Heterogenization of heteropolyacids: A general discussion on the preparation of supported acid catalysts

Heteropolyacids (HPAs) possess both acidic and redox catalytic properties and held extensive promise of practical application. These type of compound display a great potential of specific synthesis reactions for replacing sulfuric acid to satisfy the requirements of environmental protection. Heterogenizing HPAs would not only make them more useful in liquid phase oxidation with oxygen and in acid-catalyzed reaction, as the catalyst is often difficult to separate from the reaction products, but also create favorable factors for realizing heterogenization of homogeneous reaction and even utilizing new technology of catalytic distillation. In this paper, different kinds of porous materials which are well characterized, including oxides such as Al2O3, SiO2, TiO2, diatomite, bentonite, and active carbon of different sources, were used as support for heterogenizing HPAs (in different media), and the obtained results, the intrinsic characters of supports which may influence both the nature of the interaction between HPAs and supports in the heterogenization and the activity in the catalytic reaction, are explored. It is expected that these can provide a referential model for preparing supported acid catalyst used in liquid phase.

SURFACE-MODIFIED HYDROPHILIC MEMBRANES IN MEMBRANE DISTILLATION

The porosity and the hydrophobicity of membranes are two essential requirements for membrane distillation (MD) of aqueous solutions. So far, the hydrophobic porous membranes used in MD studies have been prepared from hydrophobic materials. In this work, hydrophilic cellulose acetate and cellulose nitrate membranes were modified into hydrophobic membranes by radiation grafting polymerization and plasma polymerization, and used in MD studies successfully. The results indicated that modified membranes with good performance in MD can be obtained if the modifying conditions are controlled appropriately. Especially plasma polymerization, in which many particular kinds of monomer could be polymerized onto the surface of porous materials, has become an efficient method to prepare hydrophobic porous membrane with high performance from hydrophilic membranes. It will stimulate the development and practical application of MD.

Small angle scattering characterisation of micellar systems and templated architectures

The work described in this thesis reports the structural changes induced on micelles under a variety of conditions. The micelles of a liquid crystal film and dilute solutions of micelles were subjected to high pressure CO2 and selected hydrocarbon environments. Using small angle neutron scattering (SANS) techniques the spacing between liquid crystal micelles was measured in-situ. The liquid crystals studied were templated from different surfactants with varying structural characteristics. Micelles of a dilute surfactant solution were also subjected to elevated pressures of varying gas atmospheres. Detailed modelling of the in-situ SANS experiments revealed information of the size and shape of the micelles at a number of different pressures. Also reported in this thesis is the characterisation of mesoporous materials in the confined channels of larger porous materials. Periodic mesoporous organosilicas (PMOs) were synthesised within the channels of anodic alumina membranes (AAM) under different conditions, including drying rates and precursor concentrations. In-situ small angle x-ray scattering (SAXS) and transmission electron microscopy (TEM) was used to determine the pore morphology of the PMO within the AAM channels. PMO materials were also used as templates in the deposition of gold nanoparticles and subsequently used in the synthesis of germanium nanostructures. Polymer thin films were also employed as templates for the directed deposition of gold nanoparticles which were again used as seeds for the production of germanium nanostructures. A supercritical CO2 (sc-CO2) technique was successfully used during the production of the germanium nanostructures.

3D vanadium oxide inverse opal growth by electrodeposition

Three-dimensional vanadium pentoxide (V2O5) material architectures in the form of inverse opals (IOs) were fabricated using a simple electrodeposition process into artificial opal templates on stainless steel foil using an aqueous solution of VOSO4.χH2O with added ethanol. The direct deposition of V2O5 IOs was compared with V2O5 planar electrodeposition and confirms a similar progressive nucleation and growth mechanism. An in-depth examination of the chemical and morphological nature of the IO material was performed using X-ray crystallography, X-ray photoelectron spectroscopy, Raman scattering and scanning/transmission electron microscopy. Electrodeposition is demonstrated to be a function of the interstitial void fraction of the artificial opal and ionic diffusivity that leads to high quality, phase pure V2O5 inverse opals is not adversely affected by diffusion pathway tortuosity. Methods to alleviate electrodeposited overlayer formation on the artificial opal templates for the fabrication of the porous 3D structures are also demonstrated. Such a 3D material is ideally suited as a cathode for lithium ion batteries, electrochromic devices, sensors and for applications requiring high surface area electrochemically active metal oxides.

