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176 Chapter 7 For comparison of the obtained S BET values for Ru-MOFs with the homologous Cu-MOFs, it might be more informative using m 2 /mmol units (due to substantial difference in the molecular weight of Cu and Ru and the presence of guest molecules). Thus, the S BET of the parent Ru-MOF (964 m 2 /mmol) is quite similar to that of a typical reference sample [Cu 3 (BTC) 2 ] n (1049 m 2 /mmol). More importantly, the S BET of the Ru-DEMOF solids slightly increases in comparison with both parent analogues. Due to the complexity of the composition (which has been mentioned in the section 4.2.1.2 of Chapter 4), EA was not performed for the rest Ru-DEMOFs to determine the unambiguous composition with counter-ions and guest molecules. Hence, S BET values in the unit of m 2 /mmol were not calculated for them. Figure 7.14. XPS survey scan of the parent Ru-MOF and Ru-DEMOFs (1a, 1c, 1d, 2a and 2b). 1a, 1c and 1d - 8%, 32% and 37% 5-OH-ip incorporation, respectively; 2a and 2b - 15% and 28% ip incorporation, respectively. Figure is provided by P. Guo.
Chapter 7 177 7.3.2 Catalytic reactions using Ru-DEMOFs as catalysts 7.3.2.1 Ethylene dimerization In a typical run (entry 5), 2.1 mg of the activated Ru-MOF 1c was put in a 10 ml steel reactor followed by adding of 0.81 ml of Et2AlCl (1M in heptane), 2.1 ml of toluene and 0.09 ml of undecane (0.01 M in toluene). After degassing, the reactor was flushed with C2H4 (800psi) and placed in a pre-heated oil bath at 80 °C with stirring for 2 hours. Subsequently, the reaction was stopped and the reactor was cooled down at -7 °C in a mixture of dry ice and ethylene glycol bath. Cold distilled water was added to quench the reaction. The organic layer kept cold was then quickly analyzed by gas chromatography (SRI 8610V GC, 60 m x 0.54 mm internal diameter, 5.0 µm MXT-1 capillary columns) using undecane signal as a reference. In case of no additive, the volume of toluene was changed to 2.91 ml. Other parameters are the same as entry 5 described above. 7.3.2.2 Paal-Knorr reaction In a typical run, 5 mg of the activated Ru-MOF/DEMOFs in 0.5 ml of toluene were introduced into 125 mg (1.1 mmol) of 2,5-hexadione and 95 mg (1 mmol) of aniline and were stirred at 90 °C for 24h under air. The reaction was followed by taking aliquots every hour and analyzing the products by GC-MS. The reactions were performed in closed (pressurize able) reaction vials. 7.3.3 Synthesis of [Cu3(BTC)2]n (Cu-BTC) [Cu3(BTC)2]n was prepared from a reported method [35] at a litter lower temperature (120 °C). Specifically, Cu(NO3)2∙3H2O (1.8 mmol, 438 mg) and 1, 3, 5-benzentricarboxylic acid (H3BTC, 1.0 mmol, 210 mg) were put into a Teflon vessel, and a solution of 12 ml H2O:EtOH (1:1) was added. The vessel was sealed in an autoclave and kept in a preheated oven at 100 °C for 12 h. The crude product was filtered and washed several times with distilled water and absolute ethanol, respectively. After dried under ambient conditions the obtained powder (152 mg) was further activated by heating at 120 °C for 24 h under dynamic vacuum (ca. 10 -3 mbar).
