Characterization of micro-mesoporous carbonaceous materials. Calculations of adsorption isotherm of hydrocarbons

In this paper we apply a method recently developed by Do and co-workers(1) for the prediction of adsorption isotherms of pure vapors on carbonaceous materials. The information required for the prediction is the pore size distribution and the BET constant, C, of a corresponding nonporous surface (graphite). The dispersive adsorption force is assumed to be the dominant force in adsorption mechanism. This applies to nonpolar and weakly polar hydrocarbons. We test this predictive model against the adsorption data of benzene, toluene, n-pentane, n-hexane, and ethanol on a commercial activated carbon. It is found that the predictions are excellent for all adsorbates tested with the exception of ethanol where the predicted values are about 10% less than the experimental data, and this is probably attributed to the electrostatic interaction between ethanol molecules and the functional groups on the carbon surfaces.

Analysis of adsorption data of graphitized thermal carbon black with a DFT-lattice gas theory

In this paper we analyzed the adsorption of gases and vapors on graphitised thermal carbon black by using a modified DFT-lattice theory, in which we assume that the behavior of the first layer in the adsorption film is different from those of second and higher layers. The effects of various parameters on the topology of the adsorption isotherm were first investigated, and the model was then applied in the analysis of adsorption data of numerous substances on carbon black. We have found that the first layer in the adsorption film behaves differently from the second and higher layers in such a way that the adsorbate-adsorbate interaction energy in the first layer is less than that of second and higher layers, and the same is observed for the partition function. Furthermore, the adsorbate-adsorbate and adsorbate-adsorbent interaction energies obtained from the fitting are consistently lower than the corresponding values obtained from the viscosity data and calculated from the Lorentz-Berthelot rule, respectively.

Effects of adsorbate-adsorbate interaction in the description of adsorption isotherm of hydrocarbons in micro-mesoporous carbonaceous materials

In this paper, we present a model accounting for the adsorbate-adsorbate interaction in the adsorbed phase in the description of adsorption of pure vapors on carbonaceous materials. The details of the adsorbate-adsorbate interaction of a particular species are obtained from the analysis of its adsorption data on non-porous carbon black. The predictability of the model is tested against the adsorption isotherm data for benzene, toluene, n-pentane, n-hexane, carbon tetrachloride, methanol and ethanol on microporous activated carbon. It was found that the model prediction for non-polar adsorbates are satisfactory while it under-predicts for polar adsorbates, which is attributed to their additional interaction with functional groups. (C) 2002 Elsevier Science B.V. All rights reserved.

A comparative study of carbon gasification with O-2 and CO2 by density functional theory calculations

A comparative study of carbon gasification with O-2 and CO2 was conducted by using density functional theory calculations. It was found that the activation energy and the number of active sites in carbon gasification reactions are significantly affected by both the capacity and manner of gas chemisorption. O-2 has a strong adsorption capacity and the dissociative chemisorption of O-2 is thermodynamically favorable on either bare carbon surface or even isolated edge sites. As a result, a large number of semiquinone and o-quinone oxygen can be formed indicating a significant increase in the number of active sites. Moreover, the weaker o-quinone C-C bonds can also drive the reaction forward at (ca. 30%) lower activation energy. Epoxy oxygen forms under relatively high O-2 pressure, and it can only increase the number of active sites, not further reduce the activation energy. CO2 has a lower adsorption capacity. Dissociative chemisorption of CO2 can only occur on two consecutive edge sites and o-quinone oxygen formed from CO2 chemisorption is negligible, let alone epoxy oxygen. Therefore, CO2-carbon reaction needs (ca 30%) higher activation energy. Furthermore, the effective active sites are also reduced by the manner Of CO2 chemisorption. A combination of the higher activation energy and the fewer active sites leads to the much lower reaction rate Of CO2-carbon.