Using temporal analysis of products and flux response technology to determine diffusion coefficients in catalytic monoliths

The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10^-9 m² s^-1 to 4–8×10^-10 m² s^-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

Quantification of singlet oxygen generation from photodynamic hydrogels

Recently, we described a series of novel porphyrin-impregnated hydrogels capable of producing microbicidal singlet oxygen (1O2) on photoactivation. Indirect assessment of the efficacy of 1O2 production from such hydrogels has been previously described using microbiological techniques, but here we report a novel, direct method of quantification. Anthracene-9,10-dipropionic acid (ADPA) is known to irreversibly form an endoperoxide on reaction with 1O2, causing photobleaching of its absorbance band at approximately 378 nm. Here, the reaction of this probe is exploited in a novel way to provide a simple, inexpensive, and convenient measurement of 1O2 generation from the surface of porphyrin-incorporated photosensitising hydrogels, with the ability to account for effects due to hydrogel porosity. Ingress of the probe into the materials was observed, with rates of up to 3.83 x 103 s-1. This varied by up to 200-fold with material composition and surface modification. Rates of 1O2 generation in these porphyrin-incorporated hydrogels, after compensating for ADPA ingress, ranged from 1.86x103 – 5.86x103 s-1. This work demonstrates a simple and straightforward method for direct 1O2 quantification from porous materials, with general utility.

Liquids with permanent porosity

Porous solids such as zeolites and metal-organic frameworks are useful in molecular separation and in catalysis, but their solid nature can impose limitations. For example, liquid solvents, rather than porous solids, are the most mature technology for post-combustion capture of carbon dioxide because liquid circulation systems are more easily retrofitted to existing plants. Solid porous adsorbents offer major benefits, such as lower energy penalties in adsorption-desorption cycles, but they are difficult to implement in conventional flow processes. Materials that combine the properties of fluidity and permanent porosity could therefore offer technological advantages, but permanent porosity is not associated with conventional liquids. Here we report free-flowing liquids whose bulk properties are determined by their permanent porosity. To achieve this, we designed cage molecules that provide a well-defined pore space and that are highly soluble in solvents whose molecules are too large to enter the pores. The concentration of unoccupied cages can thus be around 500 times greater than in other molecular solutions that contain cavities, resulting in a marked change in bulk properties, such as an eightfold increase in the solubility of methane gas. Our results provide the basis for development of a new class of functional porous materials for chemical processes, and we present a one-step, multigram scale-up route for highly soluble 'scrambled' porous cages prepared from a mixture of commercially available reagents. The unifying design principle for these materials is the avoidance of functional groups that can penetrate into the molecular cage cavities.

