Pyrene based Metal Organic Frameworks. Thesis submitted in accordance with the requirements of the University of Liverpool for the degree of Doctor in Philosophy by Thomas Ian Mangnall. November 2015. 1 Contents Abstract .......................................................................................................... 7 Extended Abstract ........................................................................................ 7 Acknowledgements. ..................................................................................... 11 Abbreviations. .............................................................................................. 13 1. Introduction .............................................................................................. 15 1.1. General Introduction ........................................................................... 15 1.2. Porous Materials ................................................................................. 15 1.2.1. Inorganic Porous Materials .......................................................... 16 1.2.2. Organic Porous Materials ............................................................. 20 1.2.3. Hybrid Porous Materials/Metal Organic Frameworks (MOFs) ... 21 1.2. History of Metal Organic Frameworks and Common Examples ........ 26 1.3. Applications of Metal Organic Frameworks ....................................... 31 1.3.1. Separation ..................................................................................... 31 1.3.2. Gas Storage .................................................................................. 34 1.3.3. Drug Delivery............................................................................... 40 1.3.4. Sensing ......................................................................................... 42 1.3.5. Catalysis ....................................................................................... 46 1.4. Photocatalysis ...................................................................................... 48 1.4.1. Semi-conductor Photocatalysis. ................................................... 48 1.4.2. Molecular photocatalysts. ............................................................ 54 2 1.4.3. Pyrene photocatalysis. .................................................................. 55 1.5. Conclusions ......................................................................................... 59 2. Synthetic and Experimental Techniques. ................................................. 64 2.1. Introduction. ........................................................................................ 64 2.2. Synthesis Techniques .......................................................................... 65 2.2.1. Solvothermal Synthesis of MOFs. ............................................... 65 2.3. X-Ray Diffraction. .............................................................................. 70 2.3.1. Principles of X-Ray Diffraction. .................................................. 70 2.3.2. Single Crystal X-Ray Diffraction. ............................................... 74 2.3.3. Powder X-Ray Diffraction. .......................................................... 75 2.4. Thermogravimetric Analysis. .............................................................. 76 2.5. CHN Combustion Elemental Analysis ............................................... 76 2.6. Inductively Coupled Plasma Optical Emission Spectroscopy. ........... 77 2.7. Gas Sorption. ....................................................................................... 77 2.8. Electron Microscopy. .......................................................................... 82 2.9. Optical Spectroscopy. ......................................................................... 83 2.9.1. Ultra Violet/Visible Spectroscopy. .............................................. 83 2.9.2. Fluorescence Spectroscopy. ......................................................... 84 2.10. Gas Chromatography and Thermal Conductivity Detector. ............. 86 2.11. Nuclear Magnetic Resonance Spectroscopy. .................................... 88 3. AlTBAPy ................................................................................................. 93 3 3.1. Overview. ............................................................................................ 93 3.2. Experimental ....................................................................................... 96 3.2.1. Synthesis ...................................................................................... 96 3.2.2. Photocatalysis. ............................................................................ 105 3.3. Characterisation................................................................................. 107 3.3.1. PXRD ......................................................................................... 107 3.3.2. SEM ........................................................................................... 109 3.3.3. TGA ........................................................................................... 111 3.3.4. Elemental analysis. ..................................................................... 112 3.3.5. Surface Area Measurements. ..................................................... 113 3.3.6. Optical Spectroscopy. ................................................................ 115 3.4. Water stability ................................................................................... 118 3.5. Photocatalysis. ................................................................................... 120 3.5.1. TEM ........................................................................................... 123 3.6. Pt@AlTBAPy MOF .......................................................................... 127 3.6.1. Characterisation.......................................................................... 128 3.6.2. Photocatalytic hydrogen evolution. ............................................ 138 3.7. Heat of adsorption of gasses. ............................................................ 139 3.7.1. Carbon dioxide ........................................................................... 140 3.7.2. Methane. ..................................................................................... 144 Conclusion. .............................................................................................. 148 4 4. ZrTBAPy ................................................................................................ 152 4.1. Overview. .......................................................................................... 152 4.2. Experimental ..................................................................................... 156 4.2.1. NU-1000 Synthesis. ................................................................... 156 4.2.2. Photocatalysis. ............................................................................ 157 4.3. Characterisation................................................................................. 159 4.3.1. PXRD ......................................................................................... 159 4.3.2. SEM ........................................................................................... 161 4.3.3. TGA ........................................................................................... 163 4.3.4. Elemental analysis. ..................................................................... 164 4.3.5. Surface Area Measurements. ..................................................... 165 4.3.6. Optical Spectroscopy. ................................................................ 167 4.4. Water stability ................................................................................... 170 4.5. Photocatalysis. ................................................................................... 172 4.5.1. TEM ............................................................................................ 175 4.6. Pt@NU-1000 MOF ........................................................................... 177 4.6.1. Characterisation.......................................................................... 178 4.6.2. Photocatalytic hydrogen evolution. ........................................... 190 4.7. Conclusion. ....................................................................................... 192 5. EuTBAPy ............................................................................................... 194 5.1. Overview. .......................................................................................... 194 5 5.2. MOF Synthesis. ................................................................................. 195 5.2.1. High Throughput Synthesis........................................................ 195 5.2.2. Single Crystal Synthesis. ............................................................ 200 5.2.3. Phase Pure Powder Synthesis..................................................... 202 5.3. Characterisation................................................................................. 203 5.3.1.SCXRD ....................................................................................... 203 5.3.2. PXRD ......................................................................................... 205 5.3.3. SEM ........................................................................................... 207 5.3.4. TGA ........................................................................................... 209 5.3.5.