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158 Chapter 7 to the more tightly bound electron states. Consequently, the absorption edge energy increases along with the increase of oxidation-state of the absorption site. Sample measurements details The collection of XANES spectra was performed at the Ru-K edge (22117 eV) using a Si (311) monochromator at Beamline BL8 of the synchrotron radiation facility DELTA, TU Dortmund. The samples were filled into 1 mm caplillaries in an inert Ar atmosphere glovebox before the measurement. The set-up was acquired using 15cm Ionchamber filled with Ar as I0, a 15 cm Ionchamber filled with Xe as I1 and a 30 cm Ionchamber filled with Xe as I2. Approx 30 mm above the sample was the PIN-Diode capturing a relatively wide solid angle of fluorescence radiation. The energy was calibrated by measuring a metallic Ru foil as reference simultaneously to each sample scan. The data processing and analysis were done using the program ATHENA. [301] 7.1.10 X-ray photoelectron spectroscopy (XPS) XPS spectra were recorded and analyzed by our collaboration partners, P. Guo and Dr. Y. Wang in the Laboratory of Industrial Chemistry (Prof. Dr. M. Muhler), Ruhr‐University Bochum. The discussion of the selected data was done by W. Zhang. XPS measurements were performed in a UHV setup equipped with a high-resolution Gammadata-Scienta SES 2002 analyzer. A monochromatic Al Kα X-ray source (energy 1486.6 eV) was used as incident radiation. The analyzer slit width was set at 0.3 mm and the pass energy was fixed at 200 eV for all the measurements. The overall energy resolution was better than 0.5 eV. A flood gun was used to compensate for the charging effects. All spectra reported here are calibrated to the C 1s corelevel binding energy at 285 eV. The XP spectra were deconvoluted using the CASA XPS program with a mixed Gaussian −Lorentzian function and Shirley background subtraction. 7.1.11 High Performance Liquid Chromatography (HPLC) HPLC measurements to determine the ratio of the organic components were conducted by Dr. H. B. Albada and M. Strack at the Chair of Inorganic Chemistry I-Bioinorganic Chemistry (Prof. Dr. N. Metzler-Nolte), Ruhr‐University Bochum. Experimental setup:
Chapter 7 159 Buffers: A: water/MeCN/TFA – 95/5/0.1 (%, v/v/v); B: MeCN/water/TFA – 95/5/0.1 (%, v/v/v) Gradient: start with 100 % A for 5 min; then in 15 min to 75 % B (i.e. 5 %/min); steady at 75 % B for 2.5 min; drop to 100 % A in 5 min (i.e. 20 %/min); steady at 100 % A for 2.5 min. Column: Prontosil, RP C18‐AQ, with pre‐column; dimensions: 250 x 4.6 mm (length x internal diameter), particle size: 5 μm; pore diameter: 120 Å (Knauer, Batch No. 2362, Column SN: CG 108, 25VF184PSJ). Detection: λ = 254 nm. Equipment: HPLC‐runs were performed on a Knauer HPLC‐machine. 7.1.12 Catalytic studies Catalytical tests for Paal-Knorr reaction in Chapter 4 were performed in collaboration with the group of Prof. A. Corma, in particular by K. Epp (TU Munich) and Dr. F. X. Llabrés i Xamena, in the Institute of Chemical Technologies (Instituto de Tecnología Química, ITQ), Polytechnical University of Valencia (Spain). Ethylene dimerization in Chapter 4 was carried out by W. Zhang with the assistance of M. Gonzalez (the group of Prof. J. R. Long) in the department of Chemistry, University of California, Berkeley (US). Catalytic reaction for the hydrogenation of PNP to PAP in Chapter 5 was performed by Z. Chen and M. Al- Naji (Group of Prof. R. Gläser) in the institute of Chemical Technology, University of Leipzig. Data for the catalysis was analyzed by W. Zhang with the assistance of these collaborators. Gas Chromatography measurements for monitoring the product of Paal-Knorr reaction were performed on an Agilent Technologies 7890A with FID (Flame Ionization Detector) using a capillary column HP-5 (5% phenylmethylpolysiloxane) of 30 m length and 0.32 mm internal diameter as well as BP20(WAX) of 15 m length and 0.32 mm internal diameter as another column. Thereby, the products were measured in high dilution using volatile organic solvents (usually ethanol or acetone).
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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
Page 126 and 127: 108 Chapter 4 4.3 Defects Engineeri
Page 128 and 129: Intensity, a. u. 110 Chapter 4 as-s
Page 130 and 131: weight loss, % 112 Chapter 4 100 Cu
Page 132 and 133: weight loss, % 114 Chapter 4 record
Page 134 and 135: 116 Chapter 4 4.3.2 Composition and
Page 136 and 137: V, cm 3 /g 118 Chapter 4 500 400 30
Page 138 and 139: 120 Chapter 4 Figure 4.50. From lef
Page 140 and 141: 5 Simultaneous introduction of vari
Page 142 and 143: 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 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 194 and 195: 176 Chapter 7 For comparison of the
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
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208 Appendix 05. 2015 Grant from th
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