رسالة جامعية
Synthesis of porous metal phosphonate frameworks for applications in gas separation and storage
| العنوان: | Synthesis of porous metal phosphonate frameworks for applications in gas separation and storage |
|---|---|
| المؤلفون: | Wharmby, Michael T. |
| المساهمون: | Wright, Paul Anthony |
| بيانات النشر: | University of St Andrews The University of St Andrews |
| سنة النشر: | 2013 |
| المجموعة: | University of St Andrews: Digital Research Repository |
| مصطلحات موضوعية: | Porous material, Metal phosphonate, Phosphonic acid, X-ray diffraction, STA-12, STA-13, STA-16, MIL-91, Porosity, QD305.P46W5, Phosphonates--Synthesis, Porous materials, Phosphonic acids |
| الوصف: | Porous metal phosphonate framework materials were synthesised by solvothermal reaction of bis(α-aminomethylenephosphonic acid) ligands with divalent and trivalent metal cations. The syntheses and characterisation by NMR and, where possible, single crystal X-ray diffraction of seven bisphosphonic acid ligands, including N,N′-piperazinebis(methylenephosphonic acid) (H₄L), its racemic and enantiopure (R) 2-methyl (H₄L′ and R-H₄L′) and 2,5-dimethyl (H₄L′′) derivatives, and N,N′-4,4′-bipiperidinebis(methylenephosphonic acid) (H₄LL) are reported. Syntheses of the known phase Y₂(LH₂)₃·5H₂O and the new phases, STA-13(Y) (St Andrews microporous material No. 13) and Y₂(R-L′H₂)₃·4H₂O, from reactions of Y(AcO)₃ with H₄L, H₄L′ and R-H₄L′ respectively are reported. The as-prepared and dehydrated structures of each phase have been determined from either laboratory or synchrotron powder X-ray diffraction data. Reaction of Y(AcO)₃ and H₄L′′ is shown to form a phase with a different structure. The features determining which structure crystallises are discussed. Syntheses of other rare-earth forms of STA-13 (Sc³⁺, Gd³⁺–Yb³⁺) and the porosity of each phase to N₂ are reported. STA-13(Y) is the most porous form with loadings of ∼3 mmol g⁻¹ and ∼4 mmol g⁻¹ for N₂ and CO₂ respectively. MIL-91(Fe) was synthesised for the first time from reactions of Fe³⁺ cations with H₄L. Its structure was confirmed by Rietveld refinement, but it was not porous. The first syntheses of [Fe₄L₁.₅(AcO)₁.₅(OH,H₂O)₃]·0.5NH₄5.5H₂O (L= L or L′) are reported, from reactions of H₄L or H₄L′ in the presence of an excess of Fe³⁺ cations. The phase is related to a previously reported Co phase. The synthesis of divalent metal bisphosphonate STA-12(Mg) (Mg₂(H₂O)₂L·5.6H₂O) was reported for the first time and its structure determined from single crystal X-ray diffraction. The dehydration behaviour of this material was compared with the known forms of STA-12. STA-12(Mg) is porous to both N₂ (∼5.5 mmol g⁻¹) and CO₂ (~ 8.5 mmol g⁻¹). Reaction of H₄LL with Co²⁺ and Ni²⁺ gave ... |
| نوع الوثيقة: | doctoral or postdoctoral thesis |
| وصف الملف: | application/pdf; application/zip |
| اللغة: | English |
| العلاقة: | uk.bl.ethos.569016; http://hdl.handle.net/10023/3450Test |
| الإتاحة: | http://hdl.handle.net/10023/3450Test |
| حقوق: | Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported ; http://creativecommons.org/licenses/by-nc-nd/3.0Test/ |
| رقم الانضمام: | edsbas.80D2AF35 |
| قاعدة البيانات: | BASE |
| الوصف غير متاح. |