Discovery of mesoporous materials by Mobil researchers in 1992 opened a new field in catalytic applications. The materials designated as M41S family are MCM-41 with one-dimensional hexagonal structure, MCM-48 with three-dimensional cubic structure and MCM-51 with unstable lamellar structure. This family of materials have high surface areas up to 1500 m2/g, narrow pore size distributions with pore sizes varying from 20 to 100 &Aring / . These materials can be activated by incorporation of metals or active compounds into their structures. In this study, copper and nickel incorporated MCM-41 type catalytic materials were synthesized via different methods namely, impregnation, high temperature and low temperature direct synthesis methods. The Cu-MCM-41, and Ni-MCM-41, as well as synthesized MCM-41 were characterized by using XRD, TEM, N2 sorption, SEM, XRF, EDS, AAS and TPR. MCM-41 was synthesized with high temperature direct synthesis method. High surface area values up to 1400 m2/g of MCM-41 mesoporous materials were obtained with high pore volumes up to 1.17 cc/g. Cu-MCM-41 type catalytic materials were synthesized with three different methods. Impregnation and high temperature direct synthesis methods gave better results than those of low temperature direct synthesis method. In impregnation, relatively high surface area values (730 m2/g) were obtained with Cu/Si mole ratio as high as 0.3 in the product. For the case of high temperature direct synthesis products, Cu/Si mole ratios as high as 0.26 were obtained with somewhat smaller surface areas (400 m2/g). Low temperature direct synthesis method is the least favorable method in metal loading. Ni-MCM-41 type of catalytic materials were synthesized by impregnation and high temperature direct syntheses methods. Ni incorporation by high temperature direct synthesis method gave high surface area values (560-930 m2/g) having Ni/Si mole ratios of 0.12-0.28.

Noble metal incorporated MCM-41 based nanostructured mesoporous materials have attracted the attention of material researchers in recent years. Sorption characteristics of MCM materials can be improved by surface modification techniques. Besides surface modification, metal nanoparticles can also be produced within the pores of mesoporous materials. MCM-41 can act as host for several metal nanoparticles such as palladium. The present study is focused on the synthesis of Pd-MCM-41 nanocomposite catalytic materials by using different direct synthesis procedures, as well as an impregnation method. Impregnated samples were used to synthesize Pd nanoparticles inside the pores of MCM-41. In the direct hydrothermal synthesis of Pd-MCM-41, incorporation of the Pd metal was achieved by adding PdCl2, K2PdCl4 and Pd(NH3)4(NO2)3 solutions into the synthesis mixture. Syntheses were performed in acidic and basic routes. Hydrothermal synthesis was carried out in an autoclave at 120 oC. The solid product was filtered, washed, dried, calcined at 550 oC in a stream of dry air and reduced in a stream of hydrogen at 200 oC. In the case of impregnation, PdCl2 solution was added to a suspension of MCM-41. The product was evaporated to dryness, dried under vacuum and reduced with H2 gas at 200 oC. Physical and chemical properties and surface morphology of Pd-MCM-41 nanomaterials were characterized by using XRD, XPS, EDS, BET, SEM, TEM and TPR techniques. Very high Pd/Si ratios, as high as 0.45 and 0.18 were obtained in the mesoporous materials produced by the basic and acidic direct synthesis routes, respectively. The BET surface areas of these materials were found as 999 m2/g and 694 m2/g, respectively. These results showed that the basic direct synthesis procedure was highly successful for the incorporation of Pd into the mesoporous Si structure. In addition, EDS analysis of the Pd-MCM-41 materials prepared by the impregnation technique showed that Pd/Si ratios were 0.24 and 0.12 in the two samples having surface areas of 527 m2/g and 883 m2/g, respectively. In conclusion, high surface area of the material synthesized by the basic route together with a higher Pd/Si ratio makes this material more attractive for catalytic and hydrogen storage applications.

