriedades catalíticas da MIL-101(Cr) é através de sua preparação por rotas sintéticas que conduzam à defeitos na estrutura desse sólido.

Dissertação (mestrado)—Universidade de Brasília, Instituto de Ciências Sociais, Centro de Pesquisa e Pós-Graduação Sobre as Américas, Programa de Pós-Graduação em Estudos Sobre as Américas, 2014.
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O tema do Estado desenvolvimentista tem sido estudado e discutido desde o início do século XX. Quais são suas propriedades? Qual é o papel do Estado no desenvolvimento científico-tecnológico de um país e quais são os fatores que tornam um Estado um desenvolvimentista? É neste corpo de literatura que o presente trabalho pretende se inserir. Especificamente, o trabalho apresenta uma parte da literatura mais recente sobre o Estado desenvolvimentista, investigando os fatores novos que o configuram no século XXI. Após uma discussão sobre modelos de Estados desenvolvimentista (na Ásia, Europa, Estados Unidos e Brasil), o caso do programa brasileiro Ciência sem Fronteiras (CSF) é estudado para verificar se é uma demonstração de um novo rumo de Estado Desenvolvimentista em Rede do Estado brasileiro. Para verificar isso, foram realizadas oito entrevistas com atores envolvidos com o programa. Ao sintetizar os resultados das entrevistas, a autora conclui que o programa parece mais com um Estado Desenvolvimentista Burocrático (DBS) e postula novas hipóteses a partir das entrevistas realizadas.
The Developmental State, a term which refers to state-led development with regards to the economy as well as scientific and technological sectors, has been studied and debated by social scientists since the beginning of the 20th century. Specifically, the discussion centers on questions such as: what are its properties? What is the role of the government in fostering innovation in science and technology in a particular country, and what are the factors that turn a state into a Developmental State? This thesis aims to insert itself within this body of literature, asking new questions about the role of the Developmental State in Brazil. Specifically, the thesis studies a portion of the more recent literature on the developmental state, investigating the new factors that contribute to a developmental state in the 21st century. After a theoretical discussion on different models of developmental states (in Korea and Japan, Germany and Sweden, the United States, and Brazil), an empirical study on the Brazilian Science without Borders policy is carried out, seeking to verify whether it is a demonstration of a new Developmental Network State (DNS) model in Brazil. Eight semi-structured interviews were carried out with key actors involved in the formulation and execution stages of Science without Borders. The thesis concludes that the program most resembles an extension of the current Brazilian developmental model, the Developmental Bureaucratic State (DBS), and postulates new hypotheses that could be tested in the future, on the basis of the interview results.

Depuis une quinzaine d’années, les matériaux poreux de type Metal Organic Frameworks (MOFs) offrent de nouvelles perspectives dans le cadre du stockage d’hydrogène par adsorption. Ces matériaux possèdent une structure et un réseau de pores particulièrement bien adaptés à l’adsorption des gaz. Ainsi, le téréphtalate de Chrome (III) (MIL-101(Cr)), composé chimiquement très stable, possède une grande capacité de stockage de l’hydrogène, du dioxyde de carbone et du méthane. Afin de renforcer sa capacité de stockage d’hydrogène, un dopage au charbon actif (AC) du matériau a été envisagé. Les synthèses des matériaux dopés et non-dopés ont été réalisées et, pour cela, différents agents minéralisants (acide fluorhydrique, acide acétique et acétate de sodium) ont été testés. Les matériaux synthétisés furent caractérisés par diffraction des rayons X (DRX), par microscopie électronique à balayage (MEB), par analyses thermogravimétriques (ATG) et par adsorption d’azote à 77K. Les capacités de stockage d’hydrogène de ces matériaux à 77 K et 100 bar ont été évaluées par mesures des isothermes d’adsorption d’hydrogène, réalisées par méthodes volumétrique et gravimétrique. Les résultats obtenus par ces deux méthodes sont en parfait accord et le matériau composite affiche une capacité d’adsorption de 13.5 wt%, qui est supérieure à celle du matériau non dopé (8.2 wt% dans les même conditions expérimentales). Les cinétiques d’adsorption ont été mesurées à 77 K par méthode volumétrique. Les résultats obtenus ont été comparés au modèle de la force motrice linéaire, Linear Driving Force (LDF). Un modèle de diffusion dépendant de la température a été développé afin de tenir compte des variations de températures qui se produisent durant le processus d’adsorption
Since the last 15 years, the porous solids such as Metal-Organic Frameworks (MOFs) have opened new perspectives for the development of adsorbents for hydrogen storage. The structure and the pore networks of these materials are especially adapted to the adsorption of gases. The chromium (III) terephthalate-based MIL-101(Cr) is a very stable material which exhibits good adsorption uptakes for hydrogen (H2), carbon dioxide (CO2) and methane (CH4).In this study, syntheses were carried out by different ways and several mineralizing agents such as hydrofluoric acid (HF), acetic acid (CH3COOH) and sodium acetate (CH3COONa) have been tested. Moreover, Activated Carbon (AC) has been introduced in the framework to create an AC incorporated composite material with an enhanced specific surface area. Conventional techniques such as powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and nitrogen (N2) adsorption isotherms at 77 K were used for materials characterizations.In the aim to evaluate hydrogen storage capacities of these materials, hydrogen adsorption isotherms were measured at 77 K via both volumetric and gravimetric methods, and the obtained results are in good agreement. A hydrogen uptake value of 13.5 wt% has been measured at 77 K and 100 bar for the composite material which shows a great improvement of hydrogen capacity compared to the pristine MIL-101(Cr) (8.2 wt%).Finally, hydrogen adsorption kinetics has been measured at 77 K using volumetric method. The obtained results were compared to the Linear Driving Force (LDF) and a temperature dependent diffusion model was also considered to take into account the temperature variations which occur during the adsorption process

