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II 3.2.1 Synthesis and characterization of SBU-e and Ru-MOF 5.......................... 50 3.2.2 Investigation on the Ru oxidation state and porosity of Ru-MOF 5 .... 53 3.2.3 Conclusions .................................................................................................................. 55 4 Linker-based MOF solid solutions: Defect-Engineered MOFs (DEMOFs) .................... 56 4.1 Introduction .................................................................................................................................... 58 4.1.1 Solid solutions ............................................................................................................ 58 4.1.2 Defects in MOFs and its “engineering”............................................................. 60 4.2 Ruthenium Metal-Organic Frameworks featuring Different Defect Types ......... 65 4.2.1 Synthesis and characterization of the Ru-DEMOF materials ................. 65 4.2.2 Porosity of Ru-DEMOF samples and the confirmation of the DL incorporation .............................................................................................................. 76 4.2.3 XANES, XPS and UHV-FTIR studies: ruthenium oxidation state variation as indication of defect type formation ......................................... 79 4.2.4 CO2, CO and H2 sorption properties of Ru-DEMOFs ................................... 91 4.2.5 Catalytic test reactions ......................................................................................... 100 4.2.6 Conclusions ............................................................................................................... 106 4.3 Defects Engineering in [Cu3(BTC)2]n: Effect of the synthetic parameters ......... 108 4.3.1 Preparation and characterization of Cu-DEMOF samples [Cu3(BTC)2-x(ip)x]n.................................................................................................. 109 4.3.2 Composition and porosity of the prepared Cu-DEMOFs ....................... 116 4.3.3 Oxidation state(s) of metal-sites in prepared Cu-DEMOFs .................. 119 4.3.4 Conclusions ............................................................................................................... 121 5 Simultaneous introduction of various palladium active sites into MOF via onepot synthesis: Pd@[Cu3-xPdx(BTC)2]n ......................................................................................... 122 5.1 Introduction on the selection of metal type in MOFs ................................................. 123 5.2 Preparation and Structure of the Cu/Pd-BTC_1-3 ....................................................... 126 5.3 Compositional characterization and sorption properties of the prepared Cu/Pd-BTC_1-3 ........................................................................................................................... 130
III 5.4 Synthesis, compositional characterization and sorption properties of Cu/Pd-BTC_4 ............................................................................................................................... 136 5.5 Catalytic test reaction .............................................................................................................. 143 5.6 Conclusions ................................................................................................................................... 146 6 Summary and Outlook ...................................................................................................................... 147 7 Experimental Section ........................................................................................................................ 150 7.1 General methods ........................................................................................................................ 150 7.1.1 X-ray Diffraction (XRD) ....................................................................................... 150 7.1.2 FT-IR spectroscopy ................................................................................................ 151 7.1.3 Nuclear Magnetic Resonance (NMR) Spectroscopy ................................ 153 7.1.4 Thermogravimetric analyses (TGA)............................................................... 154 7.1.5 Scanning Electron Microscopy (SEM) and Energy-dispersive X-ray spectroscopy (EDX)............................................................................................... 154 7.1.6 Transmission electron microscope (TEM) and EDX ............................... 154 7.1.7 Elemental Analysis / Atomic absorption spectroscopic (AAS) .......... 154 7.1.8 Gas Sorption ............................................................................................................. 155 7.1.9 X-ray absorption near edge structure (XANES)........................................ 157 7.1.10 X-ray photoelectron spectroscopy (XPS)..................................................... 158 7.1.11 High Performance Liquid Chromatography (HPLC) ............................... 158 7.1.12 Catalytic studies ...................................................................................................... 159 7.2 Experimental data on chapter 3........................................................................................... 160 7.2.1 Synthesis of the ruthenium precursors ([Ru2(OOCR)4X] and [Ru2(OOCCH3)4]A).................................................................................................. 160 7.2.2 Synthesis of Ru-MOFs [Ru3(BTC)2Xx]·Gg ...................................................... 168 7.3 Experimental data on chapter 4........................................................................................... 173 7.3.1 Synthesis of Ru-DEMOF samples (1a-1d, 2a-2d, 3a-3d, 4a-4c) .......... 173 7.3.2 Catalytic reactions using Ru-DEMOFs as catalysts .................................. 177 7.3.3 Synthesis of [Cu3(BTC)2]n (Cu-BTC)............................................................... 177
Page 1: Controlled Modification of Metal-Or
Page 5: This thesis is based on the work pe
Page 8 and 9: Bochum) for the study of XPS and UH
Page 10 and 11: Zhang, for their continuous support
Page 14 and 15: IV 7.3.4 Synthesis of Cu-DEMOF samp
Page 16 and 17: VI DMSO dobdc e.g. EA EDX EtOH EXAF
Page 18 and 19: VIII TOF UHV UiO UMCM vs WCA XANES
Page 20 and 21: 2 Chapter 1 limitations of the (non
Page 22 and 23: 4 Chapter 2 For the synthesis of CP
Page 24 and 25: 6 Chapter 2 cavities is able to rev
Page 26 and 27: 8 Chapter 2 2.2.2 MOF features Adva
Page 28 and 29: 10 Chapter 2 Figure 2.5. A series o
Page 30 and 31: 12 Chapter 2 the material is retain
Page 32 and 33: 14 Chapter 2 2.3 Synthetic approach
Page 34 and 35: 16 Chapter 2 Expansion of this stru
Page 36 and 37: 18 Chapter 2 (H2BPDC) [75] or other
Page 38 and 39: 20 Chapter 2 Cr III CUSs of MIL-101
Page 40 and 41: 22 Chapter 2 Figure 2.14. Schematic
Page 42 and 43: 24 Chapter 2 adsorbate-surface inte
Page 44 and 45: 3 Controlled secondary building uni
Page 46 and 47: 28 Chapter 3 3.1 Preparation and in
Page 48 and 49: 30 Chapter 3 formula of [Ru3 II,III
Page 50 and 51: Intensity, a. u. 32 Chapter 3 quali
Page 52 and 53: 34 Chapter 3 After activating the R
