Adsorption and photocatalytic bleaching of acid orange 7 on P25 titania

The observed adsorption of acid orange 7, AO7(-), on P25 titania over a range of pH values (pH 2-8) gives a good fit to data generated using a charge distribution, multisite complexation, i.e. CD-MUSIC, model, modified for aggregated dye adsorption. For this system the model predicts that both the apparent dark Langmuir adsorption constant. K-L, and the number of adsorption sites, n(o), increase with decreasing pH, and are negligible above pH 6. At pH 2 the CD-MUSIC model predicts the fraction of singly co-ordinated sites occupied by the dye,f(AO7), is ca. 32% under the in situ monitoring experimental conditions used in this work to study the photocatalytic bleaching of AO7(-) under UV light illumination ([TiO2] = 20 mgdm(-3); [AO7(-)](total) = 4.86 x 10(-5) M). Although AO7(-) adsorption on P25 titania is insignificant above pH 6 and increases almost linearly and markedly below this pH, the measured initial rate of bleaching of AO7(-), photocatalysed by titania using UV appears to only increase modestly (

Kinetic and thermodynamics of chromium ions adsorption onto low-cost dolomite adsorbent

The chromium bearing wastewater in this study was used to simulate the low concentration discharge from a major aerospace manufacturing facility in the UK. Removal of chromium ions from aqueous solutions using raw dolomite was achieved using batch adsorption experiments. The effect of; initial Cr(VI) concentration, amount of adsorbent, solution temperature, dolomite particle size and shaking speed was studied. Maximum chromium removal was found at pH 2.0. A kinetic study yielded an optimum equilibrium time of 96 h with an adsorbent dose of 1 g/L Sorption studies were conducted over a concentration range of 5-50 mg/L Cr(VI) removal decreased with an increase in temperature (q(max): 20 degrees C = 10.01 mg/g; 30 degrees C = 8.385 mg/g; 40 degrees C = 6.654 mg/g; and 60 degrees C = 5.669 mg/g). Results suggest that the equilibrium adsorption was described by the Freundlich model. The kinetic processes of Cr(VI) adsorption onto dolomite were described in order to provide a more clear interpretation of the adsorption rate and uptake mechanism. The overall kinetic data was acceptably explained by a pseudo first-order rate model. Evaluated Delta G degrees and Delta H degrees specify the spontaneous and exothermic nature of the reaction. The adsorption takes place with a decrease in entropy (Delta S degrees is negative). (C) 2011 Elsevier B.V. All rights reserved.

Effect of a biofilm on the adsorption of 4-chlorophenol on activated carbon

The adsorption of 4-chlorophenol (4-CP) on activated carbon was studied experimentally both in the presence and in the absence of an inactivated anaerobic biofilm on the surface of carbon pellets. The presence of the biofilm markedly decreased the rate of 4-CP adsorption. However, the final near-equilibrium state (at 27 h) was not affected, and the incremental amount of material adsorbed on the pellets was similar both in the presence and in the absence of the biofilm. The biosorption of 4-CP by a biofilm coating non-adsorbing pellets was also determined. It appears that the biofilm also has some adsorption capability. Freundlich-type equations were used to correlate all data, and transient and near-equilibrium isotherms were obtained for 4-CP adsorption on different adsorbing materials at different times.

Modelling and fixed bed column adsorption of Cr(VI) onto orthophosphoric acid-activated lignin

The advantage of using an available and abundant residual biomass, such as lignin, as a raw material for activated carbons is that it provides additional economical interest to the technical studies. In the current investigation, a more complete understanding of adsorption of Cr(VI) from aqueous systems onto H PO -acid activated lignin has been achieved via microcolumns, which were operated under various process conditions. The practice of using microcolumn is appropriate for defining the adsorption parameters and for screening a large number of potential adsorbents. The effects of solution pH (2-8), initial metal ion concentration (0.483-1.981 mmol·L ), flow rate (1.0-3.1 cm ·min ), ionic strength (0.01-0.30 mmol·L ) and adsorbent mass (0.11-0.465 g) on Cr(VI) adsorption were studied by assessing the microcolumn breakthrough curve. The microcolumn data were fitted by the Thomas model, the modified Dose model and the BDST model. As expected, the adsorption capacity increased with initial Cr(VI) concentration. High linear flow rates, pH values and ionic strength led to early breakthrough of Cr(VI). The model constants obtained in this study can be used for the design of pilot scale adsorption process. © 2012 Chemical Industry and Engineering Society of China (CIESC) and Chemical Industry Press (CIP).