A supply of clean, carbon neutral and sustainable energy is the most scientific and technical challenge that humanity is facing in the 21st century. Though there is enough fossil fuels available for a few centuries, their use would increase the level of CO2 in the atmosphere. This would lead to global warming and may pose serious threats such as rising of sea level, change in hydrological cycle, etc. Hence there is a need for an alternative source of fuel that is clean and sustainable. Among the many resources considered as an alternative power source, hydrogen is considered one of the most promising candidates. To use hydrogen commercially, appropriate hydrogen storage system is required. Various options to store hydrogen for onboard use include gaseous form in high-pressure tanks, liquid form in cryogenic conditions, solid form in chemical or metal hydrides, or by physisorption of hydrogen on porous materials. One of the emerging porous materials are metal-organic frameworks (MOFs) which provide several advantages over zeolites and carbon materials because the MOFs can be designed to possess variable pore size, dimensions, and metrics. In general, MOFs adsorb hydrogen through weak interactions such as London dispersion and electrostatic potential which lead to low binding enthalpies in the range of 4 to 10 kJ/mol. As a result, cryogenic conditions are required to store sufficient amounts of hydrogen inside MOFs. Up to date several MOFs have been designed and tested for hydrogen storage at variable temperature and pressure levels. The overall results thus far suggest that the use of MOFs for hydrogen storage without chemical and electronic modifications such as doping with electropositive metals or incorporating low density elements such as boron in the MOFs backbone will not yield practical storage media. Such modifications are required to meet gravimetric and volumetric constraints. With these considerations in mind, we have selected a Cr-based MOF (MIL-101; Cr(F,OH)-(H2O)2O[(O2C)-C6H4-(CO2)]3•nH2O (n ≈ 25)) to investigate the impact of nickel inclusion inside the pores of MIL-101 on its performance in hydrogen storage. MIL-101 has a very high Langmuir surface area (5900 m2/g) and two types of mesoporous cavities (2.7 and 3.4 nm) and exhibits exceptional chemical and thermal stabilities. Without any modifications, MIL-101 can store hydrogen reversibly with adsorption enthalpy of 10 kJ/mol which is the highest ever reported among MOFs. At 298 K and 86 bar, MIL-101 can store only 0.36 wt% of hydrogen. Further improvement of hydrogen storage to 5.5 wt% at 40 bar was achieved only at low temperatures (77.3 K). As reported in the literature, hydrogen storage could be improved by doping metals such as Pt. Doping is known to improve hydrogen storage by spillover mechanism and Kubas interaction. Hence we proposed that doping MIL-101 with a relatively light metal possessing large electron density could improve hydrogen adsorption. Preferential Ni doping of the MIL-101’s large cavities which usually do not contribute to hydrogen uptake is believed to improve hydrogen uptake by increasing the potential surface in those cavities. We have used incipient wetness impregnation method to dope MIL-101 with Ni nanoparticles (NPs) and investigated their effect on hydrogen uptake at 77.3 K and 298 K, at 1 bar. In addition, the impact of metal doping on the surface area and pore size distribution of the parent MIL-101 was addressed. Metal content and NPs size was investigated by ICP and TEM, respectively. Furthermore, crystallinity of the resulting doped samples was confirmed by Powder X-ray Diffraction (PXRD) technique. The results of our studies on the successful doping with Ni NPs and their impact on hydrogen adsorption are discussed.

