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3 Controlled secondary building unit approach to the formation of the isostructural Ru II,II and Ru II,III analogs of [M3(BTC)2]n Abstract Controlled secondary building unit approach (CSA) was employed to derive a series of ruthenium metal-organic frameworks (MOFs) of the general formula [Ru3(BTC)2Yy]n·G g (BTC = 1,3,5-benzenetricarboxylate; Y = counter-anion, G = guest molecules, 0 ≤ y ≤ 1.5),
Chapter 3 27 which are structural analogs of [M3(BTC)2]n (M = Cu, Zn, Ni, Cr, Mo). As Ru-precursors for CSA mixed-valence [Ru2 II,III (OOCR)4X] and [Ru2 II,III (OOCCH3)4]A compounds, with various nature of the anions X and A (strong coordinating X (like Cl - ) and weakly coordinating A (like [BF4] - or [BPh4] - )) as well as alkyl groups at the carboxylate ligand R (R = CH3 or C(CH3)3 ), were employed. Additionally, [Ru2 II,II (OOCR)4] complexes without any counterions were tested as Ru-source for Ru-MOF preparation. Systematic studies were conducted and five phase-pure Ru-MOFs were obtained. The set of characterization data support indicated the analytical compositions and the structural analogy of the prepared Ru-MOFs with the [M3(BTC)2]n family. The oxidation state of the Ru-sites in the obtained solids was studied by the X-ray absorption near edge structure (XANES) spectroscopy. The chosen Ru-precursors, optimized synthetic and activation protocols allowed improvement of the overall crystallinity, purity (in terms of residual solvent molecules) and porosity of the Ru-MOF materials.
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 12 and 13: II 3.2.1 Synthesis and characteriza
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 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]
Page 64 and 65: 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
Page 70 and 71: 52 Chapter 3 with that of the Ru II
Page 72 and 73: 54 Chapter 3 Figure 3.20. (a) XANES
Page 74 and 75: 4 Linker-based MOF solid solutions:
Page 76 and 77: 58 Chapter 4 4.1 Introduction 4.1.1
Page 78 and 79: 60 Chapter 4 framework [Cu2(ndc)2(d
Page 80 and 81: 62 Chapter 4 partial replacing of B
Page 82 and 83: 64 Chapter 4 in the case of ip intr
Page 84 and 85: 66 Chapter 4 4.2.1.1 Crystallinity
Page 86 and 87: 68 Chapter 4 suggesting the absence
Page 88 and 89: 70 Chapter 4 Table 4.1. The molar f
Page 90 and 91: 72 Chapter 4 Figure 4.11. IR spectr
Page 92 and 93: 74 Chapter 4 taking into account th
Page 94 and 95:
76 Chapter 4 As quantitative digest
Page 96 and 97:
78 Chapter 4 (Figure 4.16). Notably
Page 98 and 99:
80 Chapter 4 framework Ru-species (
Page 100 and 101:
82 Chapter 4 Figure 4.20. XANES spe
Page 102 and 103:
84 Chapter 4 It is important to not
Page 104 and 105:
86 Chapter 4 Ru δ+ have been obser
Page 106 and 107:
88 Chapter 4 Figure 4.25. UHV-IR sp
Page 108 and 109:
90 Chapter 4 Table 4.5. Possible de
Page 110 and 111:
CO 2 adsorbed, mmol/g 92 Chapter 4
Page 112 and 113:
H 2 adsorbed, mmol/g 94 Chapter 4 F
Page 114 and 115:
CO 2 adsorbed, mmol/g 96 Chapter 4
Page 116 and 117:
H 2 adsorbed, mmol/g 98 Chapter 4 8
Page 118 and 119:
H 2 adsorbed, mmol/g 100 Chapter 4
Page 120 and 121:
102 Chapter 4 presence of H2. [236]
Page 122 and 123:
104 Chapter 4 reactive metal center
Page 124 and 125:
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 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 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
Page 226:
208 Appendix 05. 2015 Grant from th
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