Page 54 and 55: 36 Chapter 3 presence of the residu
Page 56 and 57: Intensity, a. u. 38 Chapter 3 the a
Page 58 and 59: 40 Chapter 3 extent than acetic aci
Page 60 and 61: 42 Chapter 3 Ru-nodes. Therefore, r
Page 62 and 63:
44 Chapter 3 decomposition of [BF4]
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deriv. normalized E) 46 Chapter 3 F
Page 66 and 67:
48 Chapter 3 3.1.6 Summary Applying
Page 68 and 69:
50 Chapter 3 3.2 Elaboration of Ru
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52 Chapter 3 with that of the Ru II
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54 Chapter 3 Figure 3.20. (a) XANES
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4 Linker-based MOF solid solutions:
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58 Chapter 4 4.1 Introduction 4.1.1
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60 Chapter 4 framework [Cu2(ndc)2(d
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62 Chapter 4 partial replacing of B
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64 Chapter 4 in the case of ip intr
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66 Chapter 4 4.2.1.1 Crystallinity
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68 Chapter 4 suggesting the absence
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70 Chapter 4 Table 4.1. The molar f
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72 Chapter 4 Figure 4.11. IR spectr
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74 Chapter 4 taking into account th
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76 Chapter 4 As quantitative digest
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78 Chapter 4 (Figure 4.16). Notably
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80 Chapter 4 framework Ru-species (
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82 Chapter 4 Figure 4.20. XANES spe
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84 Chapter 4 It is important to not
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86 Chapter 4 Ru δ+ have been obser
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88 Chapter 4 Figure 4.25. UHV-IR sp
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90 Chapter 4 Table 4.5. Possible de
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CO 2 adsorbed, mmol/g 92 Chapter 4
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H 2 adsorbed, mmol/g 94 Chapter 4 F
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CO 2 adsorbed, mmol/g 96 Chapter 4
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H 2 adsorbed, mmol/g 98 Chapter 4 8
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H 2 adsorbed, mmol/g 100 Chapter 4
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102 Chapter 4 presence of H2. [236]
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104 Chapter 4 reactive metal center
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106 Chapter 4 4.2.6 Conclusions App
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108 Chapter 4 4.3 Defects Engineeri
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Intensity, a. u. 110 Chapter 4 as-s
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weight loss, % 112 Chapter 4 100 Cu
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weight loss, % 114 Chapter 4 record
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116 Chapter 4 4.3.2 Composition and
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V, cm 3 /g 118 Chapter 4 500 400 30
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120 Chapter 4 Figure 4.50. From lef
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5 Simultaneous introduction of vari
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124 Chapter 5 preferred like Cu 2+
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126 Chapter 5 5.2 Preparation and S
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128 Chapter 5 Figure 5.5. Pawley Fi
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130 Chapter 5 5.3 Compositional cha
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132 Chapter 5 Table 5.3. The assign
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134 Chapter 5 framework are dominan
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136 Chapter 5 5.4 Synthesis, compos
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138 Chapter 5 obtained Pd-doped sol
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140 Chapter 5 Figure 5.18. Deconvol
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V, cm 3 /g 142 Chapter 5 sorption i
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144 Chapter 5 time as well as the i
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146 Chapter 5 5.6 Conclusions In su
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148 Chapter 6 coordinating anion),
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7 Experimental Section In this Chap
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152 Chapter 7 as water and hydroxyl
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154 Chapter 7 internal standards an
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156 Chapter 7 Uppermost layer is in
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158 Chapter 7 to the more tightly b
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160 Chapter 7 7.2 Experimental data
Page 180 and 181:
162 Chapter 7 [Ru2(OOCC(CH3)3)4(H2O
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164 Chapter 7 Figure 7.7. The PXRD
Page 184 and 185:
166 Chapter 7 [Ru2(OOCCH3)4(H2O)2]B
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168 Chapter 7 [Ru2(OOCCH3)4](THF)2
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170 Chapter 7 [Ru3(BTC)2(OH)1.5]n·
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172 Chapter 7 [Ru3(BTC)2]n∙(AcOH)
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174 Chapter 7 Table 7.3. Feeding mo
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176 Chapter 7 For comparison of the
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178 Chapter 7 7.3.4 Synthesis of Cu
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180 Chapter 7 D3 The mixture of H3B
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182 Chapter 7 D5 This sample was re
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184 Chapter 7 The synthesis of D7 a
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186 Chapter 7 7.4 Experimental data
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188 Chapter 7 Figure 7.26. PXRD pat
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190 Chapter 7 7.4.2 Hydrogenation o
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192 Chapter 7 7.5 Supplementary det
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8 Bibliography [1] A. J. Ihde, The
Page 214 and 215:
196 Bibliography [61] S. Ma, D. Sun
Page 216 and 217:
198 Bibliography [121] T. K. Prasad
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200 Bibliography [180] Y. Kobayashi
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202 Bibliography [239] A. L. Harreu
Page 222 and 223:
204 Bibliography [297] A. P. Hammer
Page 224 and 225:
206 Appendix List of Presentations
Page 226:
208 Appendix 05. 2015 Grant from th
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