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52 Chapter 3 with that of the Ru II,III -BTC (Figure 3.19). The bands corresponding to the νs(COO) and νas(COO) vibrations appear at 1359 cm -1 and 1429cm -1 , respectively, suggesting the coordination of the carboxylate groups of framework BTC. However, presence of unreacted acetic acid and H3BTC cannot be strictly excluded from IR, as the bands stemming from C=O stretching in Ru-MOF samples is too small to be distinguished. The 1 H-NMR spectrum of acid-digest sample 5 displays peaks at 8.60 and 1.86 ppm (Figure 7.13). The former resonance is originated from the aromatic protons of BTC. However, the latter one can be attributed to the protons of acetate, suggesting the presence of AcO(H) in the obtained sample. H 3 BTC (C=O) Ru II,II 2 (OOCCH 3 ) 4 5 Ru II, III -BTC 4000 3500 3000 2500 2000 1500 1000 500 wavenumber, cm -1 Figure 3.19. IR spectra of the Ru-BTC 5 in comparison with Ru II,III -BTC 1, [Ru 2 (OOCCH 3 ) 4 ] and H 3 BTC. The vertical dash line corresponds to the position of ν(C=O) bands.
Chapter 3 53 3.2.2 Investigation on the Ru oxidation state and porosity of Ru-MOF 5 To get more information on the oxidation state of Ru-centers in the obtained sample 5, XANES spectra on sample 5, Ru II,III -BTC 1, used Ru-precursors (SBU-a and -e) and RuCl3 were subsequently recorded. Due to the differences in position of edge jump different valences of Ru, the oxidation state of Ru-centers in the MOF structure can be concluded from the position of the highest peak in the plot of derivative normalized absorption vs. energy. As illustrated by the Figure 3.20, Ru II,III -BTC 1 shows an edge jump position between RuCl3 and its starting precursor SBU-a, indicating its mixed valence state, as documented earlier. [82] To remark, only Ru II was found in the SBU-e. [207] Thus, the same edge jump position observed in the XANES spectra of the sample 5 suggests the presence of Ru II -center in the framework structure (Figure 3.20). Consequently, the obtained solid 5 should feature the exact Ru2-PWs as that in HKUST-1 without any counter-ions around. In the fact, EA results do not reveal the presence of any Cl in the sample Ru-MOF 5, ruling out the existence of Cl - and RuCl3 in both SBU-e employed during the synthesis and the obtained solid Ru-MOF 5. A formula of [Ru3(BTC)2]n∙(AcOH)2.3 match well with the obtained EA results, which could be another sign of the absence of counter-ions. In comparison with Ru II,III -BTC (1-4) described in Chapter 3.1, the obtained framework turns to be simpler in the absence any counter-ions, although the presence of acetic acid cannot be avoided. Furthermore, N2 sorption isotherms collected at 77 K for Ru-MOF 5 demonstrate type I isotherm (Figure 3.21), indicating the microporosity of this material. Given the greater bulk density of Ru-BTC than Cu-BTC and in order to have a better comparison with HKUST-1, SBET is calculated in the unit of m 2 /mmol. Thus, SBET of Ru-MOF 5 amounts to 1173 m 2 /mmol, which is quite comparable with the reported value of Cu- BTC (1049 m 2 /mmol), [83] indicating the same accessibility of Ru-centers as Cu-sites. Moreover, the axial positions of the diruthemium PW units in the synthesized Ru II,II -BTC (5) are expected to be open compared to the Ru II,III -BTC, where the presence of counterions (Cl - , OH - , AcO - ) is needed to balance the charge of [Ru2] 5+ units. The considerably higher BET surface area (SBET) of Ru II,II -BTC 5 (1371 m 2 /g) than that respective values reported for Ru II,III -BTC (704-1180 m 2 /g) [82-83, 138, 208] further supports an assumption on availability of Ru-CUSs in Ru II,II -BTC 5.
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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
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]
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 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
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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
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·
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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
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196 Bibliography [61] S. Ma, D. Sun
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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
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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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