Bone response is one of the key determining factors in the overall success of biomaterials intended for bone regeneration and osseointegration. Understanding the formation of bone at an implant surface may lead to the improved design of biomaterials for the future. However, due to the inhomogeneity of bone tissue at an interface, two-dimensional images often lack detail on the interfacial complexity. Furthermore, the increasing use of nanotechnology in the design and production of biomaterials demands characterization techniques on a similar nano length scale. While current analysis methods, such as X-ray tomography, transmission electron microscopy, focused ion beam microscopy and scanning electron microscopy, provide a basis for analysing biomaterials and biointerfaces, they are incapable of doing so with both nanometre resolution and three-dimensional clarity. In contrast, electron tomography may be used to characterize the three-dimensional structure of biomaterials and their interfaces to bone with nanometre resolution. In this work, hydroxyapatite scaffolds, and laser-modified titanium and Ti6Al4V implants were studied in contact with human or rabbit bone. Z-contrast electron tomography revealed that the orientation of collagen in bone apposing hydroxyapatite, titanium and Ti6Al4V implants is consistently parallel to the implant surface, where the bioactive layer that precipitates on HA is oriented perpendicular to the implant surface. With this method, complete three-dimensional nanoscale osseointegration of titanium-based implants was also established. The extension of this technique from interfacial analyses to the design of biomaterials provided an understanding of the pore structure of mesoporous titania. In further investigations, the open three-dimensional pore network, as revealed by electron tomography, showed promise as a coating that improves implant osseointegration and enables site-specific drug-delivery from an implant surface. In summary, it was demonstrated that two-dimensional characterization techniques were insufficient for the investigation of nanostructured biomaterials, as well as their interfaces to bone. Visualizing biointerfaces and biomaterials with nanometre precision in three-dimensions can expose new fundamental information on materials properties and bone response, enabling better design of biomaterials for the future.

Hydrogen is considered one of the best alternatives to fossil-fuels for the transportation sector because hydrogen can be burnt cleanly and efficiently in a fuel cell to drive an electric motor. However, due to the low density of H2 at ambient conditions the conventional H2 storage technologies (cryogenic liquid and compressed gas) cannot achieve energy densities comparable to to gasoline and diesel. A second energy storage challenge onboard electric fuel cell vehicles is fuel cell power management at peak current loads, which requires an auxiliary power source like a battery or supercapacitor. The development of efficient onboard energy storage systems for H2 and auxiliary power is critical to realisation of a hydrogen economy. Mesoporous carbons were investigated as H2 storage materials in composites with magnesium hydride (MgH2),and as electrode materials for electrochemical double-later capacitors. The mesoporous carbons were prepared by two methods: (1) from porous silica and alumina templates, and (2) by chemical activation of a waste carbon source (waste coffee grounds). The experimental approach targeted reducing the cost of mesoporous carbon preparation by using a cheaper template, where the cost of alumina template was one-fifth the cost of the silica template (at the laboratory scale), or by using a waste material as a carbon source. The alumina template was found to be suitable to produce a mesoporous carbon with an average pore size of 4.8 nm. Chemical activation of coffee grounds with ZnCl2 produced activated carbons with BET surface areas up to 1280 m2/g. Mesopore volume increased with ZnCl2 impregnation ratio, with mesopore size distributions in the range 2 - 20 nm. The theoretical H2 capacity of MgH2 is 7.6 % but MgH2 application in fuel cell vehicles is limited by slow hydrogenation kinetics and high temperatures (> 573 K) for H2 release. Magnesium was impregnated on activated carbon fibres (ACF) and mesoporous carbon (prepared from silica and alumina templates) to improve H2 storage kinetics and thermodynamics by reducing the magnesium hydride particle size. Thermal gravimetric analysis (TGA) and temperature programmed desorption (TPD) studies showed that thermal decomposition of MgCl2 supported on ACF at 1173 K in N2 and H2 can produce a Mg-ACF composite. At 573 K and 2 MPa H2 pressure