Functionality preservation with enhanced mechanical integrity in the nanocomposites of the metal-organic framework, ZIF-8, with BN nanosheets

Metal-organic frameworks (MOFs) and boron nitride both possess novel properties, the former associated with microporosity and the latter with good mechanical properties. We have synthesized composites of the imidazolate based MOF, ZIF-8, and few-layer BN in order to see whether we can incorporate the properties of both these materials in the composites. The composites so prepared between BN nanosheets and ZIF-8 have compositions ZIF-1BN, ZIF-2BN, ZIF-3BN and similar to ZIF-4BN. The composites have been characterized by PXRD, TGA, XPS, electron microscopy, IR, Raman and solid state NMR spectroscopy. The composites possess good surface areas, the actual value decreasing only slightly with the increase in the BN content. The CO2 uptake remains nearly the same in the composites as in the parent ZIF-8. More importantly, the addition of BN markedly improves the mechanical properties of ZIF-8, a feature that is much desired in MOFs. Observation of microporous features along with improved mechanical properties in a MOF is indeed noteworthy. Such manipulation of properties can be profitably exploited in practical applications.

Avaliaçao do potencial energético da biomassa florestal residual na ZIF de Arade-Alte/ São Bartolomeu de Messines

Dissertação de mest., Energias Renováveis e Gestão de Energia, Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2011

A bioenergia e o risco de incêndios florestais em paisagens rurais contemporâneas: o caso da zif Arade-Alte/ São Bartolomeu de Messines

Dissertação de mest., Arquitectura Paisagista, Faculdade de Ciências e Tecnologia, Univ. do Algarve, 2011

Expressão de zif-268 durante a aquisição, evocação e extinção de uma memória aversiva

In the behavioral paradigm of discriminative avoidance task, both short and long-term memories have been extensively investigated with behavioral and pharmacological approaches. The aim of the present study was to evaluate, using the abovementioned model, the hippocampal expression of zif-268 - a calcium-dependent immediate early gene involved with synaptic plasticity process - throughout several steps of memory formation, such as acquisition, evocation and extiction. The behavioral apparatus consisted of a modified elevaated plus-maze, with their enclosed arms disposed in "L". A pre-exposure to the maze was made with the animal using all arms enclosed, for 30 minutes, followed by training and test, during 10 minutes each. The between sections interval was 24h. During training, aversive stimuli (bright light and loud noise) were actived whenever the animals entered one of the enclosed armas (aversive arm). Memory acquisiton, retention and extinction were evaluated by the percentage of the total time spent exploring the aversive arm. The parameters evaluated (time spent in the arms and total distance traveled) were estimated with an animal tracking software (Anymaze, Stoelting, USA). Learning during training was estimated by the decrease of the time spent exploring the aversive arm. One hour after the beginning of each section, animals were anaesthetized with sodium-thiopental (i.p.) and perfused with 0.9% heparinized saline solution followed by 4% paraformaldehyde. Brains were cryoprotected with 20% sucrose, separeted in three blocks and frozen. The middle block, containing the hippocampus, was sectioned at 20 micro meters in the coronal plane and the resutant sections were submitted to zif-268 immunohistochemistry. Our results show an increased expression of zif-268 in the dentate gyrus (DG) during the evocation and extinction stages. There is a distinct participation of the DG during the memory evocation, but not during its acquisition. Inaddition, all hippocampal regions (CA1, CA3 and DG) presented an increased zif-268 expression during the process of extinction.

