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deriv. normalized E) 46 Chapter 3 Figure 3.15. N 2 adsorption (solid symbols) and desorption (open symbols) isotherms (recorded at 77 K) of the Ru-MOFs obtained from different SBUs. 1-4: before solvent exchange; 1-4_ex: after solvent exchange. Squares: 1 and 1_ex; triangles: 2 and 2_ex; diamonds: 3 and 3_ex; circles: 4 and 4_ex. 3.1.5.4 Oxidation state study SBU-a RuCl 3 SBU-b SBU-c Ru SBU-d RuO 2 22100 22120 22140 22160 energy, eV Figure 3.16. XANES spectra (derivative normalized absorption vs. energy) of the Ru-SBUs in comparison with Ru-standard samples (Ru, RuCl 3 and RuO 2 ).
deriv. normalized E) Chapter 3 47 In order to gather information on the valence of the Ru-sites in the Ru-MOFs, comparative X-ray absorption spectroscopy (XAS) measurements were subsequently carried out. The derivative of the edge-jump energy positions of Ru (22117 eV) and RuO2 (22131 eV) can be used as standards, representing the oxidation states +0 and +4, respectively. On the other hand, according to the literature, the oxidation state of Ru-center in SBU-a reveals +2.5. [203] Hence, the same position of derived edge-jump energy (ca. 22124 eV) for SBU-a - -d clearly indicates the oxidation state of Ru-centre to be +2.5 (Figure 3.16). To note, Ru- MOF sample 1_ex with the edge jump position at 22126 eV matches well with its mixed oxidation state documented in the literature by UHV-IR technique with CO probe. [82] All the other Ru-MOFs samples (2-4_ex) exhibit their edge-jump at the range of 22123-22128 eV, suggesting the mixed oxidation state of the Ru-centers in their structure as well (Figure 3.17). The study on deviation of local coordination environments within these Ru- MOFs due to the change of the counter-ions (in particular by Extended X-Ray Absorption Fine Structure (EXAFS)) is one of our further direction. Ru Ru NP 3_ex 4_ex RuO 2 2_ex 1_ex 22100 22120 22140 22160 energy, eV Figure 3.17. XANES spectra (derivative normalized absorption vs. energy) of Ru-MOFs obtained from various Ru-SBUs (1-4_ex) in comparison with Ru-standard samples (Ru, Ru NP and RuO 2 ).
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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
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 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 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
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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+
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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
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158 Chapter 7 to the more tightly b
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160 Chapter 7 7.2 Experimental data
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162 Chapter 7 [Ru2(OOCC(CH3)3)4(H2O
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164 Chapter 7 Figure 7.7. The PXRD
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166 Chapter 7 [Ru2(OOCCH3)4(H2O)2]B
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168 Chapter 7 [Ru2(OOCCH3)4](THF)2
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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
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206 Appendix List of Presentations
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208 Appendix 05. 2015 Grant from th
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