a Mg-ACF composite, containing 11.2 %wt Mg, showed improved H2 adsorption kinetics compared to bulk Mg powder, but the total capacity of the Mg-ACF composite was only 0.4 % wt H2. To achieve a target of 6 %wt for onboard H2 storage higher Mg loadings are required. Attempts to impregnate Mg in mesoporous carbon via the MgCl2 thermal decomposition process highlighted the difficulties of avoiding MgO formation, and show that MgH2 loaded carbon is unlikely to be a practical high density onboard H2 storage technology. Activated carbons from waste coffee grounds (CGCs) were used as electrode materials in electrochemical double-layer capacitors. The specific capacitance of CGCs was as high as 368 F/g in 1 mol/L H2SO4, with good capacitance retention at fast charge rates and stable cycling performance. The good electrochemical performance of CGCs is attributed to a porous structure featuring both micropores 0.5 - 1.0 nm wide, which are effective for double-layer formation, and small mesopores, which facilitate electrolyte transport at fast charge rates. The capacitance of CGCs is enhanced by pseudo-Faradaic reactions involving nitrogen and oxygen functional groups. At fast charge-discharge rates the CGCs had higher energy density and better stability than a commercial benchmark activated carbon (Maxsorb). The ZnCl2 activation process can be optimised to develop mesopores for improved capacitance at fast charge rates and capacitance in organic electrolytes. In 1 mol/L tetra ethyl ammonium tetrafluoroborate (TEABF4) / acetonitrile the CGC with the most mesopores, which was prepared with a ZnCl2 to coffee ratio of 5:1, has the highest capacitance at high power density. CGCs with greater mesopore content retained higher specific capacitance at fast charge-discharge rates as the mesopores acts as channels or reservoirs for electrolyte transport. An improved model for evaluation of contributions to capacitance from micropore surfaces and mesopore surfaces is proposed. From this model the double-layer capacitance of mesopores surface area was found to be about 14 μF/cm2 and did not change considerably with increasing current load. The contribution of micropores to capacitance is dependent on the accessibility of ions to the micropores, and this accessibility is proportional to the mesopore surface area. An exponential function was found to describe the contribution of mesopores and micropore surfaces to capacitance. The effective double-layer capacitance of the micropore surface area drops at fast charge-discharge rates as a result of restricted ion transport, and this result highlights the importance of mesopores to retain energy density for high power supercapacitor applications.

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Submitted by Dilene Paulo (dilene.fatima@ufcg.edu.br) on 2018-01-23T14:36:45Z No. of bitstreams: 1 CLARICE OLIVEIRA DA ROCHA – TESE PPGEQ 2014.pdf: 2084559 bytes, checksum: 35cd9fd0fad2c37f97e9a1e07b4e3877 (MD5) / Made available in DSpace on 2018-01-23T14:36:45Z (GMT). No. of bitstreams: 1 CLARICE OLIVEIRA DA ROCHA – TESE PPGEQ 2014.pdf: 2084559 bytes, checksum: 35cd9fd0fad2c37f97e9a1e07b4e3877 (MD5) Previous issue date: 2014-10-10 / CNPq / Propostas têm aparecido visando à remoção do enxofre nos combustíveis por intermédio dos processos de adsorção. Com isso, a utilização desse método para a dessulfurização vem se expondo como um bom potencial de aplicação, tanto do ponto de vista econômico como ambiental. As peneiras moleculares, do tipo silicoaluminofosfato (SAPO), vêm se apresentando como um excelente adsorvente, com uma ótima estabilidade térmica e hidrotérmica e com a impregnação de metais, tornando-se seletiva a adsorção. Assim, sintetizou-se SAPO-5 (microporoso) e SAPO-5M (mesoporoso), impregnados com diferentes teores dos metais de transição, níquel e/ou zinco. Esses adsorventes foram utilizados para a remoção do enxofre presente na mistura modelo (Heptano / Tiofeno). Para isso, foram realizadas técnicas de caracterização como TG, DRX, EDX e BET, bem como um acompanhamento cinético a fim de avaliar a eficiência da adsorção e as isotermas de equilíbrio. Foi confirmado a mesoporosidade do SAPO-5M, uma vez que o mesmo apresentou as isotermas características tipo IV (típica de material mesoporoso). O volume e o diâmetro dos poros do SAPO-5 microporoso e mesoporosos não foram totalmente obstruídos após a impregnação. Para os adsorventes mesoporosos houve um aumento de quatro vezes no diâmetro do poro, em relação ao micro. Embora, tenha apresentado redução na intensidade de difração de raios X após a impregnação, dos óxidos de níquel e/ou de zinco, obteve-se um material cristalograficamente ordenado. Ocorreu total remoção do