碩士
元智大學
化學工程與材料科學學系
98
Both from the point of view of global warming and from that of the inevitable exhaustion of Earth’s oil reserve, worldwide interest is focused on using a clean burning substitute such as hydrogen in place of fossil fuels. However the storage of hydrogen is one of the most important challenges impeding its practical application. Metal–organic frameworks (MOFs) are a new emerging class of crystalline porous materials, displaying very low density, significant thermal stability, and very high surface area. They offer significant opportunities for hydrogen storage. Therefore, the main objectives were to develop and investigate the synthesis methods, fine structural characterization, and capacity of hydrogen storage of MOFs using XRD, FE-SEM/EDS, TEM, BET, TGA, ESCA, and XANES/EXAFS techniques. Experimentally, MOFs were synthesized with different metal nitrates in the presence of different solvents combined with organic linkers. The solvothermal method was used to synthesize the MOFs with the reaction temperatures range from 200 to 220oC. These MOFs were named as MIL-101(Cr), and MIL-53(Al) having the particle size about 0.5~0.7 and 1~4 μm, respectively identified by FE-SEM microphotos. Since as-synthesized MOFs contain many impurities, it may cause low porosity. Therefore the cleaning methods, such as optimum calcination temperatures or washing several times with different solvents at different warm temperatures were effective and approved to improve higher specific surface area and porosity. The specific surface area of MIL-101(Cr) and MIL-53(Al) were 3241 and 1181 m2/g, respectively. N2 adsorption isotherms of MOFs were type I and the distribution of pore diameter curves revealed that MOFs were microporous and mesopores materials. The XRD patterns represented that MOFs had well crystallinity after chemical treatment. EDS data indicated that MOFs consist of C, O elements and different kinds of metals. FTIR spectra exhibited vibrational bands in the usual region of 1400~1700 cm-1 for the carboxylic function and 3000~3500 cm-1 for OH- group of these MOFs. TGA curves showed that these MOFs were stable around 200~400oC. XANES/EXAFS spectroscopy was performed to identify the fine structures of MIL-101(Cr). The XANES spectra indicated that the valence of MIL-101(Cr) was Cr(III). The EXAFS data also revealed that MIL-101(Cr) had a first shell of Cr-O bonding with bond distance of 1.97 A and the coordination number was 5.4. The hydrogen storage capacity of MIL-101(Cr) and MIL-53(Al) were 0.163 and 0.14 wt%, respectively at 450 psig (30 atm) and room temperature measured using high-pressure thermogravimetric analyzer. In order to improve the hydrogen storage capacity of MOFs, metal/activated carbons were mixed with MOFs. FE-SEM microphotos of Pt/AC and Pd/AC indicated that the particle sizes were 2~5 and 5~10 nm, respectively. By using XPS and XANES spectra, it had found that both Pt and Pd species had zero valency. The EXAFS data revealed that Pt/AC and Pd/AC have a first shell of Pt-Pt and Pd-Pd bonding with bond distances of 2.78 and 2.75 A, respectively. Coordination numbers of both nanoparticles were close to 8 with a FCC structure. The catalytic properties of Pt/AC and Pd/AC were studied for hydrogen spillover in MIL-101(Cr) modified by 5 wt % of catalyst. The hydrogen adsorption capacity of modified MIL-101(Cr) was significantly enhanced up to 0.461 wt% by using the secondary spillover by carbon bridges measured at 450 psig and room temperature. In addition, the adsorption thermodynamic of the data was also confirmed using thermodynamic equations for thermodynamic consistency. Under lower pressures, the adsorption heat is affected by adsorption behaviors. The adsorption heats decrease of increasing adsorption capacities. The adsorption heat of hydrogen onto modified MIL-101(Cr) is < 44 kJ/mol using the secondary spillover of carbon bridges under lower pressures.

