P.A.M. Mourão

Preparation of Activated Carbons from Cork by Physical Activation in Carbon Dioxide

Activated carbons (ACs) were prepared by the physical activation of cork wood, virgin cork and adult cork of different particle sizes in carbon dioxide and characterised by elemental analysis, DRIFTS, SEM and N2 adsorption at −196°C. The wood gave results similar to those obtained with other lignocellulosic precursors. On the other hand, the cork, which has a different chemical composition as well as microstructure, gave somewhat unusual results. The cork ACs retained the characteristic honeycomb structure of the precursors and had low C/O ratios with oxygen present in the form of basic carbonyl and ether groups. With increasing activation, the micropore volume approached a limiting value of ca. 0.33 cm3/g, while the mean pore width was in the range 0.8–1.1 nm and decreased slightly with increasing burn-off. It was also found that the rate of activation of the adult cork was more than 10-times faster than that of the wood or the virgin cork.

Characterisation of Surface Ionisation and Adsorption of Phenol and 4-Nitrophenol on Non-porous Carbon Blacks

The adsorption of phenol and 4-nitrophenol from aqueous solutions by carbon blacks was studied. Particular attention was paid to the characterisation of the surface chemistry and ionisation of the carbon blacks by use of a simple carbon surface ionisation model, as well as the use of a normalised form of the Freundlich equation for the analysis of the adsorption isotherms. The results indicated that the solutes interact directly with the graphene layers and that the adsorption is sensitive to the π-electron density. Phenol has a weaker interaction and is more sensitive to the system conditions. In particular, it is more sensitive to oligomerisation under certain conditions. Comparison of the results with those previously reported for activated carbons with similar points of zero charge prepared from cork confirms the existence of a significant micropore-narrowing effect in the adsorption of organic solutes by activated carbons and which can lead to up to a doubling of the value of the Freundlich exponent, nF.

Ordered mesoporous silica materials for protein adsorption

Lysozyme and BSA were used, as model proteins of considerably different dimensions, in order to evaluate the influence of the distinct pore structural characteristics of three types of ordered mesoporous silica materials (MCF, SBA-15 and MCM-41) on protein adsorption. Characterisation by X ray diffraction and nitrogen adsorption at 77K revealed the typical pore structural features of each type of material. The maximum of the pore size distributions indicated that the width of the windows of MCF (2) (mesitylene/P123 of 2) was larger than the pore diameter of the unidirectional tubular pores of SBA-15. All the materials presented similar small external surface areas but high pore volumes, with that of MCF (2) being the highest. The adsorption of lysozyme at pH=8 increased in the order MCM-41<< SBA-15< MCF (2), and the uptakes were well above those of BSA at pH=5. Although BSA is not completely excluded from the mesopores of SBA-15 and MCF (2), as happens with MCM-41, the adsorption occurs to a very limited extent. The overall behaviour of these SBA-15 and MCF (2) samples was not significantly different and both revealed potential for the separation of these proteins.

Designing activated carbons from natural and synthetic raw materials for pollutants adsorption

Over the last decades the literature has shown the possibility of producing activated carbons (AC) from a wide variety of raw materials, and to use them as one of the most environment-friendly solutions for waste disposal [1]. Simultaneously, it has been shown that the adsorption of pollutants from different sources by activated carbons is one of the most efficient techniques for remediating or solving this kind of problem [2]. In this context, phenolic compounds represent one of the most important classes of pollutant present in the environment [3]. In this perspective, we present a study involving the production of AC from cork (Quercus suber L.), PEEK (polyetheretherketone) wastes or granulated recycled PET (polyethyleneterephthalate) and their applicability for the adsorption of phenolic compounds from the liquid phase. All samples were characterised in relation to their structural properties and chemical composition, by different techniques, including nitrogen adsorption at 77 K, elemental analysis (C, H, N, O and S) and point of zero charge (PZC). The activated carbons produced demonstrated high adsorption capacities both in the gas and liquid phase as exemplified by N2 and phenolic compounds adsorption experiments. Based on the structural and chemical properties, and on the kinetic and equilibrium studies of liquid phase adsorption, it is possible to conclude that it is the porous volume of the ACs that predominantly controls the process of phenolic compounds adsorption.

Synthetic polymers blend used in the production of high activated carbon for pesticides removals from liquid phase.

ABSTRACT For the activated carbon (AC) production, we used the most common industrial and consumer solid waste, namely polyethyleneterephthalate (PET), alone or blended with other synthetic polymer such polyacrylonitrile (PAN). By mixing PET, with PAN, an improvement in the yield of the AC production was found and the basic character and some textural and chemical properties were enhanced. The PET–PAN mixture was subjected to carbonisation, with a pyrolysis yield of 31.9%, between that obtained with PET (16.9%) or PAN (42.6%) separately. The AC revealed a high surface area (1400, 1230 and 1117 m2 g−1) and pore volume (0.46, 0.56 and 0.50 cm3 g−1), respectively, for PET, PAN and PET–PAN precursors. Selected ACs were successfully tested for 4-chloro-2-methylphenoxyacetic acid (MCPA) and diuron removal from the liquid phase, showing a higher adsorption capacity (1.7 and 1.2 mmol g−1, respectively, for MCPA and diuron) and good fits with the Langmuir (PET) and Freundlich equation (PAN and PET–PAN blend). With MCPA, the controlling factor to the adsorption capacity was the porous volume and the average pore size. Concerning diuron, the adsorption was controlled essentially by the external diffusion. A remarkable result is the use of different synthetic polymers wastes, as precursors for the production of carbon materials, with high potential application on the pesticides removals from the liquid phase.

