Porous organic-inorganic hybrid aerogels based on Cr3+/Fe3+ and rigid bridging carboxylates

A general method to prepare organic-inorganic hybrid aerogels has been presented. A series of organic-inorganic hybrid aerogels were successfully produced from 3d trivalent transition metals (Cr3+, Fe3+) and bridging carboxylic acids. Gelation of the Cr(III) gels was achieved by heating the precursor solution to temperatures above 80 degrees C, which is in sharp contrast to usual supramolecular gels. Among a range of ligands used, highly porous aerogels could be prepared from rigid carboxylate, e.g. 1,4-benzenedicarboxylate and 1,3,5-benzenetricarboxylate. The porous aerogels can be described as a coherent, rigid spongy network of continuous nanometre-sized particles, which is significantly different from the usual fibrous network of supramolecular gels. The aerogels have tunable porous structures with micro-and mesoporosity depending on their reactant concentrations. Their surface areas, pore volumes, and average pore sizes were analysed by using nitrogen sorption, and the accessibility of the pores to bulky molecules was also evaluated. It represents a strategy to prepare hybrid materials with large porosity utilising structurally simple building blocks as precursors.

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.

Aplicação de zeólitos hierárquicos a reacções de acilação de Friedel-Crafts

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química

2D hexagonal mesoporous platinum films exhibiting biaxial, in-plane pore alignment

The synthesis of 2D hexagonal mesoporous platinum films with biaxial, in-plane pore alignment is demonstrated by electrodeposition through an aligned lyotropic liquid crystal templating phase. Shear force is used to align a hexagonal lyotropic liquid crystalline templating phase of an inexpensive and a commercially available surfactant, C16EO10, at the surface of an electrode. Electrodeposition and subsequent characterisation of the films produced shows that the orientation and alignment of the phase is transferred to the deposited material. Transmission electron microscopy confirms the expected nanostructure of the films, whilst transmission and grazing incidence small angle X-ray scattering analysis confirms biaxial, in plane alignment of the pore structure. In addition further electrochemical studies in dilute sulfuric acid and methanol show that the pores are accessible to electrolyte solution as indicated by a large current flow; the modified electrode therefore has a high surface area, that catalyses methanol oxidation, and the pores have a very large aspect ratio (of theoretical maximum 2 × 105). Films with such aligned mesoporosity will advance the field of nanotechnology where the control of pore structure is paramount. The method reported is sufficiently generic to be used to control the structure and order of many materials, thus increasing the potential for the development of a wide range of novel electronic and optical devices.

Dinâmica da água no solo em cultivos de milho sob plantio direto e preparo convencional

A dinâmica da água em sistema de plantio direto (PD) é alterada em relação ao preparo convencional (PC) devido a modificações na estrutura do solo e a presença de palha na superfície. Para avaliar estas diferenças foram conduzidos experimentos de campo, em 2001/02 e 2002/03, em Eldorado do Sul, RS. O objetivo geral foi quantificar alterações físico-hídricas no perfil e na superfície do solo em PD e PC, com ênfase na dinâmica da água e respostas das plantas de milho. Os sistemas de manejo do solo foram implantados na área em 1995. Foram avaliadas propriedades físicas, a movimentação e a armazenagem de água no solo. Mediu-se a infiltração e a capacidade de campo e monitorou-se a dinâmica da água durante o ciclo da cultura, enfocando a secagem do solo e a extração de água em períodos sem precipitação. Nestes períodos também foi determinada a evaporação da água na superfície e avaliadas respostas das plantas. Os efeitos do plantio direto se evidenciaram nas camadas de solo próximas à superfície. A mesoporosidade foi a propriedade física mais afetada, apresentando uma distribuição exponencial de mesoporos no plantio direto, enquanto no preparo convencional a mesma se aproximou de uma curva normal. Em geral, a condutividade hidráulica, a retenção e a disponibilidade de água foram mais elevadas em plantio direto, principalmente, próximo à superfície. O solo em PD também apresentou maior umidade volumétrica com menor energia de retenção, resultando em redução no avanço da frente de secagem do solo e extração de água. A evaporação também foi maior em PD, demonstrando que a maior umidade no solo em plantio direto se deve ao aumento na capacidade de armazenagem de água. O aprofundamento radicular foi sempre maior no preparo convencional. O plantio direto altera propriedades físicas ligadas à dinâmica da água, proporcionando maior disponibilidade hídrica no solo ao longo do tempo.