碩士
國立臺灣大學
化學工程學研究所
104
The purpose of this study is using an in-situ assisted acetic acid procedure to prepare a MIL-101 as filler in ceramic membrane. The MIL-101 membrane is firstly applied for organic solvent nanofiltration. In this study, the effects of synthetic conditions are investigated to get an invisible defect membrane and nanofiltration performance is also checked to prove the feasible application of MIL-101 membrane. Incorporation of metal organic framework (MIL-101) as filler on ceramic membrane is firstly investigated. In-situ method assisted by acid modular is utilized to synthesize uniform and defect-free MIL-101 membrane. Effect of additives such as NaOH, HF, CH3COOH and concentration of reactants are surveyed to find out the optimal synthetic conditions. Synthesis of MIL-101 membrane by using in-situ acetic acid-assisted method is proved as efficient way to prepare a compact and dense MIL-101 layer compared to other methods as thermal seeding method, layer by layer seeding method. The MIL-101 membranes are characterized by using a variety of different techniques, including X-ray thin film diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy EDX. MIL-101 is chosen as material filler for membrane in nanofiltration application because of its ability to form the largest pore size in the MOFs’ family and a number of its prominent properties for molecular separation applications such as high surface area and well-defined pore size. Besides, MIL-101 and ceramic substrate are inorganic materials, so they are able to be stable in harsh solvent such as N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), dimethylacetamide (DMAc), those usually dissolve common polymers. The MIL-101 membranes are applied in organic solvent nanofiltration (OSN) by testing separation of Rose Bengal (RB) from NMP, DMSO, DMAc and ethanol. The MIL-101 membranes show a significantly high rejection but lower permeance compared to bare ceramic membrane. The best flux and rejection of MIL-101 membrane with RB ethanol solution are 1.65 lm-2h-1bar-1 and 99.7% respectively where ratio of chromium nitrate, benzendicarboxylic acid and water is 1:1:277, respectively and 0.8 ml of CH3COOH. The MIL-101 membranes also exhibit the stability under harsh solvent with high rejection of RB and constant flux within 3 hours.

碩士
明志科技大學
化學工程系碩士班
105
In this study, mesoporous MIL-101(Cr)-SO3H was synthesized by self-made sodium 2-sulfoterephthalate (sTA-Na). The innovative preparation method is based on normal pressure, and the product is characterized by FTIR, XRD, TGA, etc. to compare with that prepared by the hydrothermal method. The experimental results show both have same functional groups, similar crystal phases and thermal stability of about 475℃. Instead of hydrothermal surrounding, MIL-101(Cr)-SO3H can be easily synthesized under normal pressure, which procedure is less energy consumption and is easier applied to mass production. In this study, metal ions Mn+ are implanted into MIL-101(Cr)-SO3H to enhance the acidity of MIL-101(Cr) and to study the synergistic effect of Lewis acid on Brönsted acid. In the acidic solid of MIL-101(Cr)-SO3H-Mn+, the sites of Brönsted acid are -SO3H and Lewis acid is Mn+ ions. By respectively adding a series of Mn+ ions, we investigated the effects of the electric charge and the ionic radius of Lewis acid on the synergistic acidity. The physicochemical properties of MIL-101(Cr)-SO3H-Mn+ are also characterized by TEM, SEM, EDS and BET. The experimental results show the ionic charge effect of acidity is much larger than that of ion radius; The Al3+ implantation increases the acidity of MIL-101(Cr)-SO3H- by 11 times, and the Fe3+ implantation increases by 18 times. MIL-101(Cr)-SO3H was further applied to be catalyst and absorbent in green technology. Using MIL-101(Cr)-SO3H and MIL-101(Cr)-SO3H-Mn+ as catalysts, vinyl chloride monomer (VCM) was prepared by the cracking of ethylene dichloride (EDC) at lower temperatures. The experimental results show compared to MIL-101(Cr)-SO3H, although MIL-101(Cr)-SO3H-Al has higher acidity, its catalytic performance is roughly the same (the maximum conversion rates are 78 % and 85 %, respectively). Compared with the commercial EDC pyrolysis, the presence of MIL-101(Cr)-SO3H catalyst can effectively reduce the cracking temperature ~50 % and enhance the conversion rate of EDC to 70 to 75 %, while maintaining the vinyl chloride selectivity more than 99 % and the catalyst life greater than 42 days. Another green application is using MIL-101(Cr)-SO3H or MIL-101(Cr)-SO3H-Al to adsorb aqueous methylene blue (MB) and helianthine B (HB, also called methyl orange). The UV-Vis analyses show MIL-101 (Cr)-SO3H-Al has good adsorption capacity (~97 %) for MB but almost no adsorption for HB, and the adsorption selectivity β at room temperature is 4831, indicating MIL-101(Cr)-SO3H has a good adsorption effect on cationic dyes, like MB.

