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Intensity, a. u. 110 Chapter 4 as-synthesized samples D2-D4_as (Figure 4.41) disappear after samples activation (i.e. heating under vacuum). Thus, the origin of these reflections might come from coordinated solvent molecules, which under employed activation conditions are subsequently removed. FT-IR spectra of all activated Cu-DEMOFs samples do not vary from the FT-IR spectrum of the parent Cu-BTC, displaying also overlapping of the characteristic bands of ip and BTC (Figure 4.42). However, the typical νs(COO) and νas(COO) bands of carboxylates are observed at around 1442 cm -1 and 1366 cm -1 , respectively. Moreover, the absence of [BF4] - (from the used Cu-salts) is confirmed, as no ν(B–F) band was found at 1073 cm –1 . [208] D4_as D3_as D2_as D1_as Cu-BTC_sim. 5 10 15 20 25 30 2, degree Figure 4.41. PXRD patterns of the as-synthesized Cu-DEMOF samples D1-4_as in comparison with the patterns simulated from the single-crystal XRD data of the reported [Cu 3 (BTC) 2 ] n (Cu- BTC_sim). Metal source: Cu(BF 4 ) 2 6H 2 O. Solvent used for synthesis of D1 and D2 (blue patterns): DMF; for D3 and D4 (red patterns): EtOH.
Chapter 4 111 H 3 BTC H 2 ip D4 D3 D2 D1 Cu-BTC 4000 3500 3000 2500 2000 1500 1000 500 wavenumber, cm -1 H 3 BTC H 2 ip D4 D3 D2 D1 Cu-BTC 2000 1500 1000 500 wavenumber, cm -1 Figure 4.42. IR spectra of the activated samples D1-D4 in comparison with the spectra of the parent Cu-BTC, H 3 BTC and H 2 ip. Bottom figure represents selected region from 2000 cm -1 to 350 cm -1 . Metal source: Cu(BF 4 ) 2 6H 2 O. Solvent used for synthesis of the D1 and D2 (blue): DMF; for the D3 and D4 (red): EtOH.
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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
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 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
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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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