direcionador, mostrando que a calcinação foi eficiente e o material é estável a altas temperaturas. Ademais, conseguiu-se atenuar a quantidade de enxofre de 500 ppm para cerca de 96,3 ppm, uma redução de 80%, para o adsorvente mesoporoso 0,25%Ni 0,75%Zn/SAPO-5M, cuja capacidade de adsorção de enxofre foi de 40 mg S/gadsorvente. O adsorvente com 1%Zn/SAPO-5, apresentou maior capacidade de adsorção (30 mg S/gadsorvente), dentre os materiais microporosos, conseguindo reduzir o teor de enxofre de 500 ppm para 163 ppm. Para os demais suportes e adsorventes ocorreu uma redução de aproximadamente 31 % do teor de enxofre na mistura modelo. Conclui-se que a síntese do mesoporoso foi eficiente e que o material utilizado se mostrou eficaz na remoção desse contaminante na mistura modelo. / Proposals have appeared aiming at the sulfur removal in fuels by means of adsorption processes. Thus, the use of this method for the desulfurization exposing themselves like a good application potential, both economically and environmentally. The molecular sieves silicoaluminiumfosfate type (SAPO), has been presented as an excellent adsorbent with optimum thermal and hydrothermal stability and metals impregnation, making it selective adsorption. Thus was synthesized SAPO-5 (microporous) and SAPO-5M (mesoporous) impregnated with different amounts of transition metals, nickel and/or zinc. These adsorbents were used for removal of sulfur present in the mixture model (Thiophene / Heptane). For this, characterization techniques as TG, XRD, EDX and BET were performed, as well as a kinetic monitoring to assess the efficiency of adsorption and equilibrium isotherms. It was confirmed mesoporosity of SAPO-5M, since the isotherms showed the same type IV characteristics (typical of mesoporous materials). The volume and pore diameter of the microporous and mesoporous SAPO-5 were not totally blocked after impregnation. For mesoporous adsorbents an increase of four times the pore diameter in relation to the microporous. Although, has shown a reduction in the intensity of X-ray diffraction after the impregnation of the oxides of nickel and/or zinc, gave a crystallographically ordered materials. Complete removal of the template occurred, showing that the calcination was efficient and the material is stable at high temperatures. Furthermore, we were able to attenuate the amount of sulfur 500 ppm to about 96.3 ppm, a reduction of 80% for the mesoporous adsorbent Ni 0.25% 0.75% Zn/SAPO-5M, whose adsorption capacity sulfur was 40 mg S/g of adsorbent. The adsorbent of 1% Zn/SAPO-5 showed higher adsorption capacity (30 mg S/g of adsorbent) among microporous materials, achieving reduced sulfur content from 500 ppm to 163 ppm. For other supports and adsorbent was reduced by approximately 31% of the sulfur content in the mixture model. It is concluded that the synthesis of mesoporous was effective and that the material used is effective in the removal of this contaminant in the mixture model.

abstract: Emergent environmental issues, ever-shrinking petroleum reserves, and rising fossil fuel costs continue to spur interest in the development of sustainable biofuels from renewable feed-stocks. Meanwhile, however, the development and viability of biofuel fermentations remain limited by numerous factors such as feedback inhibition and inefficient and generally energy intensive product recovery processes. To circumvent both feedback inhibition and recovery issues, researchers have turned their attention to incorporating energy efficient separation techniques such as adsorption in in situ product recovery (ISPR) approaches. This thesis focused on the characterization of two novel adsorbents for the recovery of alcohol biofuels from model aqueous solutions. First, a hydrophobic silica aerogel was evaluated as a biofuel adsorbent through characterization of equilibrium behavior for conventional second generation biofuels (e.g., ethanol and n-butanol). Longer chain and accordingly more hydrophobic alcohols (i.e., n-butanol and 2-pentanol) were more effectively adsorbed than shorter chain alcohols (i.e., ethanol and i-propanol), suggesting a mechanism of hydrophobic adsorption. Still, the adsorbed alcohol capacity at biologically relevant conditions were low relative to other `model' biofuel adsorbents as a result of poor interfacial contact between the aqueous and sorbent. However, sorbent wettability and adsorption is greatly enhanced at high concentrations of alcohol in the aqueous. Consequently, the sorbent exhibits Type IV adsorption isotherms for all biofuels studied, which results from significant multilayer adsorption at elevated alcohol concentrations in the aqueous. Additionally, sorbent wettability significantly