Synthesis and characterisation of organo-beidellite

Today, there are growing concerns about the presence of environmental pollutants in many parts of the world. In particular, a lot of attention has been drawn to the levels of water and soil contaminants (de Paiva et al., 2008). The majority of these contaminants consist of NOCs (non-ionic organic compounds) and can enter our waterways through industrial activities, mining operations, crop and animal production, waste disposal and accidental leakage (de Paiva et al., 2008; Park et al., 2011). Therefore, there is an increased interest in the synthesis of new materials that can be used to remove potentially carcinogenic and toxic water contaminants. Smectite type organoclays are widely used in numerous applications, such as sorbent agents for environmental remediation, due to their unique properties (Jiunn-Fwu et al., 1990; Sheng et al., 1996; Zhou et al., 2007; Bektas et al., 2011; Park et al., 2011). This investigation focuses on beidellite (SBId-1), which belongs to the smectite clay family. Their properties include high cation exchange capacity (CEC), swelling properties, porous, high surface area and consequential strong adsorption/absorption capacity (Xi et al., 2007). However, swelling clays in general are not an effective sorbent agent in nature due to their hydrophilic properties. The hydrophilic properties of the clay can be changed to organophilic by intercalating a cationic surfactant. Many applications of organoclays are strongly dependent on their structural properties and hence, a better understanding of the configuration and structural change of organoclay is crucial. Organoclays were synthesised through ion exchange of 21CODTMA (MW: 392.5 g mol-1) and characterised using XRD and FTIR spectroscopy. This study investigates the structural and conformational changes of beidellite intercalated with octadecyltrimethylammonium bromide.

Nanostructured metal oxides as adsorbents and photocatalysts

This research underlines the extensive application of nanostructured metal oxides in environmental systems such as hazardous waste remediation and water purification. This study tries to forge a new understanding of the complexity of adsorption and photocatalysis in the process of water treatment. Sodium niobate doped with a different amount of tantalum, was prepared via a hydrothermal reaction and was observed to be able to adsorb highly hazardous bivalent radioactive isotopes such as Sr2+ and Ra2+ions. This study facilitates the preparation of Nb-based adsorbents for efficiently removing toxic radioactive ions from contaminated water and also identifies the importance of understanding the influence of heterovalent substitution in microporous frameworks. Clay adsorbents were prepared via a two-step method to remove anionic and non-ionic herbicides from water. Firstly, layered beidellite clay was treated with acid in a hydrothermal process; secondly, common silane coupling agents, 3-chloro-propyl trimethoxysilane or triethoxy silane, were grafted onto the acid treated samples to prepare the adsorption materials. In order to isolate the effect of the clay surface, we compared the adsorption property of clay adsorbents with ƒ×-Al2O3 nanofibres grafted with the same functional groups. Thin alumina (£^-Al2O3) nanofibres were modified by the grafting of two organosilane agents 3-chloropropyltriethoxysilane and octyl triethoxysilane onto the surface, for the adsorptive removal of alachlor and imazaquin herbicides from water. The formation of organic groups during the functionalisation process established super hydrophobic sites along the surfaces and those non-polar regions of the surfaces were able to make close contact with the organic pollutants. A new structure of anatase crystals linked to clay fragments was synthesised by the reaction of TiOSO4 with laponite clay for the degradation of pesticides. Based on the Ti/clay ratio, these new catalysts showed a high degradation rate when compared with P25. Moreover, immobilized TiO2 on laponite clay fragments could be readily separated out from a slurry system after the photocatalytic reaction. Using a series of partial phase transition methods, an effective catalyst with fibril morphology was prepared for the degradation of different types of phenols and trace amount of herbicides from water. Both H-titanate and TiO2-(B) fibres coated with anatase nanocrystal were studied. When compared with a laponite clay photocatalyst, it was found that anatase dotted TiO2-(B) fibres prepared by a 45 h hydrothermal treatment followed by calcination were not only superior in performance in photocatalysis but could also be readily separated from a slurry system after photocatalytic reactions. This study has laid the foundation for the development of the ability to fabricate highly efficient nanostructured solids for the removal of radioactive ions and organic pollutants from contaminated water. These results now seem set to contribute to the development of advanced water purification devices in the future. These modified nanostructured materials with unusual properties have broadened their application range beyond their traditional use as adsorbents, to also encompass the storage of nuclear waste after concentrating from contaminated water.

Application of organo-beidellites for the adsorption of atrazine

The surfaces of natural beidellite were modified with cationic surfactant octadecyl trimethylammonium bromide at different concentrations. The organo-beidellite adsorbent materials were then used for the removal of atrazine with the goal of investigating the mechanism for the adsorption of organic triazine herbicide from contaminated water. Changes on the surfaces and structure of beidellite were characterised by X-ray diffraction (XRD), thermogravimetric analysis (TGA), Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and BET surface analysis. Kinetics of the adsorption studies were also carried out which show that the adsorption capacity of the organoclays increases with increasing surfactant concentration up until 1.0 CEC surfactant loading, after which the adsorption capacity greatly decreases. TG analysis reveals that although the 2.0 CEC sample has the greatest percentage of surfactant by mass, most of it is present on external sites. The 0.5 CEC sample has the highest proportion of surfactant exchanged into the internal active sites and the 1.0 CEC sample accounts for the highest adsorption capacity. The goodness of fit of the pseudo-second order kinetic confirms that chemical adsorption, rather than physical adsorption, controls the adsorption rate of atrazine.

Thermogravimetric analysis of tetradecyltrimethylammonium bromide-modified beidellites

The surfaces of natural beidellite clay were modified with cationic surfactant, tetradecyltrimethylammonium bromide, at different concentrations. The organo-beidellites were analysed using thermogravimetric analysis which shows four thermal oxidation/decomposition steps. The first step of mass loss is observed from room temperature to 130 °C due to the dehydration of adsorbed water. The second step of mass loss between 130 and 400 °C is attributed to the oxidation step of the intercalated organic surfactant with the formation of charcoal. The third mass loss happens between 400 and 500 °C which is assigned to the loss of hydroxyl groups on the edge of clays and the further oxidation step of charcoal. The fourth step is ascribed to the loss of structural OH units as well as the final oxidation/decomposition step of charcoal which takes place between 500 and 700 °C. Thermogravimetric analysis has proven to be a useful tool for estimating loaded surfactant amount.