synthesis and characterization of porous coordination ... · pdf file4.3 synthesis ......
TRANSCRIPT
Content
1. Aim of This Work .................................................................................................................................. 6
2. Introduction ........................................................................................................................................... 9
2.1 Abstract ............................................................................................................................................................. 9
2.2 Porous Coordination Polymers ............................................................................................................ 10
2.2.1 Design of Coordination Polymers ............................................................................................. 11
2.2.2 Selection of Porous Coordination Polymers ......................................................................... 13
2.2.3 Applications of Porous Coordination Polymers .................................................................. 15
2.3 PCPs and Catalysis ..................................................................................................................................... 16
2.3.1 Functional Organic Sites ............................................................................................................... 17
2.3.2 Functional Inorganic Sites ........................................................................................................... 20
2.3.3 Catalytic Functionality by Host-Guest Chemistry .............................................................. 21
2.4 Loading Techniques .................................................................................................................................. 24
2.4.1 Solvent Based Loading Techniques .......................................................................................... 24
2.4.2 Solvent Free Loading Techniques ............................................................................................. 27
3. MOx@MOF-5 (M = Zn, Ti; x = 1, 2) ................................................................................................ 29
3.1 Abstract .......................................................................................................................................................... 29
3.2 Introduction ................................................................................................................................................. 29
3.3 Synthesis ........................................................................................................................................................ 30
3.4 Characterization ......................................................................................................................................... 32
3.4.1 Microstructural Characterization ............................................................................................. 32
3.4.2 Spectroscopic Characterization ................................................................................................. 37
3.5 Conclusion ..................................................................................................................................................... 56
4. Cu@MOF-5, Cu/ZnO@MOF-5 ......................................................................................................... 57
4.1 Abstract .......................................................................................................................................................... 57
4.2 Introduction ................................................................................................................................................. 58
4.3 Synthesis ........................................................................................................................................................ 60
4.4 Characterization ......................................................................................................................................... 62
4.4.1 Microstructural Characterization of Cu@MOF-5 ............................................................... 62
4.4.2 Microstructural Characterization of Cu/ZnO@MOF-5 ..................................................... 64
4.5 Catalytic Testing ......................................................................................................................................... 65
4.5.1 Characterization after Catalytic Testing ................................................................................ 67
4.6 Conclusion ..................................................................................................................................................... 68
5. Au@MOF-5, Au/MOx@MOF-5 ........................................................................................................ 70
5.1 Abstract .......................................................................................................................................................... 70
5.2 Introduction ................................................................................................................................................. 71
5.3 Synthesis ........................................................................................................................................................ 72
5.4 Characterization ......................................................................................................................................... 75
5.4.1 Microstructural Characterization ............................................................................................. 75
5.4.2 Spectroscopic Characterization ................................................................................................. 85
5.4.3 Sorption Properties ........................................................................................................................ 92
5.4.4 Catalytic Testing ............................................................................................................................... 93
5.5 Control of Au NP Growth and Interfacial Au/MOx Contact. ...................................................... 99
5.6 Conclusion .................................................................................................................................................. 100
6. Transferability of [MLm]@PCP .................................................................................................... 101
6.1 Abstract ....................................................................................................................................................... 101
6.2 Introduction .............................................................................................................................................. 102
6.3 [MLm]n@PCP .............................................................................................................................................. 103
6.3.1 Synthesis .......................................................................................................................................... 103
6.3.2 Characterization ............................................................................................................................ 104
6.4 M@PCP ........................................................................................................................................................ 110
6.4.1 Synthesis .......................................................................................................................................... 110
6.4.2 Characterization ............................................................................................................................ 111
6.5 MOx@PCP ................................................................................................................................................... 115
6.5.1 Synthesis .......................................................................................................................................... 115
6.5.2 Characterization ............................................................................................................................ 116
6.6 M/MOx@PCP ............................................................................................................................................. 119
6.6.1 Synthesis .......................................................................................................................................... 119
6.6.2 Characterization ............................................................................................................................ 119
6.7 Conclusion .................................................................................................................................................. 123
7. Dye@PCP ............................................................................................................................................ 124
7.1 Abstract ....................................................................................................................................................... 124
7.2 Introduction .............................................................................................................................................. 125
7.3 Synthesis ..................................................................................................................................................... 126
7.4 Characterization ...................................................................................................................................... 129
7.4.1 Microstructural Characterization .......................................................................................... 129
7.4.2 Spectroscopic Characterization .............................................................................................. 130
7.4.3 Emission and Absorption Spectroscopy of Bulk Materials ......................................... 132
7.4.4 Time, Spectrally and Space Resolved Confocal Microscopy ....................................... 134
7.5 Conclusion .................................................................................................................................................. 138
8. Summary ............................................................................................................................................ 140
9. Experimental .................................................................................................................................... 143
9.1 General Techniques ............................................................................................................................... 143
9.2 Analytical and Spectroscopic Methods .......................................................................................... 144
9.3 Catalytic Testing ...................................................................................................................................... 148
9.4 Starting Materials ................................................................................................................................... 151
9.4.1 Ligand Synthesis ........................................................................................................................... 151
9.4.2 MOCVD Precursor Synthesis .................................................................................................... 151
9.5 Synthesis of Porous Coordination Polymers ............................................................................... 152
9.6 [MLm]n@PCP .............................................................................................................................................. 154
9.6.1 General Procedure ....................................................................................................................... 154
9.6.2 Materials ........................................................................................................................................... 155
9.7 M@PCP ........................................................................................................................................................ 164
9.7.1 General Procedure ....................................................................................................................... 164
9.7.2 Materials ........................................................................................................................................... 165
9.8 MOx@PCP ................................................................................................................................................... 169
9.8.1 General Procedure ....................................................................................................................... 169
9.8.2 Materials ........................................................................................................................................... 170
9.9 M/MOx@PCP ............................................................................................................................................. 172
9.9.1 Cu/MOx@PCP ................................................................................................................................. 172
9.9.2 Au/MOx@PCP ................................................................................................................................. 172
9.10 Dye@PCP .................................................................................................................................................... 174
9.10.1 General Procedure ....................................................................................................................... 174
9.10.2 Materials ........................................................................................................................................... 174
10. References ......................................................................................................................................... 176
11. Appendix ............................................................................................................................................ 185
11.1 List of Acronyms and Abbreviations ............................................................................................... 185
11.2 List of Symbols ......................................................................................................................................... 187
11.3 List of Figures ........................................................................................................................................... 188
11.4 List of Tables ............................................................................................................................................. 197
11.5 List of Schemes ......................................................................................................................................... 198
11.6 Publications ............................................................................................................................................... 198
11.7 Oral Presentations .................................................................................................................................. 199
11.8 Poster Presentations ............................................................................................................................. 199
11.9 Statement of the Authorship .............................................................................................................. 201