resolver

More documents

Recommendations

Info

64 Chapter 4 in the case of ip introduction into [Cu3(BTC)2]n. [140] It is conceivable, that such missing node defects could be formed in a correlated fashion during the MOF crystal growth process and in such a case larger areas of missing nodes may be generated to yield mesopores.
Chapter 4 65 4.2 Ruthenium Metal-Organic Frameworks featuring Different Defect Types Being mainly studied in Cu-HKUST-1, a comprehensive understanding of the nature and formation of different types of isolated local and larger scale correlated defect sites in DEMOFs of the [M3(BTC)2]n family and MOFs in general is very limited and this research is still at its infancy. [137] The work in this chapter is a follow-up of the previous investigations on defect engineering in [Ru3(BTC)2Yy]n using H2pydc as (single) defect generating linker. [138] Similar to the previous more elaborate study on defect-engineered Cu-HKUST-1 [139] , a series of 5-X-isophthalic acids (5-X-ipH2, X = OH, H, NH2, Br) are selected and mixed them with H3BTC to yield the Ru-DEMOFs of the general formula [Ru3(BTC)2-x(5-X-ip)xYy]n (Figure 4.5). The choice of the functional group X in DL is on the basis of two aspects: i) modulating the coordination binding strength between linkers and Ru-nodes, namely, changing one of the carboxylate group in parent H3BTC linker to weaker binding groups (OH, NH2) or even inert coordination groups (H, Br); ii) labeling DL with easily tracked elements such as Br, NH2, etc. for analytical purpose. Thus, a number of complementary characterization methods are applied to obtain compositional and microstructure data of the materials. The aim is to at least qualitatively assess the tendency of type A and type B defect formation as a function of synthetic conditions and the chosen 5-X-ip linker. Several catalytic reactions, such as ethylene dimerization and Paal-Knorr reaction (usually running under Lewis acidic conditions) as well as low temperature CO2→CO dissociative chemisorption in the dark under UHV conditions, have been chosen as test reactions to monitor the influence of defects on the performance of the Ru-DEMOFs. 4.2.1 Synthesis and characterization of the Ru-DEMOF materials In the following, a comprehensive account on the conducted experiments, obtained analytical and characterization data is provided for elucidation of the defect structure of Ru-DEMOFs of the general formula [Ru3(BTC)2-x(5-X-ip)xYy]n. The main goal of the presented study is to substantiate the hypothesis of type A and type B defect formation in these systems as introduced above (Figure 4.5).
Page 1:
Controlled Modification of Metal-Or
Page 5:
This thesis is based on the work pe
Page 8 and 9:
Bochum) for the study of XPS and UH
Page 10 and 11:
Zhang, for their continuous support
Page 12 and 13:
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 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 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 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),
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
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·
Page 190 and 191:
172 Chapter 7 [Ru3(BTC)2]n∙(AcOH)
Page 192 and 193:
174 Chapter 7 Table 7.3. Feeding mo
Page 194 and 195:
176 Chapter 7 For comparison of the
Page 196 and 197:
178 Chapter 7 7.3.4 Synthesis of Cu
Page 198 and 199:
180 Chapter 7 D3 The mixture of H3B
Page 200 and 201:
182 Chapter 7 D5 This sample was re
Page 202 and 203:
184 Chapter 7 The synthesis of D7 a
Page 204 and 205:
186 Chapter 7 7.4 Experimental data
Page 206 and 207:
188 Chapter 7 Figure 7.26. PXRD pat
Page 208 and 209:
190 Chapter 7 7.4.2 Hydrogenation o
Page 210 and 211:
192 Chapter 7 7.5 Supplementary det
Page 212 and 213:
8 Bibliography [1] A. J. Ihde, The
Page 214 and 215:
196 Bibliography [61] S. Ma, D. Sun
Page 216 and 217:
198 Bibliography [121] T. K. Prasad
Page 218 and 219:
200 Bibliography [180] Y. Kobayashi
Page 220 and 221:
202 Bibliography [239] A. L. Harreu
Page 222 and 223:
204 Bibliography [297] A. P. Hammer
Page 224 and 225:
206 Appendix List of Presentations
Page 226:
208 Appendix 05. 2015 Grant from th
show all

resolver

You also want an ePaper? Increase the reach of your titles

Delete template?

Save as template?