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Characterization of silica-carbon mesoporous matrix with embedded nickel nanoparticles synthesized by the polymeric precursor method

Nickel nanoparticles into silica-carbon matrix composites were prepared by using the polymeric precursor method. The effects of the polyester type and the time of pyrolysis on the mesoporosity and nickel particle dispersion into non-aqueous amorphous silica-carbon matrix were investigated by thermogravimetric analysis, adsorption/desorption isotherms and TEM. A well-dispersed metallic phase could be only obtained by using ethylene glycol. Weightier polyesters affected the pyrolysis process due to a combination of more amounts of carbonaceous residues and delaying of pyrolysis process. The post-pyrolyzed composites were successfully cleaned at 200 degrees C for I h in oxygen atmosphere leading to an increase in the surface area and without the occurrence of carbon combustion or nickel nanoparticles oxidation. The matrix composites presented predominantly mesoporous with pore size well defined in 38 angstrom, mainly when tetraethylene glycol was used as polymerizing agent. (C) 2007 Elsevier B.V. All rights reserved.

Effect of the surfactant nature on the thermo-stability of surface modified SnO2 nanoparticles

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

A comparative study of glycerol dehydration catalyzed by micro/mesoporous MFI zeolites

The catalytic properties of monomodal microporous and bimodal micro-mesoporous zeolites were investigated in the gas-phase dehydration of glycerol. The desilication methodology used to produce the mesoporous zeolites minimized diffusion limitations and increased glycerol conversion in the catalytic reaction due to the hierarchical system of secondary pores created in the zeolite crystals. The chemical and structural properties of the catalyst were studied by X-ray diffraction, nitrogen adsorption-desorption isotherms, NH3-TPD and pyridine chemisorption followed by IR-spectroscopy. Although the aim was to desilicate to create mesoporosity in the zeolite crystals, the desilication promoted the formation of extra-framework aluminum species that affected the conversion of glycerol and the products distribution. The results clearly show that the mesoporous zeolites with designed mesopore structure allowed a rapid diffusion and consequently improved the reaction kinetics. However, especial attention must be given to the desilication procedure because the severity of the treatment negatively interfered on the Brønsted and Lewis acid sites relative concentration and, consequently, in the efficiency of the catalysis performed by these materials. On the other hand, during the catalytic reaction, the intracrystalline mesopores allowed carbonaceous compounds to be deposited herein, resulting in less blocked micropores and catalysts with higher long-term stability.

Transformação do glicerol em compostos de interesse petroquímico catalisada por zeólitas com ordem hierárquica de poros

Pós-graduação em Química - IQ

Síntese de aluminas macro-mesoporosas pelo método sol-gel acompanhado de separação de fases

