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This thesis is based on the work performed during the time of October 2012 and July 2016 under the supervision of Prof. Dr. Roland A. Fischer at the Chair of Inorganic Chemistry II, Organometallic & Materials, of the Ruhr‐University Bochum. 1 st referee: Prof. Dr. Roland A. Fischer 2 nd referee: Prof. Dr. Nils Metzler‐Nolte Herein I declare that I have written this thesis independently and without unauthorized help. Further, I assure that I have used no other sources, auxiliary means or quotes than those stated. I further declare that I have not submitted this thesis in this or in a similar form to any other university or college. Besides, I declare that I have not already undertaken an unsuccessful attempt to obtain a doctorate from another college or university. Wenhua Zhang July 2016
Page 1: Controlled Modification of Metal-Or
Page 7 and 8: Acknowledgements First of all, I si
Page 9 and 10: attending conferences, my research
Page 11 and 12: Table of Contents Table of Contents
Page 13 and 14: III 5.4 Synthesis, compositional ch
Page 15 and 16: V Abbreviations 4-btapa 5-Br-ip 5-B
Page 17 and 18: VII MTV Mw NMR NP PAP PivO PivOH PN
Page 19 and 20: 1 Motivation Looking through the es
Page 21 and 22: 2 General introduction The aim of t
Page 23 and 24: Chapter 2 5 On the other hand, link
Page 25 and 26: Chapter 2 7 2.2 Definition, Chemist
Page 27 and 28: Chapter 2 9 inorganic SBU can be co
Page 29 and 30: Chapter 2 11 Figure 2.7. a, Three c
Page 31 and 32: Chapter 2 13 concentrated sodium hy
Page 33 and 34: Chapter 2 15 afford a good way to s
Page 35 and 36: Chapter 2 17 concentrations (e.g. 8
Page 37 and 38: Chapter 2 19 the rection of H2dacob
Page 39 and 40: Chapter 2 21 metal-precursors are e
Page 41 and 42: Chapter 2 23 appealing perspectives
Page 43 and 44: Chapter 2 25 asymmetric catalysis.
Page 45 and 46: Chapter 3 27 which are structural a
Page 47 and 48: Chapter 3 29 between gas molecules
Page 49 and 50: Chapter 3 31 In this Chapter CSA is
Page 51 and 52: Chapter 3 33 All Ru-MOFs 1-4 of the
Page 53 and 54: Intensity, a. u. Chapter 3 35 3.1.3
Page 55 and 56:
Chapter 3 37 Table 3.1. Comparison
Page 57 and 58:
Chapter 3 39 Figure 3.9. IR spectra
Page 59 and 60:
Chapter 3 41 exchange. This might s
Page 61 and 62:
Chapter 3 43 Figure 3.12. Possible
Page 63 and 64:
Chapter 3 45 m 2 /mmol (based on th
Page 65 and 66:
deriv. normalized E) Chapter 3 47 I
Page 67 and 68:
Chapter 3 49 were investigated as w
Page 69 and 70:
Intensity, a. u. Chapter 3 51 and a
Page 71 and 72:
Chapter 3 53 3.2.2 Investigation on
Page 73 and 74:
V, cm 3 /g Chapter 3 55 400 350 300
Page 75 and 76:
Chapter 4 57 techniques. Interestin
Page 77 and 78:
Chapter 4 59 This is the most strai
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Chapter 4 61 active catalytic cente
Page 81 and 82:
Chapter 4 63 compared with the pare
Page 83 and 84:
Chapter 4 65 4.2 Ruthenium Metal-Or
Page 85 and 86:
Chapter 4 67 incorporated 5-X-ip li
Page 87 and 88:
Chapter 4 69 4.2.1.2 The incorporat
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Chapter 4 71 molecule in the pores
Page 91 and 92:
Chapter 4 73 ii) owing to the compe
Page 93 and 94:
Chapter 4 75 the Cl-amount was subs
Page 95 and 96:
Chapter 4 77 Figure 4.15. N 2 sorpt
Page 97 and 98:
Chapter 4 79 increasing feeding of
Page 99 and 100:
Chapter 4 81 XANES spectra (Figure
Page 101 and 102:
Chapter 4 83 Interestingly, the pos
Page 103 and 104:
Chapter 4 85 Figure 4.23. Deconvolu
Page 105 and 106:
Chapter 4 87 evidence on the valenc
Page 107 and 108:
Chapter 4 89 explains the observed
Page 109 and 110:
Chapter 4 91 appear to dominate ove
Page 111 and 112:
CO uptake, mmol/g Chapter 4 93 Tabl
Page 113 and 114:
-Q st , kJ/mol Chapter 4 95 DEMOFs
Page 115 and 116:
CO 2 adsorbed, mmol/g H 2 adsorbed,
Page 117 and 118:
CO 2 adsorbed, mmol/g Chapter 4 99
Page 119 and 120:
Chapter 4 101 samples 1a (8% of 5-O
Page 121 and 122:
Chapter 4 103 reaction of benzyl am
Page 123 and 124:
Yield, % Chapter 4 105 Table 4.8. C
Page 125 and 126:
Chapter 4 107 performance reasonabl
Page 127 and 128:
Intensity, a. u. Chapter 4 109 4.3.
