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5 Simultaneous introduction of various palladium active sites into MOF via one-pot synthesis: Pd@[Cu3-xPdx(BTC)2]n ‡ Abstract Simultaneous structural incorporation of palladium within Pd-Pd and/or Pd-Cu paddlewheels as framework-nodes and Pd nanoparticles (NPs) dispersion into MOF have been achieved for the first time via one-pot synthesis. The substitution of Cu 2+ by Pd 2+ within polymer carcass as well as the loading of Pd NPs have been confirmed in particular by XPS. Solids featuring such both Pd-sites show enhanced activity (compared to the parent “Pd-free” Cu-BTC) in the hydrogenation of p-nitrophenol (PNP) to p-aminophenol (PAP) using NaBH4 as a reducing agent. ‡ Work in this chapter is covered in the manuscript submitted to Dalton Trans.
Chapter 5 123 5.1 Introduction on the selection of metal type in MOFs High structural and compositional design ability of metal-organic frameworks (MOFs) and, hence, the ability of tailoring their properties made MOFs to be among the most topical materials over last decades. Along with linker(s) modification [64, 123, 251] and guest(s) inclusion, [252-253] variation of the metal center(s) is also a powerful tool to fine tune MOFs functionalities. In fact, both control over coordinatively unsaturated metal sites (CUS) (e.g., via “defects-engineering”) [137] and partial metal substitution (e.g., via mixed-metal “solid solution” approach) could considerably enhance MOFs activity, especially in catalysis [138, 141, 254] and selective gas sorption/separation. [255-256] Figure 5.1. Partial metal (Cu vs Mn, Zn, Co) substitution in Cu-BTC. Reprinted with permission from D. F. Sava Gallis, M. V. Parkes, J. A. Greathouse, X. Zhang and T. M. Nenoff, Chem. Mater., 2015, 27, 2018-2025. Copyright (2015) American Chemical Society. [256] Combination of distinct metal-ions, which are closely related in coordination chemistry and have similar effective ionic radii (rion), like Cu 2+ (73 pm) / Zn 2+ (74 pm) couple [257] for instance, within single MOF has been reported for several structural types. [131, 255, 258] In fact, partial substitution of Cu 2+ by Zn 2+ and some other metals of 3d-row, namely Co, Fe and Mn, in HKUST-1 ([Cu3(BTC)2]n, BTC = benzene-1,3,5-tricarboxylate) has been recently reported (Figure 5.1). [133, 256] Curiously, in later case doping with second metal caused enhanced selective sorption of O2 vs N2. [256, 259] What is more challenging however, is to take benefits of solid solution approach to introduce more distinct metals of 4d- [134] or 5drow [260] as framework-nodes. In particular, metals of the platinum group are highly attractive as catalytic- / strong sorption-centers. Besides, square planar coordination is
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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
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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
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 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·
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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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