Sodalite solid solution systems [Elektronische Ressource] : synthesis, topotactic transformations and investigation of framework guest and guest-guest interactions / vorgelegt von Henning Trill

Henning Trill Sodalite Solid Solution Systems: Synthesis, Topotactic Transformations, and Investigation of Framework-Guest and Guest-Guest Interactions 2002 Meinem Vater zum 65. Geburtstag Physikalische Chemie Sodalite Solid Solution Systems: Synthesis, Topotactic Transformations, and Investigation of Framework-Guest and Guest-Guest Interactions Inaugural-Dissertation zur Erlangung des Doktorgrades der Naturwissenschaften im Fachbereich Chemie und Pharmazie der Mathematisch-Naturwissenschaftlichen Fakultät der Westfälischen Wilhelms-Universität Münster vorgelegt von Henning Trill aus Ahaus - 2002 - Dekan: Prof. Dr. V. Leute Erster Gutachter: Prof. Dr. H. Eckert Zweiter Gutachter: Prof. Dr. R. Pöttgen Tag der mündlichen Prüfung: 12. 11. 2002 Tag der Promotion: 12. 11. 2002 Table of Contents I Table of Contents 1 Introduction .................................................................................................... 1 2 Theory............................................................................................................. 5 2.1 Nuclear Magnetic Resonance ...........................................................................................5 2.1.1 Semi-classical Description..........
Publié le : mardi 1 janvier 2002
Lecture(s) : 23
Source : MIAMI.UNI-MUENSTER.DE/SERVLETS/DERIVATESERVLET/DERIVATE-190/TRILL_DISSERTATION.PDF
Nombre de pages : 187
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Henning Trill




Sodalite Solid Solution Systems:

Synthesis, Topotactic Transformations, and Investigation
of Framework-Guest and Guest-Guest Interactions














2002





















Meinem Vater
zum 65. Geburtstag





Physikalische Chemie




Sodalite Solid Solution Systems:

Synthesis, Topotactic Transformations, and Investigation
of Framework-Guest and Guest-Guest Interactions



Inaugural-Dissertation
zur Erlangung des Doktorgrades
der Naturwissenschaften im Fachbereich Chemie und Pharmazie
der Mathematisch-Naturwissenschaftlichen Fakultät
der Westfälischen Wilhelms-Universität Münster



vorgelegt von

Henning Trill

aus Ahaus

- 2002 -






























Dekan: Prof. Dr. V. Leute
Erster Gutachter: Prof. Dr. H. Eckert
Zweiter Gutachter: Prof. Dr. R. Pöttgen
Tag der mündlichen Prüfung: 12. 11. 2002
Tag der Promotion: 12. 11. 2002 Table of Contents I

Table of Contents




1 Introduction .................................................................................................... 1
2 Theory............................................................................................................. 5
2.1 Nuclear Magnetic Resonance ...........................................................................................5
2.1.1 Semi-classical Description.........................................................................................5
2.1.2 Quantum Mechanical Description .............................................................................9
2.1.3 Zeeman Interaction ..................................................................................................11
2.1.4 Internal Interactions .................................................................................................12
2.1.5 Modern Experimental Methods ...............................................................................17
2.1.6 MAS of Quadrupolar Nuclei...................................................................................19
2.2 Magnetic Measurements.................................................................................................26
2.2.1 The SQUID..............................................................................................................26
2.2.2 Methods ...................................................................................................................26
3 Structural Aspects of Sodalite Solid Solutions ............................................ 28
3.1 Relations between Lattice Parameters and Sodalite Cage Geometry.............................28
3.2 Statistical Description of Sodalite Solid Solutions.........................................................30
3.3 NMR Studies of Sodalites ..............................................................................................30
3.3.1 NMR of Framework Atoms.....................................................................................31
3.3.2 NMR of extra Framework Species ..........................................................................32
3.4 Magnetically Coupled Spins...........................................................................................33
4 Experimental ................................................................................................ 36
4.1 Synthesis.........................................................................................................................36
4.1.1 Mixed Halide Sodalites............................................................................................36
4.1.2 Mixed Salt-bearing/Salt-free Sodalites....................................................................37
4.1.3 Halide/Electro Sodalites ..........................................................................................37
4.2 X-ray Diffraction ............................................................................................................39
4.3 Thermogravimetric Analysis (TGA) ..............................................................................39
4.4 Nuclear Magnetic Resonance .........................................................................................40
4.5 Computational Methods .................................................................................................41 Table of Contents II
4.5.1 Ab Initio Calculations..............................................................................................41
4.5.2 The Point Charge Model..........................................................................................42
4.6 Magnetic Measurements.................................................................................................43
5 Halide inclusion............................................................................................ 44
5.1 Experimental Observations.............................................................................................44
5.2 Growth Simulations........................................................................................................47
5.3 Discussion of the Experimental Data along the Growth Model.....................................53
6 Mixed Halide Sodalites ................................................................................ 56
6.1 Experimental Observations.............................................................................................56
6.1.1 27
Al MAS NMR..........................................................................................................56
6.1.2 23
Na MAS NMR .........................................................................................................57
6.1.3 35 81 127Cl, Br and I MAS NMR ....................................................................................60
6.2 Discussion.......................................................................................................................62
6.2.1 Solid Solution Effects on the Framework................................................................62
6.2.2 The extra Framework Species..................................................................................63
6.2.3 Halide Chemical Shift Trends in the Mixed Sodalites ............................................67
6.3 Ion Mobility....................................................................................................................68
7 Topotactic Transformations of the Sodalite Lattice..................................... 71
7.1 Experimental Lattice Constants......................................................................................71
7.1.1 Halide/Hydro Sodalites............................................................................................71
7.1.2 Halide/Dry Sodalites................................................................................................72
7.1.3 Halide/Electro Sodalites ..........................................................................................73
7.2 Discussion.......................................................................................................................74
8 Mixed Salt-bearing/Salt-free Sodalites ........................................................ 75
8.1 Observation and Assignment of NMR Resonances .......................................................75
8.1.1 27
Al MAS NMR..........................................................................................................75
8.1.2 The Halide NMR Spectra ........................................................................................82
8.1.3 Sodium.....................................................................................................................84
8.2 Discussion of the Observed NMR Spectra. ....................................................................90
8.2.1 Solid Solution Effects on the Framework................................................................91
8.2.2 Solid Solution Effects on the Extra-framework Species .........................................96
8.3 Ion and Molecular Dynamics in Mixed Halide/Salt-free Sodalites..............................102
8.3.1 The Pure Hydro and Br/hydro Sodalite Systems...................................................102
8.3.2 Dry and Br/dry Sodalites. ......................................................................................116 Table of Contents III
9 Mixed Halide/Electro Sodalites ................................................................. 119
9.1 Experimental Observations...........................................................................................119
9.1.1 27 29
Al and Si MAS NMR ..........................................................................................119
9.1.2 MAS NMR of the Central Anions .........................................................................122
9.1.3 23Na MAS NMR .......................................................................................................124
9.2 Discussion.....................................................................................................................126
9.2.1 The Framework Atoms ..........................................................................................126
9.2.2 The Central Halide Environments. ........................................................................133
9.2.3 Sodium Environments in Mixed Halide/Electro Sodalite Solid Solutions............135
9.3 Temperature Dependent NMR Studies.........................................................................141
9.3.1 Experimental Results and Observations ................................................................141
9.3.2 Discussion..............................................................................................................144
9.4 Bulk Magnetic Measurements ......................................................................................150
10 Conclusion and Outlook ......................................................................... 154
11 Summary................................................................................................. 157
12 Literature................................................................................................. 161

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