Pós-graduação em Química - IQ

Electrode Materials for Ionic Liquid Based-Supercapacitors

The development of safe, high energy and power electrochemical energy-conversion systems can be a response to the worldwide demand for a clean and low-fuel-consuming transport. This thesis work, starting from a basic studies on the ionic liquid (IL) electrolytes and carbon electrodes and concluding with tests on large-size IL-based supercapacitor prototypes demonstrated that the IL-based asymmetric configuration (AEDLCs) is a powerful strategy to develop safe, high-energy supercapacitors that might compete with lithium-ion batteries in power assist-hybrid electric vehicles (HEVs). The increase of specific energy in EDLCs was achieved following three routes: i) the use of hydrophobic ionic liquids (ILs) as electrolytes; ii) the design and preparation of carbon electrode materials of tailored morphology and surface chemistry to feature high capacitance response in IL and iii) the asymmetric double-layer carbon supercapacitor configuration (AEDLC) which consists of assembling the supercapacitor with different carbon loadings at the two electrodes in order to exploit the wide electrochemical stability window (ESW) of IL and to reach high maximum cell voltage (Vmax). Among the various ILs investigated the N-methoxyethyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (PYR1(2O1)TFSI) was selected because of its hydrophobicity and high thermal stability up to 350 °C together with good conductivity and wide ESW, exploitable in a wide temperature range, below 0°C. For such exceptional properties PYR1(2O1)TFSI was used for the whole study to develop large size IL-based carbon supercapacitor prototype. This work also highlights that the use of ILs determines different chemical-physical properties at the interface electrode/electrolyte with respect to that formed by conventional electrolytes. Indeed, the absence of solvent in ILs makes the properties of the interface not mediated by the solvent and, thus, the dielectric constant and double-layer thickness strictly depend on the chemistry of the IL ions. The study of carbon electrode materials evidences several factors that have to be taken into account for designing performing carbon electrodes in IL. The heat-treatment in inert atmosphere of the activated carbon AC which gave ACT carbon featuring ca. 100 F/g in IL demonstrated the importance of surface chemistry in the capacitive response of the carbons in hydrophobic ILs. The tailored mesoporosity of the xerogel carbons is a key parameter to achieve high capacitance response. The CO2-treated xerogel carbon X3a featured a high specific capacitance of 120 F/g in PYR14TFSI, however, exhibiting high pore volume, an excess of IL is required to fill the pores with respect to that necessary for the charge-discharge process. Further advances were achieved with electrodes based on the disordered template carbon DTC7 with pore size distribution centred at 2.7 nm which featured a notably high specific capacitance of 140 F/g in PYR14TFSI and a moderate pore volume, V>1.5 nm of 0.70 cm3/g. This thesis work demonstrated that by means of the asymmetric configuration (AEDLC) it was possible to reach high cell voltage up to 3.9 V. Indeed, IL-based AEDLCs with the X3a or ACT carbon electrodes exhibited specific energy and power of ca. 30 Wh/kg and 10 kW/kg, respectively. The DTC7 carbon electrodes, featuring a capacitance response higher of 20%-40% than those of X3a and ACT, respectively, enabled the development of a PYR14TFSI-based AEDLC with specific energy and power of 47 Wh/kg and 13 kW/kg at 60°C with Vmax of 3.9 V. Given the availability of the ACT carbon (obtained from a commercial material), the PYR1(2O1)TFSI-based AEDLCs assembled with ACT carbon electrodes were selected within the EU ILHYPOS project for the development of large-size prototypes. This study demonstrated that PYR1(2O1)TFSI-based AEDLC can operate between -30°C and +60°C and its cycling stability was proved at 60°C up to 27,000 cycles with high Vmax up to 3.8 V. Such AEDLC was further investigated following USABC and DOE FreedomCAR reference protocols for HEV to evaluate its dynamic pulse-power and energy features. It was demonstrated that with Vmax of 3.7 V at T> 30 °C the challenging energy and power targets stated by DOE for power-assist HEVs, and at T> 0 °C the standards for the 12V-TSS and 42V-FSS and TPA 2s-pulse applications are satisfied, if the ratio wmodule/wSC = 2 is accomplished, which, however, is a very demanding condition. Finally, suggestions for further advances in IL-based AEDLC performance were found. Particularly, given that the main contribution to the ESR is the electrode charging resistance, which in turn is affected by the ionic resistance in the pores that is also modulated by pore length, the pore geometry is a key parameter in carbon design not only because it defines the carbon surface but also because it can differentially “amplify” the effect of IL conductivity on the electrode charging-discharging process and, thus, supercapacitor time constant.

