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H 2 adsorbed, mmol/g 100 Chapter 4 that the enhancement of sorption of small molecules (CO2 and H2) attributed to defects A is stronger than the influence caused from defects B. 8 6 4 2 parent Ru-MOF 2a 2b 0 0 200 400 600 800 1000 P, mbar Figure 4.36. H 2 isotherms measured at 77 K for the parent Ru-MOF and its derivatives 2a (15%) and 2b (28%) with ip DL. Black circles – parent Ru-MOF; blue triangles – 2a; dark cyan diamonds – 2b. 4.2.5 Catalytic test reactions Ethylene dimerization utilizing MOF supported catalysts has recently attracted a lot of attention due to its modifiable characteristic under molecular level. [231-234] Most of the reported MOF catalysts bear isolated single-metal (e.g., Ni, Ir) active-sites. Ru-MOF materials as heterogeneous catalysts for the ethylene dimerization have not been studied yet, although chemisorbed Ru-complex on de-aluminated zeolite Y and Ru-complex itself catalyzing ethylene to butene have been already reported. [235-237] It is known that the redox activity of Rh in RhCa-X Zeolite plays an important role on catalyzing ethylene dimerization. [238] Having distinct Ru-CUS available in the Ru-DEMOFs (i.e., different Ru n+ - species being potentially involved into the redox-process(es) of the reaction flow),
Chapter 4 101 samples 1a (8% of 5-OH-ip) and 1c (32% of 5-OH-ip) have been selected for testing them as catalysts for ethylene dimerization. In addition, parent Ru-MOF has been used as a reference. Thus, activated Ru-DEMOFs were loaded into a reactor to catalyze ethylene Table 4.7. The conversion of ethylene to butene in toluene under different conditions. Entry Catalyst (mg) Temperature ( °C) Time (h) Additive TOF (h -1 ) 1 1c (2.5) 80 24 ---- 0.92 2 1c (2) 80 1 Et 2 AlCl 4.38 3 1c (2) 80 1 ---- 0.88 4 1c (2.4) 26 2 Et 2 AlCl 2.15 5 1c (2.1) 80 2 Et 2 AlCl 4.36 6 1a (2) 80 2 Et 2 AlCl 2.3 7 Parent Ru-MOF (1.8) 80 2 Et 2 AlCl 2.05 dimerization in toluene at different temperatures under the pressure of 800 psi (≈ 55 bar). In general, all reactions led to the formation of butene without producing any other α- olefins (Tables 4.7). Addition of Et2AlCl as co-catalyst accelerates the conversion (Table 4.7, entry 2 vs. entry 3). When the reaction has been conducted at 26 °C, lower yield has been obtained compared to those at 80 °C (Table 4.7, entry 4 vs. entry 5). However, reactions conducted for 1 h and 24 h give almost the same TOF (0.88 vs. 0.92 h -1 ), suggesting that the Ru-DEMOF 1c does not suffer the deactivation as a function of onstream time. Therefore, parent Ru-MOF and Ru-DEMOFs 1a and 1c have been employed to study the dimerization of ethylene in toluene under optimized condition (800 psi, 80 °C, 2 h) in the presence of Et2AlCl. The obtained product was analyzed by gas chromatography. As it can be seen from entry 5-7 in Table 4.7 and Figure 4.37, the TOF value of 1a and 1c increase along with increase of the incorporation level of DL in comparison with the parent Ru-MOF. Since the contents of the reduced Ru δ+ -sites in 1c is the highest among the 1a-d series (according to our study above), there should be more M-CUSs in 1c and therefore it affords the chance to enhance the catalytic activity in the reaction. Indeed, the transformation of ethylene to butene is the highest (TOF = 4.36 h -1 ) when employing 1c as a catalyst. This value is still much lower than that using zeolite supported Ru-complex catalysts in the presence of H2 (4.36 vs. 216 h -1 ). However, it is higher than the TOF value (1 × 10-4 s -1 = 0.36 h -1 ) in the reported reaction without the
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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
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 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),
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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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