Templating approaches to the synthesis of new microporous materials for gas adsorption and separation
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Structure direction in the synthesis of phosphate-based materials (aluminophosphates, AlPOs; magnesiumaluminophosphates, MgAPOs; silicoaluminophosphates, SAPOs; magnesiumsilicoaluminophosphates, MgAPSOs), has been investigated through co-templating synthesis studies supported by molecular modelling. These solids have been characterised by diffraction and solid-state NMR, and their properties in gas adsorption and catalysis have been measured. The parameters in the hydrothermal synthesis of SAPO STA-7, St Andrews porous solid number 7, (SAV), in which the macrocycle 1,4,7,11- tetraazacyclotetradecane (cyclam) and tetraethylammonium (TEA) cations are used as co-templates, were investigated in detail. A new route involving a reversal of the mixing order of reagents leads to the formation of single crystals up to 50 μm with perfect tetragonal prismatic morphology that was not achieved via previous synthetic routes. For the first time in SAPO STA-7, X-ray diffraction locates the tetraethylammonium cation (TEA) in tg.tg. conformation. The synthesis and full characterisation of a novel aluminophosphate structure designated STA-14 (KFI) represents the first example of a designed synthesis of a zeotype. The synthesis route is based on a co-templating approach supported by molecular modelling to design the specific template for one of the two types of cages within the structure. The first, a larger type of cage, also present in AlPO-42 (LTA), is templated by the azaoxacryptand 4,7,13,16,21,41-diaza-1,10-bicyclo[8,8,8]- hexocosane (‘Kryptofix 222’, hereafter K222). The modelled co-template configuration, in this case TEA in the tt.tt configuration, was experimentally observed by X-ray diffraction. Modifying the gel chemistry leads to SAPO and MgAPSO STA-14, which display high pore volumes for N₂ adsorption, similar to those of STA-7 and SAPO-34 (CHA). Furthermore, during these synthetic studies, a novel fully tetrahedrally- coordinated magnesiumaluminophosphate layer phase has been prepared, with a structure of relevance to hypothetical VPI-5 (VFI) type extended structures. Molecular modelling was also applied in another aluminophosphate-based material, that of STA-2 (SAT), to predict a template that could be prepared from inexpensive reagents. Existing routes required the use of expensive quinuclidine as a precursor to the template 1,4-bisquinuclidinium butane. The template suggested by modelling, 1,4-diazabicyclo (2,2,2)octane butane (NC₆H₁₂N⁺-C₄H₈-⁺NC₆H₁₂N), labelled DABCO_C4, templated AlPO STA-2 successfully. Structure characterisation of the as- prepared form of AlPO STA-2 using X-ray synchrotron data suggest the formation of Al- OH-Al units to accommodate the positively-charged template within the neutral framework and a combination of ¹³C, ¹⁴N and ¹⁵N NMR studies have been used to give further details of the template environment in the cages. The gas adsorption behaviour of the stable materials STA-7, STA-14 and STA-2 was evaluated for CO₂. High pressure adsorption (0 to 40 bars) on STA-7 and STA-14 shows similar behaviour due to their structural and chemical similarities. The total uptake of CO₂ for SAPO STA-7 is less than for the zeolite NaX (FAU) (3.4 and 5.2 mmolg -1 respectively at 373 K and 12 bars) but the usable capacity for pressure swing adsorption technology (PSA) between 1 to 20 bar for STA-7 is twice the value for NaX. The affinity of adsorption towards CO₂ and its low uptake at 1 bar made SAPO STA-7 a desirable sorbent for PSA. The zeotype affinity of adsorption for different probe gases is different, CO₂ >> CH₄ > CO, to that for zeolite NaX CO₂ >> CO > CH₄. Low pressure CO₂ adsorption (0 to 1 bar) in STA-7, STA-14 and STA-2 at temperatures between 273 and 303 K demonstrates that the topology and therefore the total free pore volume accessible to the gas molecules is the most important factor in determining the uptake in these solids, but that the composition and distribution of the silicon cations within the framework also has an important effect. For example at 273 K and 1 bar, the uptake of the STA-2 framework in the SAPO form is ca. 2wt% higher than in the AlPO form, but compared with SAPO STA-7, the uptake due to pore volume limitations is 10wt% lower under same conditions. In addition, the high quality of the SAPO STA-7 crystals obtained by the new route made them suitable in collaborations for the direct observation of diffusion of methanol by interference microscopy (IFM) and the study of their crystal growth by combined atomic force microscopy (AFM) and high resolution scanning electron microscopy (HRSEM). The catalytic applications of the STA-7 and STA-14 for the methanol-to-olefins reaction (MTO) and the argon adsorption at 87 K were also performed collaboratively. The results are reported and discussed here in the light of their structure and composition.
Thesis, PhD Doctor of Philosophy
Embargo Date: Print and electronic copy restricted until 29th October 2009 (Restriction now expired. Awaiting final permissions to release full text)
Embargo Reason: Thesis restricted in accordance with University regulations
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