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2 Chapter 1 limitations of the (non-doped) parent MOFs. In particular, increased sorption capacity, selectivity and enhanced catalytic activity could be expected. Up to date, only limited reports have been dealing with the studies on DEMOFs and their application. Among the MOFs featuring CUSs and showing good performance on applications, HKUST- 1 ([Cu3(BTC)2]n) is one of the widely and well investigated MOFs. Besides, its mixedvalence structural analogue [Ru3(BTC)2Yy]n (Y = counter-ions, 0≤y≤1.5) exhibits sufficient chemical and thermal stability, and can offer rich photo/redox chemistry. Hence, in this thesis those two kinds of MOFs with the general formula [M3(BTC)2]n have been chosen as candidates on the study of defect-engineering. However, before starting with the exploration of such intriguing DEMOFs, the formation of both “intrinsic” and “intentional” defects in MOFs should be wisely taken into account. Especially, in the case of [Ru3(BTC)2Yy]n, due to the kinetic reason, its formation should be carefully monitored. Hence, Chapter 3 in this thesis mainly focus on the parent [Ru3(BTC)2Yy]n for the study of possible intrinsic defects, optimized exclusion of the guest molecules and elaboration of mono-valence Ru analog of HKUST-1. Further, intentional introduction of defects to [Cu3(BTC)2]n and [Ru3(BTC)2Yy]n respectively by linker and/or metal doping will be worth investigating. Modifications of the metal sites, generation of (additional) accessible coordination sites as well as the complexity of the developed DEMOFs will be studied in detail in Chapters 4 and 5. Moreover, the impact of the defects engineering on gas sorption and catalysis properties of the resulting DEMOFs will be explored. It is expected that these study show a comprehensive picture on the DEMOF derivatives of the selected M-BTC structure and give us deep insights on the defectengineering of other MOFs.
2 General introduction The aim of this chapter is to give a general introduction on the research progress of metalorganic frameworks (MOFs) including the origin of MOFs, their chemistry, structural features, synthetic approaches, modification on the structure as well as their applications. 2.1 Origin of MOFs - Coordination polymers In 1833, J. J. Berzelius firstly use the term “polymer” to describe any compound that could be formulated as consisting of multiple units of a basic building block. [1] Later, Werner for the first time, proposed the correct structure [Co(NH3)6]Cl3 for coordination compounds containing complex ions in 1893, which developed the groundwork for the study of coordination polymers (CPs). In 1916, to define dimers and trimers of various cobalt(II) ammine nitrates, the term “CPs” was firstly employed by Y. Shibata [2] and has been continuously used in the scientific literature since the 1950's. Moreover, the first review on CPs was published in 1964. [3] The International Union of Pure and Applied Chemistry (IUPAC) Red Book of inorganic nomenclature from 2005 gives the following definition of coordination compounds: “A coordination compound is any compound that contains a coordination entity. A coordination entity is an ion or neutral molecule that is composed of a central atom, usually that of a metal, to which is attached a surrounding array of atoms or groups of atoms, each of which is called a ligand”. [4] Consequently, CPs can be conceptually considered as coordination compounds with extended arrays structures of one, two or three dimensions (Figure 2.1). [5] Typically, CP consists of two central components: metal ions (serving as connectors) and ligands (serving as linkers). Apart from these two components, blocking ligands, counter-anions, non-bonding guests or template molecules can be also included (Figure 2.2). The number and orientation of the binding sites (i.e. coordination numbers and geometries) are the important characteristics of the connectors and linkers. Their combination in numerous ways via a self-assembly enables the formation of practically an infinite number of CPs (Figure 2.1).
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 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
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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
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60 Chapter 4 framework [Cu2(ndc)2(d
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62 Chapter 4 partial replacing of B
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64 Chapter 4 in the case of ip intr
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66 Chapter 4 4.2.1.1 Crystallinity
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68 Chapter 4 suggesting the absence
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70 Chapter 4 Table 4.1. The molar f
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72 Chapter 4 Figure 4.11. IR spectr
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74 Chapter 4 taking into account th
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76 Chapter 4 As quantitative digest
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78 Chapter 4 (Figure 4.16). Notably
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80 Chapter 4 framework Ru-species (
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82 Chapter 4 Figure 4.20. XANES spe
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84 Chapter 4 It is important to not
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86 Chapter 4 Ru δ+ have been obser
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88 Chapter 4 Figure 4.25. UHV-IR sp
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90 Chapter 4 Table 4.5. Possible de
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CO 2 adsorbed, mmol/g 92 Chapter 4
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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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