Silylation of layered double hydroxides via a calcination−rehydration route

Silylated layered double hydroxides (LDHs) were synthesized through a surfactant-free method involving an in situ condensation of silane with the surface hydroxyl group of LDHs during its reconstruction in carbonate solution. X-ray diffraction (XRD) patterns showed the silylation reaction occurred on the external surfaces of LDHs layers. The successful silylation was evidenced by 29Si cross-polarization magic-angle spinning nuclear magnetic resonance (29Si CP/MAS NMR) spectroscopy, attenuated total reflection Fourier transform infrared (ATR FTIR) spectroscopy, and infrared emission spectroscopy (IES). The ribbon shaped crystallites with a “rodlike” aggregation were observed through transmission electron microscopy (TEM) images. The aggregation was explained by the T2 and T3 types of linkage between adjacent silane molecules as indicated in the 29Si NMR spectrum. In addition, the silylated products show high thermal stability by maintained Si related bands even when the temperature was increased to 1000 °C as observed in IES spectra.

Silylation of layered double hydroxides via an induced hydrolysis method

A series of layered double hydroxides (LDHs) based composites were synthesized by using induced hydrolysis silylation method (IHS), surfactant precursor method, in-situ coprecipitation method, and direct silylation method. Their structures, morphologies, bonding modes and thermal stabilities can be readily adjusted by changing the parameters during preparation and drying processing of the LDHs. The characterization results show that the direct silylation reaction cannot occur between the dried LDHs and 3-aminopropyltriethoxysilane (APS) in an ethanol medium. However, the condensation reaction can proceed with heating process between adsorbed APS and LDHs plates. While using wet state substrates with and without surfactant and ethanol as the solvent, the silylation process can be induced by hydrolysis of APS on the surface of LDHs plates. Surfactants improve the hydrophobicity of the LDHs during the process of nucleation and crystallization, resulting in fluffy shaped crystals; meanwhile, they occupy the surface –OH positions and leave less “free –OH” available for the silylation reaction, favoring formation of silylated products with a higher population in the hydrolyzed bidentate (T2) and tridentate (T3) bonding forms. These bonding characteristics lead to spherical aggregates and tightly bonded particles. All silylated products show higher thermal stability than those of pristine LDHs.

Sulfate intercalated layered double hydroxides prepared by the reformation effect

The removal of the sulfate anion from water using synthetic hydrotalcite (Mg/Al LDH) was investigated using powder x-ray diffraction (XRD) and thermogravimetric analysis (TG). Synthetic hydrotalcite Mg6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation method from aluminum and magnesium chloride salts. The synthetic hydrotalcite was thermally activated to a maximum temperature of 380°C. Samples of thermally activated hydrotalcite where then treated with aliquots of 1000ppm sulfate solution. The resulting products where dried and characterized by XRD and TG. Powder XRD revealed that hydrotalcite had been successfully prepared and that the product obtained after treatment with sulfate solution also conformed well to the reference pattern of hydrotalcite. The d(003) spacing of all samples was found to be within the acceptable region for a LDH structure. TG revealed all products underwent a similar decomposition to that of hydrotalcite. It was possible to propose a reasonable mechanism for the thermal decomposition of a sulfate containing Mg/Al LDH. The similarities in the results may indicate that the reformed hydrotalcite may contain carbonate anion as well as sulfate. Further investigation is required to confirm this.

Zinc aluminium layered double hydroxides for the removal of iodine and iodide from aqueous solutions

129I is a radioactive isotope of iodine that is readily absorbed by the body. In this paper we investigated the potential of a 3:1 Zn/Al layered double hydroxide (LDH) as a sorbent for the removal of iodine and iodide from water. Synthetic Zn6Al2(OH)16(CO3)∙4H2O was prepared by the co-precipitation before thermal activation. The LDH was treated with solutions containing iodide and iodine. It was found that iodine could be more easily removed from solution than iodide. Powder X-ray diffraction revealed the destruction of the LDH structure during thermal activation and the successful reformation of a similar LDH material after treatment with the iodide or iodine solution. Thermal decomposition of all samples studied by thermogravimetry appeared to be similar. A new decomposition mechanism similar to one previously described in the literature was proposed for the Zn/Al LDH. The total mass loss of samples treated with iodide and iodine was significantly lower than that of the original LDH indicating that iodine species may form non-removable anions when intercalated into the LDH structure. Evolved gas mass spectrometry failed to detect any iodine species lost as gases during the decomposition of iodide treated LDH however, small quantities of iodine species were observed during decomposition of samples treated with iodine solution.

Driving selective aerobic oxidation of alkyl aromatics by sunlight on alcohol grafted metal hydroxides

It is very difficult to selectively oxidise stable compounds such as toluene and xylenes to useful chemicals with molecular oxygen (O 2) under moderate conditions. To achieve high conversion and less over-oxidised products, a new class of photocatalysts, metal hydroxide nanoparticles grafted with alcohols, is devised. They can efficiently oxidise alkyl aromatic compounds with O 2 using visible or ultraviolet light or even sunlight to generate the corresponding aldehydes, alcohols and acids at ambient temperatures and give very little over-oxidation. For example toluene can be oxidised with a 23% conversion after a 48-hour exposure to sunlight with 85% of the product being benzaldehyde, and only a trace of CO 2.The surface complexes grafted onto metal hydroxides can absorb light, generating free radicals on the surface, which then initiate aerobic oxidation of the stable alkyl aromatic molecules with high product selectivity. This mechanism is distinctly different from those of any known catalysts. The use of the new photocatalysts as a controlled means to generate surface radicals through light excitation allows us to drive the production of fine organic chemicals at ambient temperatures with sunlight. The process with the new photocatalysts is especially valuable for temperature-sensitive syntheses and a greener process than many conventional thermal reactions. © 2012 The Royal Society of Chemistry.

