Application of Organo-Magadiites for the Removal of Eosin Dye from Aqueous Solutions: Thermal Treatment and Regeneration.

Na-magadiite exchanged with cetyl-trimethylammonium cations provided organophilic silicate materials that allowed for the effective removal of the acidic dye "eosin". The organic cations were intercalated into the interlayer spacing of the layered silicate via an exchange reaction between the organic cations from their bromide salt and the solid Na-magadiite at room temperature. Different techniques were used to characterize the effect of the initial concentration of the surfactant on the structure of the organo-magadiites. The C, H, and N analysis indicated that a maximum of organic cations of 0.97 mmol/g was achieved and was accompanied by an expansion of the basal spacing of 3.08 nm, with a tilted angle of 59° to the silicate layers. The conformation of the organic surfactants was probed using solid-state 13C, finding mainly the trans conformation similar to that of the starting cetyl trimethylammonium bromide salt (C16TMABr). Thermal gravimetric analysis was carried out to study the thermal stability of the resulting organo-magadiites. The intercalated surfactants started to decompose at 200 °C, with a mass loss percentage of 8% to 25%, depending on the initial loading of the surfactant, and was accompanied by a decrease of the basal spacing from 3.16 nm to 2.51 nm, as deduced from the in situ X-ray diffraction studies. At temperatures below 220 °C, an expansion of the basal spacing from 3.15 to 3.34 nm occurred. These materials were used as a removal agent for the anionic dye eosin. The maximum amount of the dye removed was related to the organic cation content and to the initial concentration of eosin, with an improvement from 2.5 mg/g to 80.65 mg/g. This value decreased when the organo-magadiite was preheated at temperatures above 200 °C. The regeneration tests indicated that an 85% removal efficiency was maintained after six cycles of use for the organo-magadiite using Ci of 200 mg/L.

Removal Properties of Anionic Dye Eosin by Cetyltrimethylammonium Organo-Clays: The Effect of Counter-Ions and Regeneration Studies.

The organo-clays (OCs) were prepared by a cation exchange reaction between surfactant (cetyltrimethylammonium, C16TMA) from different counterions (Bromide, Chloride, and Hydroxide). The effect of the counterions was investigated on the physico-chemical properties of the prepared organo-clays. The highest uptake of organic cations (1.60 mmol/g) was achieved using cetyl trimethylammonium bromide solution and the lowest value (0.93 mmol/g) was obtained after modification with cetyl trimethylammonium hydroxide solution starting from the same initial ratio of mmol/g of clay greater than 2.40. The arrangement of C16TMA cations within the interlayer space was assumed to be perpendicular with a tilt angle of 32° to the plane of clay sheets instead of being parallel to the clay surface using C16TMAOH solution at the same ratio. Different techniques were used to characterize these materials. The thermal stability of these organ-clays was investigated using an in-situ X-ray diffraction (XRD) technique. The decomposition of the surfactant moiety occurred at temperatures higher than 215 °C and was accompanied with a shrinkage of the basal spacing value to 1.42 nm. These materials were applied in the removal of an acid dye "eosin." The removed amount of eosin depended on the initial concentrations and the content of surfactants in the organo-clays. The removal of eosin was found to be an endothermic process. The maximum amount of 90 mg/g was achieved. The preheated treatment temperature of two selected OCs did affect the removal properties of eosin. A progressive reduction was observed at temperatures higher than 200 °C. The regeneration of spent OCs was studied and acceptable removal efficiency was maintained after 4 to 6 cycles depending on the used initial concentrations.

Modification of the surface adsorption properties of alumina-supported Pd catalysts for the electrocatalytic hydrogenation of phenol.

The electrocatalytic hydrogenation (ECH) of phenol has been studied using palladium supported on gamma-alumina (10% Pd-Al2O3) catalysts. The catalyst powders were suspended in aqueous supporting electrolyte solutions containing methanol and short-chain aliphatic acids (acetic acid, propionic acid, or butyric acid) and were dynamically circulated through a reticulated vitreous carbon cathode. The efficiency of the hydrogenation process was measured as a function of the total electrolytic charge and was compared for different types of supporting electrolyte and for various solvent compositions. Our results show that these experimental parameters strongly affect the overall ECH efficiency of phenol. The ECH efficiency and yields vary inversely with the quantity of methanol present in the electrolytic solutions, whereas the presence of aliphatic carboxylic acids increased the ECH efficiency in proportion to the chain length of the specific acids employed. In all cases, ECH efficiency was directly correlated with the adsorption properties of phenol onto the Pd-alumina catalyst in the studied electrolyte solution, as measured independently using dynamic adsorption isotherms. It is shown that the alumina surface binds the aliphatic acids via the carboxylate terminations and transforms the catalyst into an organically functionalized material. Temperature-programmed mass spectrometry analysis and diffuse-reflectance infrared spectroscopy measurements confirm that the organic acids are stably bound to the alumina surface below 200 degrees C, with coverages that are independent of the acid chain length. These reproducibly functionalized alumina surfaces control the adsorption/desorption equilibrium of the target phenol molecules and allow us to prepare new electrocatalytic materials to enhance the efficiency of the ECH process. The in situ grafting of specific aliphatic acids on general purpose Pd-alumina catalysts offers a new and flexible mechanism to control the ECH process to enhance the selectivity, efficiency, and yields according to the properties of the specific target molecule.