affects the dynamic binding efficiency within a packed adsorption column. Second, mesoporous carbons were evaluated as biofuel adsorbents through characterization of equilibrium and kinetic behavior. Variations in synthetic conditions enabled tuning of specific surface area and pore morphology of adsorbents. The adsorbed alcohol capacity increased with elevated specific surface area of the adsorbents. While their adsorption capacity is comparable to polymeric adsorbents of similar surface area, pore morphology and structure of mesoporous carbons greatly influenced adsorption rates. Multiple cycles of adsorbent regeneration rendered no impact on adsorption equilibrium or kinetics. The high chemical and thermal stability of mesoporous carbons provide potential significant advantages over other commonly examined biofuel adsorbents. Correspondingly, mesoporous carbons should be further studied for biofuel ISPR applications. / Dissertation/Thesis / M.S. Chemical Engineering 2011

Améliorer la stabilité de l’interface dentine adhésif est primordial si on veut prolonger la durée de vie et la longévité des restaurations en composite. La reminéralisation utilisant des matériaux relarguant des ions semble etre une approche prometteuse pour protéger la couche hybride de la dégradation hydrolytique et enzymatique. Les verres bioactifs mésoporeux (MBG) présentent des caractéristiques de surface intéressantes qui permettent de les utiliser comme charges au sein de l’adhésif qui favorisent d’une part la reminéralisation par la libération d’ions, d’autre part la fonctionnalisation des pores par des médicaments antibactériens. Ces caractéristiques permettent de lutter contre la reprise de carie. Le présent travail porte sur la synthèse et l'évaluation de nouveaux MBG pouvant être utilisés comme charges dans les adhésifs dentaires. Les MBG ont été préparés dans un système sol-gel à base d'acétate avec des précurseurs industriellement sûrs et non toxiques. Les MBG préparés à grande échelle (50g) offrent des caractéristiques de surface améliorées par rapport aux MBG à petite échelle (10g). L'étude de l'influence des modificateurs de réseau (CaO: Na2O) sur les caractéristiques de surface des MBG a révélé que la porosité était influencée par la teneur en CaO dans la composition. Une surface spécifique très élevée (535 m2g-1) et un volume de pores (0,33 cm3) ont été atteints dans le MBG avec la plus forte teneur en CaO. Par la suite, l'ordre de l'effet d'addition des précurseurs sur les caractéristiques de surface des MBG a été étudié. En maintenant la composition fixée et en faisant varier l'ordre d'addition du précurseur pendant la synthèse sol-gel, on a obtenu une augmentation de 1,5 fois du volume des pores et une diminution de 1,2 fois de la taille moyenne des pores. La méthode démontrée est une voie simple et directe pour améliorer la porosité et l'homogénéité des MBG. De plus, la modulation de la taille moyenne des pores pour une composition fixe est également utile pour une éventuelle application d’administration de médicament. En ce qui concerne la bioactivité, les charges de MBG ayant la plus forte teneur en CaO ont augmenté le précipité de phosphate de calcium dans le SBF après 7 jours, par opposition au MBG avec une teneur élevée en Na2O. De plus, tous les échantillons testés étaient non cytotoxiques pour les fibroblastes gingivaux humains (HGF) in vitro. De manière positive, les MBG traités à basse température ont significativement augmenté l'activité métabolique des HGF. Le broyage à boulets a été utilisé pour réduire la taille des particules primaires de MBG à moins de 3 µm. Le fraisage a visiblement eu un effet néfaste sur la porosité des charges MBG. Néanmoins, une certaine porosité est restée. L'adhésif commercial a été mélangé avec 3, 10, 20 et 30% en poids de charge MBG. L'adhésif rempli de MBG jusqu'à 10% en poids de charge a une viscosité fluide compatible avec l’application d'un adhésif. Le MBG ainsi développé avec une haute porosité et un contenu en CaO représentent des charges prometteuses pour des futures applications en dentisterie restaurative et régénérative / Improving the stability of adhesive dentin interface is crucial to extend the longevity of composite restorations. Remineralization through use of ion releasing materials is a promising approach to protect the hybrid layer from hydrolytic and enzymatic degradation. Mesoporous bioactive glasses (MBGs) offer attractive surface features (enhanced surface area and porosity) to use them as fillers in dental adhesives to promote remineralization through ions release. Moreover, the functionalization of pores with antibacterial drugs is a good way to combat secondary caries. The present work focused