Beyond the H2/CO2 upper bound: one-step crystallization and separation of nano-sized ZIF-11 by centrifugation and its application in mixed matrix membranes

The synthesis of nano-sized ZIF-11 with an average size of 36 ± 6 nm is reported. This material has been named nano-zeolitic imidazolate framework-11 (nZIF-11). It has the same chemical composition and thermal stability and analogous H2 and CO2 adsorption properties to the conventional microcrystalline ZIF-11 (i.e. 1.9 ± 0.9 μm). nZIF-11 has been obtained following the centrifugation route, typically used for solid separation, as a fast new technique (pioneering for MOFs) for obtaining nanomaterials where the temperature, time and rotation speed can easily be controlled. Compared to the traditional synthesis consisting of stirring + separation, the reaction time was lowered from several hours to a few minutes when using this centrifugation synthesis technique. Employing the same reaction time (2, 5 or 10 min), micro-sized ZIF-11 was obtained using the traditional synthesis while nano-scale ZIF-11 was achieved only by using centrifugation synthesis. The small particle size obtained for nZIF-11 allowed the use of the wet MOF sample as a colloidal suspension stable in chloroform. This helped to prepare mixed matrix membranes (MMMs) by direct addition of the membrane polymer (polyimide Matrimid®) to the colloidal suspension, avoiding particle agglomeration resulting from drying. The MMMs were tested for H2/CO2 separation, improving the pure polymer membrane performance, with permeation values of 95.9 Barrer of H2 and a H2/CO2 separation selectivity of 4.4 at 35 °C. When measured at 200 °C, these values increased to 535 Barrer and 9.1.

Enhanced hydrogen separation by vertically-aligned carbon nanotube membranes with zeolite imidazolate frameworks as a selective layer

Vertically-aligned carbon nanotube (VACNT) membranes show very high permeation fluxes due to the inherent smooth and frictionless nature of the interior of the nanotubes. However, the hydrogen selectivities are all in the Knudsen range and are quite low. In this study we grew molecular sieve zeolite imidazolate frameworks (ZIFs) via secondary seeded growth on the VACNT membranes as a gas selective layer. The ZIF layer has a thickness of 5–6 μm and shows good contact with the VACNT membrane surface. The VACNT supported ZIF membrane shows much higher H2 selectivity than Ar (7.0); O2 (13.6); N2 (15.1) and CH4 (9.8). We conclude that tailoring metal–organic frameworks on the membrane surface can be an effective route to improve the gas separation performance of the VACNT membrane.

Porous polyethersulfone-supported zeolitic imidazolate framework membranes for hydrogen separation

ZIF-8 thin layer has been synthesized on the asymmetric porous polyethersulfone (PES) substrate via secondary seeded growth. Continuous and dense ZIF-8 layer, containing microcavities, has good affinity with the PES support. Single gas permeance was measured for H2, N2, CH4, O2, and Ar at different pressure gradients and temperatures. Molecular sieving separation has been achieved for selectively separating hydrogen from larger gases. At 333 K, the H2 permeance can reach ∼4 × 10−7 mol m−2 s−1 Pa−1, and the ideal separation factors of H2 from Ar, O2, N2, and CH4 are 9.7, 10.8, 9.9, and 10.7, respectively. Long-term hydrogen permeance and H2/N2 separation performance show the stable permeability of the derived membranes.

Synthesis by extrusion: continuous, large-scale preparation of MOFs using little or no solvent

Grinding solid reagents under solvent-free or low-solvent conditions (mechanochemistry) is emerging as a general synthetic technique which is an alternative to conventional solvent-intensive methods. However, it is essential to find ways to scale-up this type of synthesis if its promise of cleaner manufacturing is to be realised. Here, we demonstrate the use of twin screw and single screw extruders for the continuous synthesis of various metal complexes, including Ni(salen), Ni(NCS)(2)(PPh3)(2) as well as the commercially important metal organic frameworks (MOFs) Cu-3(BTC)(2) (HKUST-1), Zn(2-methylimidazolate)(2) (ZIF-8, MAF-4) and Al(fumarate)(OH). Notably, Al(fumarate)(OH) has not previously been synthesised mechanochemically. Quantitative conversions occur to give products at kg h(-1) rates which, after activation, exhibit surface areas and pore volumes equivalent to those of materials produced by conventional solvent-based methods. Some reactions can be performed either under completely solvent-free conditions whereas others require the addition of small amounts of solvent (typically 3-4 mol equivalents). Continuous neat melt phase synthesis is also successfully demonstrated by both twin screw and single screw extrusion for ZIF-8. The latter technique provided ZIF-8 at 4 kg h(-1). The space time yields (STYs) for these methods of up to 144 x 10(3) kg per m(3) per day are orders of magnitude greater than STYs for other methods of making MOFs. Extrusion methods clearly enable scaling of mechanochemical and melt phase synthesis under solvent-free or low-solvent conditions, and may also be applied in synthesis more generally.