碩士
明志科技大學
化學工程系碩士班
107
In our previous study, MIL-101(Cr)-SO3H powders were synthesized by hydrothermal method or normal pressure method. Although having good application performance, both of them have problems of poor yield, long process time and low specific surface area. The three-stage synthesis method is used to improve this disadvantage, and the MIL-101(Cr)-SO3H powders with better physical properties were obtained and applied to dye adsorption. In order to obtain a better pore specific surface area to further improve the adsorption efficiency of the dye, MIL-101(Cr)-SO3H powders were synthesized post-functionalized in this study. In this study, MIL-101(Cr) catalytic supporter was first synthesized from chromium nitrate and terephthalic acid, and then was further functionalized with sulfonic acid. Since MIL-101(Cr) powders contains a large amount of unreacted material inside their pores, they need to be cleaned and purified before attaching the sulfonic acid of functional group. The unreacted impurities inside the pores are removed by the organic solvent DMSO. If reducing the powder amount of MIL-101 (Cr), we can obtain the octahedron morphology of single crystal. The products were analyzed by FTIR, XRD, BET and TGA. The analysis results show the sample has the same functional groups and similar crystal phases compared with the threestage method, the specific surface area increasing from 330.5 m²/g to 882.9 m²/g and the heat resistant temperature is raised from 475 ̊C to 530 ̊C. MIL-101(Cr)-SO3H powders synthesized by post-functionalized method were further applied as adsorbent to adsorb dye methylene blue (MB), malachite green (MG) and methyl orange (HB) in water, and compared with previous studies. The adsorption performance was analyzed by UV-Vis. The experiment showed that the adsorption capacity of MIL-101(Cr)-SO3H adsorbent on methylene blue (MB) was ~98%, and the adsorption amount on malachite green (MG) was ~72%, better than the MIL-101(Cr)-SO3H adsorbent prepared by the three-stage method. Key words: metal organic framework (MOF), MIL-101(Cr)-SO3H, post functionalized method, dye adsorption.

碩士
明志科技大學
化學工程系碩士班
106
In this study, a self-made sodium 2-sulfo-terephthalalic acid(sTA-Na) was used to synthesize MIL-101(Cr)-SO3H with acidic functional groups by a new three-step process. In addition, purchased 2-amino-terephthalic acid (TA-NH2) was used to synthesize MIL-101(Cr)-NH2 with a basic functional groups by a conventional hydrothermal method. The products were characterized by FTIR, synchrotron XRD, DSC/TGA and other physicochemical analyses. The results of DSC/TGA analysis show that the thermal stability of MIL-101(Cr)-SO3H and MIL-101(Cr)-NH2 are respectively, 475°C and 400°C meaning they all. can be used in the heating environment (100°C~120°C) to produce saccharide from lignocellulose hydrolysis. 　　To investigate the effect of concentrations on the product yield in the three-step preparation of MIL-101(Cr)-SO3H.Experimental results show that the higher the concentration, the higher yield will be; the optimum concentration is 30%. For the sake of the possible toxicity of Cr3+, Cr3+ was replaced with Fe3+ to synthesize MIL-101(Fe)-SO3H. In the synthesis of MIL-101(Cr)-NH2 hydrothermal method and reflux method were respectively used. XRD analysis of the product showed that MIL-101(Cr)-NH2 has good crystallinity and hydrothermal method could obtain a double yield. This study further applied functionalized MIL-101(Cr) as a catalyst for lignocellulose hydrolysis hydrolyze saccharides from corn stalk. In a variety of pretreatments of lignocellulose, hydrothermal and ethanol washing had significantly effect on removing hemicellulose and lignin. experimental data of cellulose hydrolysis showed that MIL-101(Cr)-SO3H has a better catalyst efficiency for producing saccharide, while MIL-101(Cr)-NH2 has hardly omg catalyst performance. This may be lecause MIL-101(Cr)-SO3H has Brönsted acid reactive sites in the functional group -SO3H.