Controllable assembly of graphene hybrid materials and their application in energy storage and conversion

Hybrid Elektrodenmaterialien (HEM) sind der Schlüssel zu grundlegenden Fortschritten in der Energiespeicherung und Systemen zur Energieumwandlung, einschließlich Lithium-Ionen-Batterien (LiBs), Superkondensatoren (SCs) und Brennstoffzellen (FCs). Die faszinierenden Eigenschaften von Graphen machen es zu einem guten Ausgangsmaterial für die Darstellung von HEM. Jedoch scheitern traditionelle Verfahren zur Herstellung von Graphen-HEM (GHEM) scheitern häufig an der fehlenden Kontrolle über die Morphologie und deren Einheitlichkeit, was zu unzureichenden Grenzflächenwechselwirkungen und einer mangelhaften Leistung des Materials führt. Diese Arbeit konzentriert sich auf die Herstellung von GHEM über kontrollierte Darstellungsmethoden und befasst sich mit der Nutzung von definierten GHEM für die Energiespeicherung und -umwandlung. Die große Volumenausdehnung bildet den Hauptnachteil der künftigen Lithium-Speicher-Materialien. Als erstes wird ein dreidimensionaler Graphen Schaumhybrid zur Stärkung der Grundstruktur und zur Verbesserung der elektrochemischen Leistung des Fe3O4 Anodenmaterials dargestellt. Der Einsatz von Graphenschalen und Graphennetzen realisiert dabei einen doppelten Schutz gegen die Volumenschwankung des Fe3O4 bei dem elektrochemischen Prozess. Die Leistung der SCs und der FCs hängt von der Porenstruktur und der zugänglichen Oberfläche, beziehungsweise den katalytischen Stellen der Elektrodenmaterialien ab. Wir zeigen, dass die Steuerung der Porosität über Graphen-basierte Kohlenstoffnanoschichten (HPCN) die zugängliche Oberfläche und den Ionentransport/Ladungsspeicher für SCs-Anwendungen erhöht. Desweiteren wurden Stickstoff dotierte Kohlenstoffnanoschichten (NDCN) für die kathodische Sauerstoffreduktion (ORR) hergestellt. Eine maßgeschnittene Mesoporosität verbunden mit Heteroatom Doping (Stickstoff) fördert die Exposition der aktiven Zentren und die ORR-Leistung der metallfreien Katalysatoren. Hochwertiges elektrochemisch exfoliiertes Graphen (EEG) ist ein vielversprechender Kandidat für die Darstellung von GHEM. Allerdings ist die kontrollierte Darstellung von EEG-Hybriden weiterhin eine große Herausforderung. Zu guter Letzt wird eine Bottom-up-Strategie für die Darstellung von EEG Schichten mit einer Reihe von funktionellen Nanopartikeln (Si, Fe3O4 und Pt NPs) vorgestellt. Diese Arbeit zeigt einen vielversprechenden Weg für die wirtschaftliche Synthese von EEG und EEG-basierten Materialien.

Synthesis of high surface area TiO2 nanoparticles by mild acid treatment with HCl or HI for photocatalytic propene oxidation

Nanostructured TiO2 photocatalysts with small crystalline sizes have been synthesized by sol-gel using the amphiphilic triblock copolymer Pluronic P123 as template. A new synthesis route, based on the treatment of TiO2 xerogels with acid-ethanol mixtures in two different steps, synthesis and extraction-crystallization, has been investigated, analyzing two acids, hydrochloric and hydriodic acid. As reference, samples have also been prepared by extraction-crystallization in ethanol, being these TiO2 materials amorphous and presenting higher porosities. The prepared materials present different degrees of crystallinity depending on the experimental conditions used. In general, these materials exhibit high surface areas, with an important contribution of microporosity and mesoporosity, and with very small size anatase crystals, ranging from 5 to 7 nm. The activity of the obtained photocatalysts has been assessed in the oxidation of propene in gas phase at low concentration (100 ppmv) under a UVA lamp with 365 nm wavelength. In the conditions studied, these photocatalysts show different activities in the oxidation of propene which do not depend on their surface areas, but on their crystallinity and band gap energies, being sample prepared with HCl both during synthesis and in extraction-crystallizations steps, the most active one, with superior performance than Evonik P25.

Desilication of TS-1 zeolite for the oxidation of bulky molecules

A series of modified TS-1 samples have been produced by desilication of the original TS-1 (4 wt.% Ti) using a chemical treatment with NaOH. Desilicated TS-1 zeolites exhibit a large BET surface area together with a well-developed mesoporosity. The hierarchical catalysts from desilication of TS-1 zeolite show a good catalytic activity for the oxidation of small molecules and a significantly higher activity for the oxidation of bulky molecules.