Adsorption of aromatic compounds by activated carbon: Effects of functional groups and molecular size

The adsorption of three aromatic compounds on to an untreated carbon was investigated. The solution pH was lowered in all experiments so that all the solutes were in their molecular forms. It was shown that the difference in the maximum adsorption of the solutes was mainly a result of the difference in the sizes of the molecules and their functional groups. Further-more, it was illustrated that the packing arrangement was most likely edge-to-face (sorbate-sorbent) with various tilt angles. On the other hand, the affinity and heterogeneity of the adsorption systems were apparently related to the pK(a) values of the solutes.

Thin films of a tetracationic porphyrin

Langmuir-Blodgett films of the tetracationic porphyrin tetrakis( octadecyl-4-pyridinium) porphinatozinc(ii) bromide transferred from subphases containing different salts were studied using X-ray photoelectron spectroscopy (XPS) and X-ray reflectometry. In contrast to previous results at the air/water interface, we found that the porphyrin adopted a fixed conformation at the air/solid interface regardless of composition of the subphase or whether the films were transferred above or below the primary phase transition. This conformation was assigned to the formation of an interdigitated bilayer structure.

Multiple ordered phases in Langmuir-Blodgett films of cadmium arachidate at elevated temperatures

Using synchrotron X-ray grazing incidence diffraction, superlattice structures have been observed to develop in Langmuir-Blodgett films of cadmium arachidate as the temperature is raised. The previously reported superstructure in the stacked lamellae at room temperature changes at about 70 degreesC and there are further changes at about 90 and 103 degreesC before the major phase transition from stacked lamellae to hexagonally packed rods occurs at 107 degreesC (Langmuir 1997, 13, 1602). Between 70 and 103 degreesC there is a 1 x 10 one-dimensional in-plane superstructure, which is commensurate with the local structure and has an interlayer shift along [01] by a distance of b (of the local structure) at lower temperatures, and a further shift at about 90 degreesC. At lower (

Synthesis of optically complex core-shell colloidal suspensions: Pathways to multiplexed biological screening

The ability to generate enormous random libraries of DNA probes via split-and-mix synthesis on solid supports is an important biotechnological application of colloids that has not been fully utilized to date. To discriminate between colloid-based DNA probes each colloidal particle must be 'encoded' so it is distinguishable from all other particles. To this end, we have used novel particle synthesis strategies to produce large numbers of optically encoded particle suitable for DNA library synthesis. Multifluorescent particles with unique and reproducible optical signatures (i.e., fluorescence and light-scattering attributes) suitable for high-throughput flow cytometry have been produced. In the spectroscopic study presented here, we investigated the optical characteristics of multi-fluorescent particles that were synthesized by coating silica 'core' particles with up to six different fluorescent dye shells alternated with non-fluorescent silica 'spacer' shells. It was observed that the diameter of the particles increased by up to 20% as a result of the addition of twelve concentric shells and that there was a significant reduction in fluorescence emission intensities from inner shells as an increasing number of shells were deposited.

Structural definition of the low-temperature phase transition of tris(ethane-1,2-diamine)zinc(II) dinitrate

The 93 K X-ray crystal structure of tris(ethane-1,2-diamine)zinc(II) dinitrate is reported. As predicted by the spectroscopic studies of other workers, there is a reversible phase transition of the structure at low temperature. We have determined this temperature to be 143 K. The structure at this temperature and below resembles that of the room temperature structure, except the crystallographic D-3 symmetry of the complex cation (296 K) is lowered to C-2 ( below 144 K) by subtle changes in cation-anion hydrogen bonding. No change in the conformation of the cation or its bond lengths and angles was found.

Ageing effects on the wettability behavior of laser textured silicon

In the present work we investigate the ageing of acid cleaned femtosecond laser textured < 100 > silicon surfaces. Changes in the surface structure and chemistry were analysed by Rutherford backscattering spectrometry (RBS) and X-ray photoelectron spectroscopy (XPS), in order to explain the variation with time of the water contact angles of the laser textured surfaces. It is shown that highly hydrophobic silicon surfaces are obtained immediately after laser texturing and cleaning with acid solutions (water contact angle >120 degrees). However these surfaces are not stable and ageing leads to a decrease of the water contact angle which reaches a value of 80 degrees. XPS analysis of the surfaces shows that the growth of the native oxide layer is most probably responsible for this behavior. (C) 2010 Elsevier B.V. All rights reserved.

