NMR studies of silicate and aluminosilicate solutions as precursors for zeolites

The search for a detailed understanding of the mechanism of zeolite synthesis has, over the past two decades, promoted many investigations into the species present in (alumino)silicate solutions. It is generally accepted that dissolved (alumino)silicate species are involved as precursors in the nucleation of zeolites. Several techniques have been employed to understand the mechanism of formation of these complex structures. NMR spectroscopy has been shown to be a very powerful tool for the detection and characterization of (alumino)silicate species in the solutions in question. This thesis presents a comprehensive study of certain silicate solutions employmg (^29)Si NMR which has extended the knowledge gained in previous studies. The role of structure-direction on the distribution of silicate species in silicate solutions is discussed, the results providing more understanding of this effect. The effects of pH, temperature, Si/cation ratio and silica concentration on the distribution of silicate anions were also studied.Aluminium-27 NMR was applied to investigate the local structure about alummium atoms in a series of alumino silicate solutions with Si:Al mole ratios pertinent to zeolite synthesis. The kinetics of the reaction of aluminate with silicate anions have been studied by investigating the temporal evolutions of (^29)Al NMR spectra and by 2D NMR exchange spectroscopy. Structural analyses of two new silicate crystals were carried out by single-crystal X-ray diffraction. Liquid- and solid-state NMR spectroscopy were employed to characterize the mother liquors, the powdered polycrystalline products, and their melts.The Zeolite SUZ-9 was characterized by application of multinuclear magnetic resonance spectroscopy : (^29)Si, (^27)Al, (^13)C and (^1)H NMR spectra of this zeolite were studied

Fibre optic absorbance meter with low limit of detection for waterborne cations

We report an evanescent wave based fibre optic absorbance meter that enables the colorimetric detection of waterborne cations with water insoluble chromoionophoric sensitisers. This establishes an alternative to the PVC membrane based transducers that are conventionally used for this purpose. Here, a water insoluble sensitiser is coated as a thin film on an unclad section of a multimode optical fibre to overlap with the evanescent field of a light beam propagating along the fibre core. The colorimetric response of the sensitiser when in contact with waterborne cation leads to increased absorption of virtual photons associated with the evanescent field. The resulting intensity loss of the propagating beam is detected by a bespoke newly designed self- referenced evanescent wave absorbance meter with beam intensity modulation and Lock-in amplification. We validate our transducer with the well characterised water insoluble sensitizer, 1-(2-pyridylazo)-2-naphthol (PAN), for the detection of aqueous Zn2+ cations. We find a limit of detection (LoD) of 54 nM Zn2+, 28 times lower compared to a PVC membrane based sensor using same sensitiser for same cation (Albero et al., Journal of Pharmaceutical and Biomedical Analysis 29 (2002), 779). Our evanescent wave absorbance meter can easily be adapted to other colorimetric sensitisers, including chromoionophoric complex forming macrocycles

Synthesis of stoichiometrically controlled reactive aluminosilicate and calcium-aluminosilicate powders

Aluminosilicate and calcium-aluminosilicate powders are synthesised via an organic steric entrapment route under conditions permitting strict stoichiometric control, utilising polyvinyl alcohol and polyethylene glycol as polymeric carriers. Polyethylene glycol is superior to polyvinyl alcohol for synthesis of calcium-aluminosilicate powders via this method, producing a more controllable product which generated less fine ash during calcination. This paper presents detailed description of synthesis and characterisation of the powders produced through this approach, including new insight into the nanostructures within the calcined powders. Aluminium environments are a mixture of 4-, 5- and 6-coordinated, while silicon is tetrahedral and shows a broad range of connectivity states. The powders are X-ray amorphous, display a high degree of homogeneity, and thus offer potential for utilisation as precursors for synthesis of hydrous aluminosilicates in the quaternary CaO-Na2O-Al2O3-SiO2 system

Current Mathematical Methods Used in QSAR/QSPR Studies

This paper gives an overview of the mathematical methods currently used in quantitative structure-activity/property relationship (QASR/QSPR) studies. Recently, the mathematical methods applied to the regression of QASR/QSPR models are developing very fast, and new methods, such as Gene Expression Programming (GEP), Project Pursuit Regression (PPR) and Local Lazy Regression (LLR) have appeared on the QASR/QSPR stage. At the same time, the earlier methods, including Multiple Linear Regression (MLR), Partial Least Squares (PLS), Neural Networks (NN), Support Vector Machine (SVM) and so on, are being upgraded to improve their performance in QASR/QSPR studies. These new and upgraded methods and algorithms are described in detail, and their advantages and disadvantages are evaluated and discussed, to show their application potential in QASR/QSPR studies in the future