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70 Chapter 4 Table 4.1. The molar fractions (%) of the DLs used for the synthesis and observed in the final Ru- DEMOFs in respect to the total amount of linkers (H 3 BTC + 5-X-ipH 2 = 100%). The values were obtained from the integrals of proton peaks in 1 H-NMR spectra of the acid-digest sample. For the samples 1a-1d DL is 5-OH-ip; for 2a-2c – ip; for 4a-4c – 5-Br-ip, respectively. Sample Feeding (used for synthesis) Obtained 1a 10% 8% 1b 20% 20% 1c 30% 32% 1d 50% 37% 2a 10% 15% 2b 20% 28% 2c 30% 47% 4a 10% 17% 4b 20% 25% 4c 30% 42% A similar scenario was observed also for the samples with ip DL (series 2a-c). Resonances corresponding to the protons of ip are seen at 8.4 ppm, 8.1 ppm and 7.6 ppm (Figure 4.10). The framework incorporation amount of ip in 2a-c increases upon increasing the concentration of the DL in the reactant solutions. However, the incorporated amount of ip was found to be higher than expected from the H3BTC:H2ip feeding ratio, which is in contrast with that in the case of Ru-DEMOF series 1 where the incorporation of 5-OH-ip stay the same (or a little less) than the feeding concentration in the starting reactants. This result might be attributed to the slightly different coordination equilibria that correlate with the Brønsted acid dissociation constants of the used linkers: pKa (H3BTC) = 3.12, 3.89, 4.70 and pKa (H2ip) = 3.46, 4.46. [224] However, the pKa differences are small and a conclusive explanation based on pKa is not straightforward. Dincă et al. argued that deprotonated BTC could serve as a counter-ion to provide the charge balance of [Ru2] 5+ units in Ru-analogue of Cu-HKUST-1. [83] From our earlier investigation we concluded that H3BTC is present in the pores of [Ru3(BTC)2Yy]n in the form of fully protonated species, rather than as deprotonated counter-ions. [208] Both studies indicate that the linker used for the synthesis could still be present in the obtained materials. Hence, it is conceivable that the defect generating H2ip linker can also reside either as a counter-ion or as a guest
Chapter 4 71 molecule in the pores of the Ru-DEMOFs (2a and 2b). On the basis of these arguments it can be understood why the amount of incorporated ip can be higher than expected from the H2ip:H3BTC feeding ratio. Indeed, very weak IR-bands in the range of ν(C=O), ν(C=C) or νas(COO) vibrations (1736-1521 cm -1 ) have been observed in case of samples 2a-2d. However, the small separation of the ν(C=O) bands of non-coordinated acetic acid (1715- 1640 cm -1 ), [225] protonated/non-coordinated H2ip (1670 cm -1 ) and H3BTC (1680 cm -1 ) (see Figure 4.11.2) makes it hard to unambiguously determine the exact origin of these weak vibrations. Figure 4.10. 1 H-NMR spectra of the Ru-DEMOFs (2a-2c) digested in DCl/DMSO-d 6 mixture. DL is ip. H 3 O + comes from H 2 O and HCl contained in DCl. Due to the sensitivity of H 2 O peak to the solution conditions, the proton resonance of H 3 O + varies here along with the variation of pH value of the total solution.
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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
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 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 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
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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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