Hydrogen adsorption on functionalized nanoporous activated carbons

There is considerable interest in hydrogen adsorption on carbon nanotubes and porous carbons as a method of storage for transport and related energy applications. This investigation has involved a systematic investigation of the role of functional groups and porous structure characteristics in determining the hydrogen adsorption characteristics of porous carbons. Suites of carbons were prepared with a wide range of nitrogen and oxygen contents and types of functional groups to investigate their effect on hydrogen adsorption. The porous structures of the carbons were characterized by nitrogen (77 K) and carbon dioxide (273 K) adsorption methods. Hydrogen adsorption isotherms were studied at 77 K and pressure up to 100 kPa. All the isotherms were Type I in the IUPAC classification scheme. Hydrogen isobars indicated that the adsorption of hydrogen is very temperature dependent with little or no hydrogen adsorption above 195 K. The isosteric enthalpies of adsorption at zero surface coverage were obtained using a virial equation, while the values at various surface coverages were obtained from the van't Hoff isochore. The values were in the range 3.9-5.2 kJ mol(-1) for the carbons studied. The thermodynamics of the adsorption process are discussed in relation to temperature limitations for hydrogen storage applications. The maximum amounts of hydrogen adsorbed correlated with the micropore volume obtained from extrapolation of the Dubinin-Radushkevich equation for carbon dioxide adsorption. Functional groups have a small detrimental effect on hydrogen adsorption, and this is related to decreased adsorbate-adsorbent and increased adsorbate-adsorbate interactions.

Hysteretic adsorption and desorption of hydrogen by nanoporous metal-organic frameworks

Adsorption and desorption of hydrogen from nanoporous materials, such as activated carbon, is usually fully reversible. We have prepared nanoporous metal-organic framework materials with flexible linkers in which the pore openings, as characterized in the static structures, appear to be too small to allow H-2 to pass. We observe hysteresis in their adsorption and desorption kinetics above the supercritical temperature of H-2 that reflects the dynamical opening of the "windows" between pores. This behavior would allow H-2 to be adsorbed at high pressures but stored at lower pressures.

Protecting group and switchable pore-discriminating adsorption properties of a hydrophilic-hydrophobic metal-organic framework

Formed by linking metals or metal clusters through organic linkers, metal-organic frameworks are a class of solids with structural and chemical properties that mark them out as candidates for many emerging gas storage, separation, catalysis and biomedical applications. Important features of these materials include their high porosity and their flexibility in response to chemical or physical stimuli. Here, a copper-based metal-organic framework has been prepared in which the starting linker (benzene-1,3,5-tricarboxylic acid) undergoes selective monoesterification during synthesis to produce a solid with two different channel systems, lined by hydrophilic and hydrophobic surfaces, respectively. The material reacts differently to gases or vapours of dissimilar chemistry, some stimulating subtle framework flexibility or showing kinetic adsorption effects. Adsorption can be switched between the two channels by judicious choice of the conditions. The monoesterified linker is recoverable in quantitative yield, demonstrating possible uses of metal-organic frameworks in molecular synthetic chemistry as 'protecting groups' to accomplish selective transformations that are difficult using standard chemistry techniques.

Chemically blockable transformation and ultraselective low-pressure gas adsorption in a non-porous metal organic framework

Metal organic frameworks (MOFs) are among the most exciting materials discovered recently, attracting particular attention for their gas-adsorption and -storage properties. Certain MOFs show considerable structural flexibility in response to various stimuli. Although there are several examples of 'breathing' MOFs, in which structural changes occur without any bond breaking, examples of transformations in which several bonds are broken and made are much rarer. In this paper we demonstrate how a flexible MOF, Cu-2(OH)(C8H3O7S)(H2O)center dot 2H(2)O, can be synthesized by careful choice of the organic linker ligand. The flexibility can be controlled by addition of a supplementary coordinating molecule, which increases the thermal stability of the solid sufficiently for direct imaging with electron microscopy to be possible. We also demonstrate that the MOF shows unprecedented low-pressure selectivity towards nitric oxide through a coordination-driven gating mechanism. The chemical control over these behaviours offers new possibilities for the synthesis of MOFs with unusual and potentially exploitable properties.