Page 129 and 130:
Chapter 4 111 H 3 BTC H 2 ip D4 D3
Page 131 and 132:
Intensity, a. u. Intensity, a.u. Ch
Page 133 and 134:
Chapter 4 115 H 3 BTC H 2 ip D8 D7
Page 135 and 136:
V, cm 3 /g Chapter 4 117 more) in c
Page 137 and 138:
Chapter 4 119 (e.g. H2ip, H3BTC, et
Page 139 and 140:
Chapter 4 121 DEMOFs. Moreover, as
Page 141 and 142:
Chapter 5 123 5.1 Introduction on t
Page 143 and 144:
Chapter 5 125 pm) [257] via solid s
Page 145 and 146:
Chapter 5 127 (Figure 5.3). This is
Page 147 and 148:
Chapter 5 129 Figure 5.6. Crystal s
Page 149 and 150:
Chapter 5 131 NPs, as no typical O
Page 151 and 152:
Chapter 5 133 spectra of all prepar
Page 153 and 154:
Chapter 5 135 Figure 5.12. N 2 sorp
Page 155 and 156:
Chapter 5 137 The phase purity and
Page 157 and 158:
Chapter 5 139 it is hard to disting
Page 159 and 160:
weight loss, % Chapter 5 141 Table
Page 161 and 162:
Chapter 5 143 5.5 Catalytic test re
Page 163 and 164:
Chapter 5 145 Surprisingly, the nor
Page 165 and 166:
6 Summary and Outlook Among all MOF
Page 167 and 168:
Chapter 6 149 DEMOFs). These result
Page 169 and 170:
Chapter 7 151 Single crystal XRD da
Page 171 and 172:
Chapter 7 153 Figure 7.2. Schematic
Page 173 and 174:
Chapter 7 155 measured under Ar. At
Page 175 and 176:
Chapter 7 157 adsorbed at different
Page 177 and 178:
Chapter 7 159 Buffers: A: water/MeC
Page 179 and 180:
Chapter 7 161 Figure 7.3. PXRD patt
Page 181 and 182:
Chapter 7 163 Table 7.1. Cell param
Page 183 and 184:
Chapter 7 165 [Ru2(OOCCH3)4(THF)2]B
Page 185 and 186:
Chapter 7 167 hours, a deep red bro
Page 187 and 188:
Chapter 7 169 [Ru3(BTC)2Cl(AcO)0.5]
Page 189 and 190:
Chapter 7 171 Figure 7.12. PXRD pat
Page 191 and 192:
Chapter 7 173 7.3 Experimental data
Page 193 and 194:
Chapter 7 175 Table 7.4. BET surfac
Page 195 and 196:
Chapter 7 177 7.3.2 Catalytic react
Page 197 and 198:
Chapter 7 179 D2 This sample was pr
Page 199 and 200:
Chapter 7 181 D4 This sample was pr
Page 201 and 202:
Chapter 7 183 D6 This sample was ob
Page 203 and 204:
Page 205 and 206:
Chapter 7 187 Figure 7.24. XPS surv
Page 207 and 208:
Chapter 7 189 Cu/Pd-BTC_4 For sampl
Page 209 and 210:
Absorbance, a. u. Chapter 7 191 O 2
Page 211 and 212:
Page 213 and 214:
Bibliography 195 [30] D. J. Tranche
Page 215 and 216:
Bibliography 197 [90] W. Ouellette,
Page 217 and 218:
Bibliography 199 [146] M. J. Cliffe
Page 219 and 220:
Bibliography 201 [208] W. Zhang, O.
Page 221 and 222:
Bibliography 203 [266] I. Cabria, M
Page 223 and 224:
Appendix List of Publications Sever
Page 225 and 226:
Appendix 207 Curriculum Vitae Perso
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