Adsorption of Bovine Serum Albumin onto Mesocellular Silica Foams with Differently Sized Cells and Windows

As a model protein with quite large dimensions, Bovine Serum Albumin (BSA) has been used to evaluate the influence of the distinct pore structural characteristics of three mesocellular foam (MCF) materials prepared with or without the addition of ammonium fluoride and with varying 1,3,5-trimethylbenzene/Pluronic P123 (TMB/P123) ratios. SBA-15 was also studied for comparative purposes. Characterisation by X-ray diffraction and electron microscopy confirmed the characteristic spheroid cell structure of the MCF pores. Nitrogen adsorption/desorption isotherms at 77 K revealed the different pore structural parameters of the MCF, viz. pore volume (1.8–2.4 cm3/g), cell size (24.6–28.5 nm) and window size (11.3–17.3 nm), as obtained by the NLDFT method. The equilibrium adsorption isotherms and the kinetic adsorption data for BSA at 298 K and pH 5 were well fitted by the Langmuir model and pseudo-second-order kinetic model, respectively. The results showed that adsorption onto the material possessing a window size of 11.3 nm was mostly restricted to the external surface, while a considerable increase in the maximum adsorption capacity from 120 mg/g to 500–600 mg/g was observed when the window size was above the critical dimension of 13.9 nm. In the latter cases, the maximum adsorption capacities could be related to the pore volume rather than to the total surface area. The confined BSA molecules were strongly immobilised in the cells, since only a small proportion was desorbed from the material with windows of 17.3 nm dimensions on contact with a buffer solution of pH 7.

Textural Development of Activated Carbon Prepared from Recycled PET with Different Chemical Activation Agents

Activated carbons (AC) were prepared from waste granulated Polyethyleneterephthalate (PET) by chemical activation with phosphoric acid, sodium hydroxide and potassium hydroxide. All AC were characterised by N2 adsorption at 77 K, and those prepared with H3PO4 had a narrow pore size around 0.8 nm, those prepared with NaOH had a larger pore size higher than 1.52 nm and those prepared with KOH presented a pore size varying between 0.66 and 1.58 nm. The results suggest that H3PO4 and NaOH are not the most suitable activating agents for preparing AC with a high pore volume from waste PET. The AC produced with KOH presented a very high porosity, which passed through a maximum of 0.75 cm3g-1, due to an enlargement of the small micropores with an increase of the carbonisation temperature.

Activated Carbons Prepared from Natural and Synthetic Raw Materials with Potential Applications in Gas Separations

A carbon molecular sieve for the purification of a gas mixtures containing O2, N2 and CO2, CH4 was produced from a waste granulated PET by means of a single carbonisation step at 973 K. Activated carbon materials presenting good adsorption capacity and some selectivity for O2/N2 and CO2/CH4 were prepared from granulated PET and cork oak with pore mouth narrowing using CVD from benzene. The diffusion coefficients of O2, N2, CO2 and CH4 in these materials were calculated and are comparable to published values determined on Takeda 3A and on a carbon molecular sieve prepared from PET textile fibres by means of carbonisation and subsequent CVD with benzene. However, the selectivities were not quite as good as those given by Takeda 3A. However, taking into account that this is a first attempt at producing CMS from PET, the results are encouraging, and it is to be expected that further development of the experimental procedure will result in new materials with improved performance.

Reactivity of Cork and Lignin for the Production of Activated Carbons

Activated carbons have been prepared by physical activation in CO2 of commercial byproduct kraft lignin (as received, after de-ashing and after impregnation with NaCl) and natural cork. The results obtained show that the presence of natural inorganic impurities increases the reactivity of cork and lignin significantly and also results in limiting values for the micropore volume and in widening of the micropore size. Pure de-ashed lignin is exceptionally non-reactive but allows microporous activated carbons to be obtained which have very narrow micropore widths of ~0.5-0.6nm. When the de-ashed lignin is impregnated with NaCl similar micropore volumes and widths can be obtained but in a considerably shorter time (~30min instead of ~8h) which would result in a considerable energy saving and is therefore a promising procedure for the production of microporous activated carbons from low-cost kraft lignin.

Valorisation of Tectona Grandis tree sawdust through the production of high activated carbon for environment applications

This work presents a first approach concerning the use of Tectona Grandis tree sawdust (from East Timor) for high activated carbon production, by physical activation with carbon dioxide at different temperatures. The activated carbons (AC) obtained exhibit a well-developed porous structure with a pore size distribution varying from micro to mesopores. Selected AC was successfully evaluated for pesticide removal, specific to 4-chloro-2-methylphenoxyacetic acid, from the liquid phase. The results presented are very promising, allowing to establish that Tectona Grandis sawdust is as an excellent precursor for the basic AC production and allow to expect good performance of theses adsorbents on the removal of a broad range of pollutants. It should also be noted that, this achievement is very relevant for developing countries, such East Timor, where Tectona Grandis sawdust is available and may constitute a source of income creating a handle to the technical and industrial development of this region.