Um modelo bioeconómico para a gestão sustentável das florestas mediterrâneas

Tese de doutoramento, Ciências Agrárias (Território e Ambiente), Faculdade de Ciências e Tecnologia, Universidade do Algarve, 2013

Os pequenos proprietários e a gestão da propriedade na Zona de Intervenção Florestal Entre Douro e Sousa

O presente trabalho pretende criar um instrumento de apoio aos proprietários florestais particulares da ZIF EDS na decisão a melhor forma de rentabilizar as suas propriedades. Para responder a esta questão foi necessário, numa primeira fase, identificar quais as suas necessidades e preferências de forma a oferecer as propostas mais adequadas. Para o efeito recorreu-se a um inquérito, o qual permitiu saber quais as principais fontes de receitas. Complementarmente também permitiu recolher informação adicional sobre o comportamento e expectativas desses mesmos proprietários. Após identificado o âmbito de intervenção, fez-se um levantamento das alternativas mais adequadas, para as quais foi efetuado um estudo de rentabilidade.

Vecindad sin límites : encuentro fronterizo colombo-venezolano. Zona de integración fronteriza entre el departamento de Norte de Santander y el estado Táchira

Este libro reúne las ideas que académicos y funcionarios expresaron en el encuentro fronterizo colombo-venezolano “Vecindad sin límites”, que tuvo lugar en la ciudad de Cúcuta, con el objetivo de analizar las dinámicas de la región fronteriza, en particular aquellas concernientes a la Zona de Integración Fronteriza (ZIF) entre el departamento de Norte de Santander y el estado Táchira. La puesta en marcha de esta zona de integración ha generado grandes expectativas entre los nativos de estas regiones, ya que ha para ellos la ZIF se puede convertir en un instrumento que permita mejorar sus condiciones de vida; tendiendo en cuenta que, tradicionalmente, las regiones de frontera son las que menos se benefician del desarrollo de sus países, por lo que sus habitantes se ven obligados a enfrentar múltiples problemáticas en el día a día. De la misma manera, para ambos países la ZIF es la oportunidad para avanzar en varios proyectos de integración y cooperación fronteriza. A Colombia y Venezuela los une una vecindad inexorable y compleja, sin límites, que requiere ser comprendida en el ánimo de fortalecerla. Esta publicación va dirigida a los ciudadanos interesados en las dinámicas y perspectivas de la región fronteriza y de las relaciones binacionales entre ambos países.

Análisis del proceso de consolidacion de la zona de integración fronteriza entre el departamento de Norte de Santander (Colombia) y el Estado de Táchira (Venezuela) en el periodo de 1987 al 2007.

El presente caso de estudio, tiene el propósito de analizar el proceso de consolidación de la ZIF Táchira-Norte de Santander, con el fin de demostrar que los procesos de integración local y binacional, así como también, sus aspectos Políticos, económicos y jurídicos, Inciden e influyen significativamente en la creación de mecanismos de integración supranacional. En este caso, la creación de una ZIF Táchira-Norte de Santander bajo el marco supranacional de la Comunidad Andina de Naciones.

Análisis de la formulación de los mecanismos de integración y desarrollo fronterizo terrestre colombiano con Ecuador en las relaciones políticas bilaterales. Periodo 2001 – 2010.

La presente investigación analiza en qué medida el estado de las relaciones políticas bilaterales con Ecuador han determinado los alcances y desafíos en los mecanismos de integración y desarrollo fronterizos terrestre colombiano, específicamente la ZIF y la COVIEC dentro del periodo 2001 – 2010.