Removal of sulfamethoxazole from solution by raw and chemically treated walnut shells

Purpose: The sorption of sulfamethoxazole, a frequently detected pharmaceutical compound in the environment, onto walnut shells was evaluated. Methods: The sorption proprieties of the raw sorbent were chemically modified and two additional samples were obtained, respectively HCl and NaOH treated. Scanning electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric (TG/DTG) techniques were applied to investigate the effect of the chemical treatments on the shell surface morphology and chemistry. Sorption experiments to investigate the pH effect on the process were carried out between pH 2 and 8. Results: The chemical treatment did not substantially alter the structure of the sorbent (physical and textural characteristics) but modified the surface chemistry of the sorbent (acid–base properties, point of zero charge—pHpzc). The solution pH influences both the sorbent’s surface charge and sulfamethoxazole speciation. The best removal efficiencies were obtained for lower pH values where the neutral and cationic sulfamethoxazole forms are present in the solution. Langmuir and Freundlich isotherms were applied to the experimental adsorption data for sulfamethoxazole sorption at pH 2, 4, and 7 onto raw walnut shell. No statistical difference was found between the two models except for the pH 2 experimental data to which the Freundlich model fitted better. Conclusion: Sorption of sulfamethoxazole was found to be highly pH dependent in the entire pH range studied and for both raw and treated sorbent.

Preparação de catalisadores heterogéneos para a produção de biodiesel

A produção de biodiesel como combustível para motores diesel, aumentou fortemente nos últimos anos e espera-se que cresça mais e mais num futuro próximo. O aumento do consumo de biodiesel exige processos de produção optimizados que permitam grandes capacidades de produção, operações simplificadas, rendimentos altos, bem como a utilização de matérias-primas mais económicas. Por isso, o desenvolvimento de processos de produção de baixo custo exige a especificação de catalisadores heterogéneos eficientes na promoção da reacção de transesterificação, permitindo a imediata separação da glicerina pura, não necessitando de uma purificação dispendiosa deste subproduto. Os xerogéis de carbono surgem então como materiais promissores para aplicação como catalisadores heterogéneos para a produção de biodiesel, devido às suas excelentes propriedades ao nível da sua textura e superfície química. Neste trabalho o principal objectivo foi a preparação de um xerogel de carbono, com o intuito de posteriormente ser aplicado na produção de biodiesel por catálise heterogénea. Amostras de xerogel de carbono foram preparadas pelo método sol-gel e oxidadas em fase líquida sendo posteriormente caracterizados os seus grupos funcionais e a sua área específica. Os resultados obtidos mostram que é possivel obter um xerogel de carbono com área superficial alta, tendo sido atingido um valor máximo para a amostra número dois (803 m2/g). Os resultados atingidos ao nível da preparação do catalisador permitem concluir que as condições de operação influenciam a estrutura final do xerogel de carbono. Quanto à caracterização da química superficial do xerogel, foi possível verificar que a diferença do número de acidez entre as amostras oxidadas e não oxidadas do mesmo lote é alta, o que permite afirmar que a oxidação do material de carbono incrementa a concentração de grupos oxigénio à superfície do xerogel. O valor máximo para o número de acidez foi obtido com a amostra número três (Amostra oxidada - 916 μmol/g, Amostra não oxidada - 207 μmol/g). Apesar de terem sido realizados ensaios para a produção de biodiesel os resultados obtidos foram nulos. A escolha das condições de reacção para a catálise heterogénea com este tipo de material poderá não ter sido a mais indicada, assim como a quantidade e o tipo de grupos funcionais introduzidos no catalisador não terem acidez suficiente para permitir uma catálise efectiva.

Preparação de adsorventes mesoporosos para a adsorção de poluentes em águas

Mestrado Engenharia Química. Ramo Tecnologias de Protecção Ambiental