碩士
明志科技大學
化學工程系碩士班
106
In this study, a self-made sodium sulfoisophthalate (sTA-Na) was used to synthesize mesoporous MIL-101(Cr)-SO3H. Although MIL-101(Cr)-SO3H prepared by the hydrothermal method in our laboratory has good application performance in catalyst, but it has only 206 m2/g of the specific surface area in BET pore analysis. Therefore, the three-step method was used for improving the synthesis and its concentration effect was investigated. The products were characterized by FTIR, XRD and TGA. The experimental data showed that had the same functional group, similar crystal phase, and heat resistance about 475°C, while the three-step synthesis can increase the yield from 58.33% to 94.08%. In addition, the nucleation and nucleation growth rates of MIL-101(Cr)-SO3H were adjusted by the reaction temperature and time effects to obtain single crystals with a higher specific surface area. 　　In this study, MIL-101(Cr)-SO3H was further used as an adsorbent to study the adsorption effect of methylene blue (MB), malachite green (MG) and helianthine B (HB) in water. The adsorption efficiency was analyzed by UV-Vis. Experimental data showed that the adsorption of methylene blue (MB) by the MIL-101(Cr)-SO3H adsorbent reachs~88%; the adsorption of malachite green (MG) reachs~54%;but have adsorption performance, but have hardly any adsorption efficiency (~0%) for anionic helianthine B (HB), which indicates that MIL-101(Cr)-SO3H has a good adsorption of cationic dyes. On the other hand, when MIL-101(Cr)-NH2 was used as an adsorbent for anionic dye helianthine B (HB) the adsorption capacity can reach 99%, indicating that MIL-101(Cr)-NH¬2 has a good adsorption effect on anionic dye HB. 　　In this study, adsorption experiments were conducted under different pH conditions. The results showed that MIL-101(Cr)-SO3H has hardly any adsorption effect on malachite green (MG) in alkaline environments, but it has good adsorption performance in environments with pH<7. Therefore, in the recycle experiments, the need MIL-101(Cr)-SO3H was washed with an aqueous solution of pH=9 or hot water. The crystal phases refuse and offer washing are unchanged, and four runs of adsorption experiments were performed by using the recycled MIL-101(Cr)-SO3H . The adsorption efficiencies are~48.49% and ~51.17%, similar of~54.5% for the first adsorption experiment. All have good adsorption efficiencies.

碩士
國立臺灣大學
化學工程學研究所
106
High performance metal-organic framework (MOF) nanocomposite membranes with simple and rapid synthesis process were highly deserved in this century. Beside that, MOF nanoparticles compatibility and membrane thickness as the key of MOF membrane preparation are still being investigated until now. Herein, we report a first-time continuous film-like chromium benzenedicarboxylate framework MIL-101(Cr) on ceramic hollow fiber membrane via in situ growth hydrothermal method. The MOF membranes were prepared along with the MOF nanoparticles in one synthesis step. MIL-101(Cr) has a large surface area, pore size between 1,2-1,6 nm, and good hydrophilicity which can increase the flux enhancement and suitable for organic dye removing application. Dead-end nanofiltration using several type of dyes were carried out to verify the membrane quality. As a result, the nearly zero thickness of MIL-101(Cr) layer on the membrane surface allowed the outstanding water permeation value (41.4 and 46.6 L.m-2hr-1bar-1 for Brilliant Blue and Rose Bengal) which is the best result reported to date. Furthermore, well-intergrown and defect-free of MIL-101(Cr) layer on the membrane performed 100% rejection of Brilliant Blue and Acid Fuchsin from water. This energy-efficient and cost-effective strategy will be useful for the fabrication of MOF membranes for wastewater treatment nanofiltration application.

碩士
明志科技大學
化學工程系碩士班
104
In this study we successfully synthesized MIL-101-Cr-SO3H and MIL-101-Cr-SO3H-Al3+ catalysts. MIL-101 (Material of Institut Lavoisier-101) was developed by Material of Institut Lavoisier in France. MIL-101-Cr-SO3H is a metal organic framework (MOF) and made from sodium 2-sulfoterephthalic acid as the organic ligand and chromium trioxide as the trinuclear Cr. FTIR (Fourier transform infrared) analysis show sodium 2-sulfoterephthalic acid as synthesized from p-xylene has -SO3H and –COOH functional groups. XRD (X-ray Diffraction) analysis show the structure of MIL-101-Cr-SO3H is the same as the report. XPS (X-ray photoelectron spectroscopy) analysis show the atomic composition ratio of MIL-101-Cr-SO3H is the same as the theoretical values and the presence of Al3+ was verified. TGA (Thermogravimetry Analysis) analysis appear both MIL-101-Cr-SO3H and MIL-101-Cr-SO3H-Al(III) were able to withstand upto 350℃. Moreover, using TEM, SEM, EDS, BET and other equipment for characterization. In futher study, MIL-101-Cr-SO3H-Al (III) was applied to 1,2-Dichloroethane (EDC) thermal cracking reaction at lower temperature for the green synthesis. The experimental results showed that MIL-101-Cr-SO3H-Al (III) has the function of Brönsted acid assisted Lewis acid(BLA). The temperature of dehydrochlorination reaction is decreased to <350℃. Conversion of EDC is lowered to 50% ~ 80%. Selectivity of vinyl chloride is > 99%. Life of catalyst is greater than 45 days.