on the synthesis and evaluation of novel MBGs suitable to be used as fillers in dental adhesives. The MBGs were prepared in an acetate based sol-gel system with industrially safe and non-toxic precursors. MBGs prepared in large scale (50g) offered enhanced surface characteristics in comparison to small scale (10g) MBGs. The investigation on the influence of network modifiers (CaO:Na2O) on the surface characteristics of MBGs revealed that the porosity was driven by CaO content in the composition. Notable, very high surface area (535m2g-1) and pore volume (0.33cm3g-1) was attained in the MBG with highest CaO content. Next, the order of precursor addition effect on the surface characteristics of MBGs has been studied. By Keeping the composition fixed and varying the order of precursor addition during sol-gel synthesis a doubling of surface area, 1.5 times increase in pore volume and 1.2 times decrease in mean pore size was obtained. The demonstrated method is a simple and straightforward route to improve the porosity and homogeneity of MBGs. Furthermore, modulation of mean pore size for a fixed composition is also useful to tailor the pores of the fillers for drug delivery application. With regards to bioactivity, the MBG fillers with highest CaO content had increased calcium phosphate precipitate in SBF after 7 days as opposed to MBG with high Na2O content. Furthermore, all tested samples were non-cytotoxic to Human Gingival Fibroblasts (HGFs) in vitro. Positively, MBGs treated at lower temperature significantly enhanced the metabolic activity of HGFs. Ball milling was employed to reduce the primary particle size of MBG to less than 3μm. Milling seemingly had an adverse effect on the porosity of the MBG filler. Nevertheless, some porosity remained. The commercial adhesive was mixed with 3, 10, 20 and 30 weight percentage of MBG filler. MBG filled adhesive up to10 weight percent filler content had flowable viscosity suitable for adhesive application. The developed MBG with high porosity and CaO content appears as a new step in the development of dental adhesives and also other bioactive dental materials

Assisted reproductive technology (ART) has been rapidly expanding since the birth of Louise Brown, the first test tube baby, in 1978. Although an increasingly complex array of laboratory skills and procedures have been developed for infertility treatments, the success rate of ART remains low. In an attempt to make ART safer and more efficient, international medical practice is trending towards single embryo transfers and the use of innovative, sophisticated technologies to identify promising gametes and embryos with the highest potential to generate a pregnancy. Laser technology is increasingly being used to accomplish these aims. The application of lasers for ART has been successfully employed in clinical practice for some time now and is continually the subject of investigative research in order to generate new methods to improve operations. Moreover, lasers serve as a powerful tool at the forefront of investigative research in the reproductive sciences, assisting in broadening our understanding of reproductive and developmental biology. Nevertheless, there is a paucity of literature pertaining to the safe standardisation of such laser procedures with evidence at the molecular level. The primary aim of this thesis was to optimise applications of laser technology for clinical ART and research applications in the reproductive sciences. This thesis utilised the mouse embryo model to investigate potential deleterious effects of different laser treatment applications, both by the operator and hardware manufacturer. Safe and unsafe laser operator parameters were elucidated by assessing deleterious effects to the plasma membrane integrity, blastocyst survival rate, DNA fragmentation levels, and changes in gene expression of key developmental genes. The effect of altering the laser hardware to lower the power output was evaluated and it was determined that if a lower power laser is used to deliver a set amount of energy over a longer period of time, a smaller amount of damage is incurred. Work in this thesis also established a new method in which laser technology can be used as a research tool for the reproductive sciences, by creating a novel stimuli-responsive laser-activated nanoparticle delivery system with spatial control and increased efficiency in a mammalian cell model. The field of reproductive science continues to benefit greatly from laser application clinically to improve infertility treatments, and in research, to elucidate mechanisms underlying infertility, with a hope of increasing our understanding and eventually developing new treatment options.