Synthesis and characterisation of layered double hydroxides and their application for water purification

Layered doubly hydroxides (LDHs) also known as hydrotalcites or anionic clays are a group of clay minerals that have shown promise for the removal of toxic anions from water through both anion exchange and a process known as the reformation effect. This project has involved the preparation and characterisation of LDH materials as well as the investigation of their ability to remove selected anions from aqueous solutions by the reformation effect. The LDH materials were successfully prepared from magnesium, aluminium, zinc and chromium chloride salts using the co-precipitation method. Samples were characterised using powder X-ray diffraction (XRD) and thermogravimetry (TG) to confirm the presence of LDHs. Powder XRD revealed a characteristic LDH structure for all LDH samples. Thermal Analysis showed decomposition usual occurred through a three or four step process as expected for LDHs. Preliminary investigations of the removal of sulfate, nitrate and fluoride by an Mg/Al LDH were carried out, and the products were characterised using XRD and TG which showed that an LDH material similar to the original hydrotalcite was formed after reformation. A Zn/Al LDH was investigated as a potential sorbent material for the removal of iodine and iodide from water. It was found that the LDH was a suitable adsorbent which is able to remove almost all of the iodine present in the test solutions. Again, the products were characterised by XRD, TG and evolved gas mass spectrometry (EGMS) in an attempt to better understand the iodine removal process. Powder XRD showed successful reformation of the LDH structure and TG/EGMS showed that only a small amount of iodine species were lost during thermal decomposition. Finally, the mineral stichtite a Mg/Cr LDH was successfully synthesised and investigated using XRD, TG and EGMS. Unfortunately, due to lack of time it was not possible to identify any new uses for the mineral stichtite in the current project.

Layered double hydroxides as iodine sorbents

This study investigates the potential of a Zn/Al layered double hydroxides (LHDs) as an adsorbent for the removal of iodine species from potable water (Theiss et al., 2011b). In this paper the resultant materials were characterised using powder x-ray diffraction (XRD) and thermogravimetry (TG) coupled with evolved gas mass spectrometry (EGMS) (Frost, et al, 2005, Rives, et al, 2001).

Thermogravimetric analysis of selected layered double hydroxides

Thermogravimetric analysis (TG) and powder X-ray diffraction (PXRD) were used to study some selected Mg/Al and Zn/Al layered double hydroxides (LDHs) prepared by co-precipitation. A Mg/Al hydrotalcite was investigated before and after reformation in fluoride and nitrate solutions. Little change in the TG or PXRD patterns was observed. It was proposed that successful intercalation of nitrate anions has occurred. However, the absence of any change in the d(003) interlayer spacing suggests that fluoride anions were not intercalated between the LDH layers. Any fluoride anions that were removed from solution are most likely adsorbed onto the outer surfaces of the hydrotalcite. As fluoride removal was not quantified it is not possible to confirm that this has happened without further experimentation. Carbonate is probably intercalated into the interlayer of these hydrotalcites, as well as fluoride or nitrate. The carbonate most likely originates from either incomplete decarbonation during thermal activation or adsorption from the atmosphere or dissolved in the deionised water. Small and large scale co-precipitation syntheses of a Zn/Al LDH were also investigated to determine if there was any change in the product. While the small scale experiment produced a good quality LDH of reasonable purity; the large scale synthesis resulted in several additional phases. Imprecise measurement and difficulty in handling the large quantities of reagents appeared to be sufficient to alter the reaction conditions causing a mixture of phases to be formed.

Removal of boron species by layered double hydroxides : a review

Boron, which is an essential element for plants, is toxic to humans and animals at high concentrations. Layered double hydroxides (LDHs) and thermally activated LDHs have shown good uptake of a range of boron species in laboratory scale experiments when compared to current available methods, which are for the most part ineffective or prohibitively expensive. LDHs were able to remove anions from water by anion exchange, the reformation (or memory) effect and direct precipitation. The main mechanism of boron uptake appeared to be anion exchange, which was confirmed by powder X-ray diffraction (XRD) measurements. Solution pH appeared to have little effect on boron sorption while thermal activation did not always significantly improve boron uptake. In addition, perpetration of numerous LDHs with varying boron anions in the interlayer region by direct co-precipitation and anion exchange have been reported by a number of groups. The composition and orientation of the interlayer boron ions could be identified with reasonable certainty by applying a number of characterisation techniques including: powder XRD, nuclear magnetic resonance spectroscopy (NMR), X-ray photoelectron spectroscopy (XPS) and infrared (IR) spectroscopy. There is still considerable scope for future research on the application of LDHs for the removal of boron contaminants.