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.

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.

碩士
輔仁大學
化學系
106
Part.Ⅰ Polymer monolith microextraction (PMME) based on capillary monolithic column is an effective and useful technique to preconcentrate trace analytes from environmental and biological samples. A wide variety of household, medical systems and industrial waste waters have been discharged into groundwater, rivers and oceans without sewage treatment. Many organic compounds that have adverse effects on the human body have been detected such as non-steroidal anti-inflammatory drugs and endocrine disrupting compounds are collectively called environmental pollutant. The sample preparation methods was developed with environmental pollutant, including Naproxen (Na), 2,4-diclorophenol (2,4-DCP), Diclofenac (Di), Estradiol (E2), Ibuprofen (Ibu), Phenothiazine (Ptz), and Mefenamic acid (Me) by UPLC-DAD ( Ultra performance liquid chromatography- Diode array detection，UPLC-DAD). The PMME optimal parameters, silanized with MSMA about 5 hr, polymerized about 1 hr, loading speed for the PMME was 0.9 mL/hr and the elute solvent was 200 μL 25 mM ammonium acetate pH 5.0: MeOH (4:6,v/v). The coefficients of correlation (r2) for the UPLC-DAD calibration curves were greater than 0.9997. The limits of detection (LOD) and limits of quantificantion LOQ) were determined within 0.20 to 2.12 ng/mL and 0.68 to 7.07 ng/mL. The recovery of environmental pollutant in spike urine were 40.0 % to 102.0 %. Though the recovery was't very well, it could effectively reduce the matrix effect. These results shown this capillary monolithic column could be used for extraction environmental pollutant from human urine sample or reduce the matrix effect such as sorbent. Part.Ⅱ Acetaminophen (AC), is a medicine used to treat pain and fever. It is typically used for mild to moderate pain relief. However, long-term exposure or excessive use of acetaminophen causes accumulation of toxic metabolites, which leads to kidney and liver disease thus precise determination and quantitation is important. Development of highly sensitive and selective electrochemical sensors using chitosan (CHS) and metal-organic frameworks (MOFs) modified glassy carbon electrode (GCE) is creating fast and simple method for determination of acetaminophen in environmental water Development of highly sensitive and selective electrochemical sensors using chitosan (CHS) and metal-organic frameworks (MOFs) modified glassy carbon electrode (GCE) is creating fast and simple method for determination of acetaminophen in environmental water . In this optimal conditions, the results shown the modified GCE have properties of excellent electron transfer characteristics, low electron transfer resistance and increase the oxidation current by differential pulse voltammetry (DPV) and electrochemical impedance analysis (EIS). In the other hand the bare electrode and modified electrode were characterized by scanning electron microscope (SEM), energy dispersive spectrometer (EDS) and powder X - ray diffraction (PXRD), which confirmed that chitosan/ metal-organic frameworks modified electrode can be successfully prepared . The chitosan/metal-organic frameworks modified electrode shown a linear response for acetaminophen in the concentration range of 0.1 to 50 μM with detection limit of 30 nM at S/N = 3, respectively. In addition, the reproducibility and stability of this chitosan/ metal-organic frameworks modified electrode were discussed. Its relative standard deviation (RSD) of intra day and inter day were less than 4.74 % and 3.12 %, respectively. Stability still remanined above 100.84 % during one week. These results have confirmed that this modified electrode have satisfactory reproducbility and stability. Finally, this chitosan/ metal-organic frameworks modified electrode was successfully applied in the determination of acetaminophen in environmental water. The recovery was between 98.47 to 112.66 %. These results have confirmed that this modified electrode have good accuracy.