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Controlled Modification of Metal-Or
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This thesis is based on the work pe
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Bochum) for the study of XPS and UH
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Zhang, for their continuous support
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II 3.2.1 Synthesis and characteriza
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IV 7.3.4 Synthesis of Cu-DEMOF samp
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VI DMSO dobdc e.g. EA EDX EtOH EXAF
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VIII TOF UHV UiO UMCM vs WCA XANES
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2 Chapter 1 limitations of the (non
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4 Chapter 2 For the synthesis of CP
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6 Chapter 2 cavities is able to rev
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8 Chapter 2 2.2.2 MOF features Adva
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10 Chapter 2 Figure 2.5. A series o
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12 Chapter 2 the material is retain
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14 Chapter 2 2.3 Synthetic approach
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16 Chapter 2 Expansion of this stru
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18 Chapter 2 (H2BPDC) [75] or other
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20 Chapter 2 Cr III CUSs of MIL-101
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22 Chapter 2 Figure 2.14. Schematic
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24 Chapter 2 adsorbate-surface inte
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3 Controlled secondary building uni
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28 Chapter 3 3.1 Preparation and in
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30 Chapter 3 formula of [Ru3 II,III
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Intensity, a. u. 32 Chapter 3 quali
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34 Chapter 3 After activating the R
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36 Chapter 3 presence of the residu
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Intensity, a. u. 38 Chapter 3 the a
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40 Chapter 3 extent than acetic aci
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42 Chapter 3 Ru-nodes. Therefore, r
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44 Chapter 3 decomposition of [BF4]
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deriv. normalized E) 46 Chapter 3 F
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48 Chapter 3 3.1.6 Summary Applying
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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+
Page 144 and 145: 126 Chapter 5 5.2 Preparation and S
Page 146 and 147: 128 Chapter 5 Figure 5.5. Pawley Fi
Page 148 and 149: 130 Chapter 5 5.3 Compositional cha
Page 150 and 151: 132 Chapter 5 Table 5.3. The assign
Page 152 and 153: 134 Chapter 5 framework are dominan
Page 154 and 155: 136 Chapter 5 5.4 Synthesis, compos
Page 156 and 157: 138 Chapter 5 obtained Pd-doped sol
Page 158 and 159: 140 Chapter 5 Figure 5.18. Deconvol
Page 160 and 161: V, cm 3 /g 142 Chapter 5 sorption i
Page 162 and 163: 144 Chapter 5 time as well as the i
Page 164 and 165: 146 Chapter 5 5.6 Conclusions In su
Page 166 and 167: 148 Chapter 6 coordinating anion),
Page 168 and 169: 7 Experimental Section In this Chap
Page 170 and 171: 152 Chapter 7 as water and hydroxyl
Page 172 and 173: 154 Chapter 7 internal standards an
Page 174 and 175: 156 Chapter 7 Uppermost layer is in
Page 176 and 177: 158 Chapter 7 to the more tightly b
Page 178 and 179: 160 Chapter 7 7.2 Experimental data
Page 180 and 181: 162 Chapter 7 [Ru2(OOCC(CH3)3)4(H2O
Page 182 and 183: 164 Chapter 7 Figure 7.7. The PXRD
Page 184 and 185: 166 Chapter 7 [Ru2(OOCCH3)4(H2O)2]B
Page 186 and 187: 168 Chapter 7 [Ru2(OOCCH3)4](THF)2
Page 188 and 189: 170 Chapter 7 [Ru3(BTC)2(OH)1.5]n·
Page 190 and 191: 172 Chapter 7 [Ru3(BTC)2]n∙(AcOH)
Page 192 and 193: 174 Chapter 7 Table 7.3. Feeding mo
Page 196 and 197: 178 Chapter 7 7.3.4 Synthesis of Cu
Page 198 and 199: 180 Chapter 7 D3 The mixture of H3B
Page 200 and 201: 182 Chapter 7 D5 This sample was re
Page 202 and 203: 184 Chapter 7 The synthesis of D7 a
Page 204 and 205: 186 Chapter 7 7.4 Experimental data
Page 206 and 207: 188 Chapter 7 Figure 7.26. PXRD pat
Page 208 and 209: 190 Chapter 7 7.4.2 Hydrogenation o
Page 210 and 211: 192 Chapter 7 7.5 Supplementary det
Page 212 and 213: 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
Page 218 and 219: 200 Bibliography [180] Y. Kobayashi
Page 220 and 221: 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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