Catalytic routes to convert saccharides to furanic aldehydes

The conversion of plant biomass-derived carbohydrates (preferably non-edible) into added-value products is envisaged to be at the core of the future biorefineries. Carbohydrates are the most abundant natural organic polymers on Earth. This work deals with the chemical valorisation of plant biomass, focusing on the acid-catalysed conversion of carbohydrates (mono and polysaccharides) to furanic aldehydes, namely 2-furaldehyde (Fur) and 5-hydroxymethyl-2-furaldehyde (Hmf), which are valuable platform chemicals that have the potential to replace a variety of oil derived chemicals and materials. The investigated reaction systems can be divided into two types depending on the solvent used to dissolve the carbohydrates in the reaction medium: water or ionic liquid-based systems. The reaction temperatures were greater than 150 ºC when the solvent was water, and lower than 150 º C in the cases of the ionic liquid-based catalytic systems. As alternatives to liquid acids (typically used in the industrial production of Fur), solid acid catalysts were investigated in these reaction systems. Aiming at the identification of (soluble and insoluble) reaction products, complementary characterisation techniques were used namely, FT-IR spectroscopy, liquid and solid state NMR spectroscopy, TGA, DSC and GC´GC-ToFMS analyses. Complex mixtures of soluble reaction products were obtained and different types of side reactions may occur. The requirements to be put on the catalysts for these reaction systems partly depend on the type of carbohydrates to be converted and the reaction conditions used. The thermal stability is important due to the fact that formation of humins and catalyst coking phenomena are characteristically inherent to these types of reactions systems leading to the need to regenerate the catalyst which can be effectively accomplished by calcination. Special attention was given to fully inorganic nanoporous solid acids, amorphous or crystalline, and consisting of nano to micro-size particles. The investigated catalysts were silicoaluminophosphates, aluminosilicates and zirconium-tungsten mixed oxides which are versatile catalysts in that their physicochemical properties can be fine-tuned to improve the catalytic performances in the conversion of different substrates (e.g. introduction of mesoporosity and modification of the acid properties). The catalytic systems consisting of aluminosilicates as solid acids and water as solvent seem to be more effective in converting pentoses and related polysaccharides into Fur, than hexoses and related polysaccharides into Hmf. The investigated solid acids exhibited fairly good hydrothermal stabilities. On the other hand, ionic liquid-based catalytic systems can allow reaching simultaneously high Fur and Hmf yields, particularly when Hmf is obtained from D-fructose and related polysaccharides; however, catalyst deactivation occurs and the catalytic reactions take place in homogeneous phase. As pointed out in a review of the state of the art on this topic, the development of truly heterogeneous ionic liquid-based catalytic systems for producing Fur and Hmf in high yields remains a challenge.

Engineering bio-based polymers using alternative solvents and processes

The work presented in this thesis explores novel routes for the processing of bio-based polymers, developing a sustainable approach based on the use of alternative solvents such as supercritical carbon dioxide (scCO2), ionic liquids (ILs) and deep eutectic solvents (DES). The feasibility to produce polymeric foams via supercritical fluid (SCF) foaming, combined with these solvents was assessed, in order to replace conventional foaming techniques that use toxic and harmful solvents. A polymer processing methodology is presented, based on SCF foaming and using scCO2 as a foaming agent. The SCF foaming of different starch based polymeric blends was performed, namely starch/poly(lactic acid) (SPLA) and starch/poly(ε-caprolactone) (SPCL). The foaming process is based on the fact that CO2 molecules can dissolve in the polymer, changing their mechanical properties and after suitable depressurization, are able to create a foamed (porous) material. In these polymer blends, CO2 presents limited solubility and in order to enhance the foaming effect, two different imidazolium based ILs (IBILs) were combined with this process, by doping the blends with IL. The use of ILs proved useful and improved the foaming effect in these starch-based polymer blends. Infrared spectroscopy (FTIR-ATR) proved the existence of interactions between the polymer blend SPLA and ILs, which in turn diminish the forces that hold the polymeric structure. This is directly related with the ability of ILs to dissolve more CO2. This is also clear from the sorption experiments results, where the obtained apparent sorption coefficients in presence of IL are higher compared to the ones of the blend SPLA without IL. The doping of SPCL with ILs was also performed. The foaming of the blend was achieved and resulted in porous materials with conductivity values close to the ones of pure ILs. This can open doors to applications as self-supported conductive materials. A different type of solvents were also used in the previously presented processing method. If different applications of the bio-based polymers are envisaged, replacing ILs must be considered, especially due to the poor sustainability of some ILs and the fact that there is not a well-established toxicity profile. In this work natural DES – NADES – were the solvents of choice. They present some advantages relatively to ILs since they are easy to produce, cheaper, biodegradable and often biocompatible, mainly due to the fact that they are composed of primary metabolites such as sugars, carboxylic acids and amino-acids. NADES were prepared and their physicochemical properties were assessed, namely the thermal behavior, conductivity, density, viscosity and polarity. With this study, it became clear that these properties can vary with the composition of NADES, as well as with their initial water content. The use of NADES in the SCF foaming of SPCL, acting as foaming agent, was also performed and proved successful. The SPCL structure obtained after SCF foaming presented enhanced characteristics (such as porosity) when compared with the ones obtained using ILs as foaming enhancers. DES constituted by therapeutic compounds (THEDES) were also prepared. The combination of choline chloride-mandelic acid, and menthol-ibuprofen, resulted in THEDES with thermal behavior very distinct from the one of their components. The foaming of SPCL with THEDES was successful, and the impregnation of THEDES in SPCL matrices via SCF foaming was successful, and a controlled release system was obtained in the case of menthol-ibuprofen THEDES.

Sol-Gel Mesoporous Silica Aerogels and Bio Hybrids for Functional Applications

The thesis covers a systematic investigation on the synthesis of silica aerogels and microspheres with tailored porosity, at ambient conditions by varying the experimental parameters as well as using organic templates. Organically modified silica-gelatin and silica-chitosan hybrids were developed for the first time using alkylalkoxysilanes such as MTMS and VTMS. Application of novel silica-biopolymer antiwetting coatings on different substrates such as glass, leather and textile is also demonstrated in the thesis.

‘‘catalysis by nano sulfated titania modified by transition metals"

in the present study, we have prepared and evaluated the physical and chemical properties and catalytic activities of transition metal loaded sulfated titania via the sol-gel route. Sol-gel method is widely used for preparing porous materials having controlled properties and leads to the formation of oxide particles in nano range, which are spherical or interconnected to each other. Characterization using various physico-chemical techniques and a detailed study of acidic properties are also carried out. Some reactions of industrial importance such as Friedel-Crafts reaction, fen-butylation of phenol,Beckmann rearrangement of cyclohexanone oxime, nitration of phenol and photochemical degradation of methylene blue have been selected for catalytic activity study in the present venture. The work is organized into eight chapters

Ordering in thin films of block copolymers: fundamentals to potential applications

The ordering of block copolymers in thin films is reviewed, starting, from the fundamental principles and extending to recent promising developments as templates for nanolithography which may find important applications in the semiconductor industry. Ordering in supported thin films of symmetric and asymmetric AB diblock and ABA triblock copolymers is discussed, along with that of more complex materials such as ABC triblocks and liquid crystalline block copolymers Techniques to prepare thin films, and to characterise ordering within them, are summarized. Several methods to align Hock copolymer nanostructures, important in several applications are outlined A number of potential applications in nanolithography, production of porous materials, templating. and patterning of organic and inorganic materials are then presented. The influence of crystallization on the morphology of a block copolymer film is briefly discussed, as are structures in grafted block copolymer films. (C) 2009 Elsevier Ltd All rights reserved.

Obtenção de placas cerâmico a partir de formulações de massas triaxiais de resíduos de caulim, chamote de telha e cinza vegetal

The production of red ceramic is an industrial activity that causes an intense impact. The manufacture of its products considerably increases the demand for natural resources, mainly with the extraction of raw material. The ceramic material produced generates waste, such as ash firewood and chamote. The residue from the beneficiation of kaolin is deposited in a poor, degrades the environment and contaminate water sources and soil, constituting in this manner, ecological disasters. The main objective of this work is to develop the formulation of a ceramic product consisting solely of industrial solid wastes, from ceramic tiles, (chamote) residue of kaolin and ash firewood. It is assumed that this product made in the laboratory can be used in coatings, wall and floor. The aim is to facilitate the replacement of the raw material of original composition of a ceramic body, for waste, while the process of production equal to the conventionally used, so that the properties of the product are reproduced. This work is characterized waste as its chemical composition, analysis of particle size, X-ray diffraction and thermal behavior. Several formulations were studied. The mass of waste was prepared by dry process, pressed to 25 MPa, and then burned in muffle type oven to 850, 950, 1050 and 1150 °C. The results showed that it is technically possible to produce porous tiles only with waste. It was found that the formulations of bodies play a key role in the properties of the final product, as well as the sintering temperature and heating rates. RN in the waste of kaolin is estimated at 15,000 t/month, about 3,000 gray t/month and chamote with 10 million pieces/month damaged. The presence of carbonates of calcium and magnesium at 1050 ° C results in an appropriate porosity and mechanical strength. The formulation M3JE, composed of 69% waste of kaolin, 7.7% and 23.3% of chamote of gray, became suitable for porous materials with the strength and absorption within the level of national and international standards