Metal-Organic Frameworks With Heterogeneous Structures

215 Pages·2021·25.119 MB·English

by  Ali Morsali, Kayhaneh Berijani

Metal-Organic Frameworks
With Heterogeneous Structures
Scrivener Publishing
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Martin Scrivener ([email protected])
Phillip Carmical ([email protected])
Metal-Organic Frameworks
With Heterogeneous
Structures
Ali Morsali and Kayhaneh Berijani
Department of Chemistry, Tarbiat Modares University,
Tehran, Islamic Republic of Iran
This edition first published 2021 by John Wiley & Sons, Inc., 111 River Street, Hoboken, NJ 07030, USA
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Library of Congress Cataloging-in-Publication Data
ISBN 978-1-119-79204-8
Cover image: Pixabay.com
Cover design by Russell Richardson
Set in size of 12pt and Minion Pro by Manila Typesetting Company, Makati, Philippines
Printed in the USA
10 9 8 7 6 5 4 3 2 1
Contents
List of Illustrations vii
List of Tables xv
List of Schemes xvii
Preface xix
Abbreviations xxi
1 Introduction: A Brief Introduction About Metal-Organic
Frameworks 1
1.1 Metal-Organic Frameworks 1
1.2 Conclusion 8
References 8
2 Metal-Organic Frameworks Complexity 13
2.1 Perspectives on Complexity in MOFs 13
2.2 Conclusion 21
References 22
3 Complexity Based on Ligand—Part 1 27
3.1 Mixed Ligand 27
3.2 Conclusion 50
References 51
4 Complexity Based on Ligand—Part 2 57
4.1 Polytopic Linkers 57
4.2 Multi-Heterotopic Ligands 63
4.3 Conclusion 66
References 66
v
vi Contents
5 Complexity Based on Metal Node 71
5.1 Mixed Metal 71
5.2 Multiple SBUs 81
5.3 Conclusion 92
References 92
6 Complexity Based on Chiral Framework—Part 1 105
6.1 Inherent Chirality 105
6.2 Direct Chirality 109
6.3 Conclusion 120
References 121
7 Complexity Based on Chiral Framework—Part 2 127
7.1 Chiral-Template Synthesis 127
7.2 Post-Synthesis 131
7.3 Conclusion 144
References 144
8 Complexity Based on Structural Defects 149
8.1 Inherent Defect 149
8.2 Designed Defect 154
8.3 Conclusion 161
References 162
9 Complexity Based on Heterogeneous Pores 171
9.1 Heterogeneous Pores 171
9.2 Conclusion 178
References 179
10 Complexity Based on Mixed MOFs 185
10.1 Complex Mixed MOFs 185
10.2 Conclusion 192
References 193
Index 199
List of Illustrations
Figure 1.1 Simple description of 3D MOF chemistry. 2
Figure 1.2 Some examples of metal nodes, organic linkers,
and MOFs (definition of atom types: blue: metal;
red: oxygen; purple: nitrogen; gray: carbon; and
green: chlorine). 3
Figure 1.3 Some examples of MOFs synthesis methods. 7
Figure 2.1 Simple language to understand concept of
complexity. 14
Figure 2.2 Overview of this book based on the effective
factors in the construction MOFs with
heterogeneous structures. 16
Figure 2.3 Classification of complexity key factors in MOFs
(further details in text). 16
Figure 2.4 A cost-effective mixed-metal mixed-ligand MOF,
which exhibits highly efficient photocatalytic H
2
generation. 19
Figure 2.5 D efective linker concept for defect-engineered
MOFs. 20
Figure 3.1 A photocatalyst MOF with three different ditopic
linkers. 33
Figure 3.2 S tructural analyses of a MOF-based
photocatalyst with three different ditopic linkers.
(a) Percent of BPDC-(HN ) incorporation
2 2
in ReMOF-NH (X%). (b) PXRD patterns:
2
Re-MOF, Re-MOF-NH (33%), Re-MOF-NH
2 2
(80%) and Re-MOF simulated pattern. (c) SEM
images: Re-MOF-NH (33%) and Re-MOF-NH
2 2
(80%). (d) N adsorption isotherms: Re-MOF,
2
Re-MOF-NH (33%) and Re-MOF-NH (80%).
2 2
vii
viii List of Illustrations
(e) IR spectra: Re-MOF, Re-MOF-NH (33%)
2
and Re-MOF-NH (80%). 34
2
Figure 3.3 (a) Copper-phosphonate CBU polyhedral.
Octahedral Cu1 and square pyramidal Cu2:
dark blue and light blue, respectively. PO C
3
tetrahedral: green. (b) The original structure of
the considered isoreticular MOF. 36
Figure 3.4 S chematic representations of the happened
processes in MOF with increased porosity.
(a and b) Organic linker installation and linker
labilization, respectively. (c) The produced
hierarchically porous MOF through linker
labilization (top). UV-vis analysis of linker
exchange process. (a) Concentration of AZDC
in supernatant as a function of incubation time
in CBAB solutions with different concentrations.
(b) Relationship between CBAB exchanged/
CBAB added, exchange ratio, and CBAB
molarity. (c) PCN-160 crystals images with
various exchange ratios. 38
Figure 3.5 S chematic representations of construction
mechanism. (a) Formed micropores, (b and c)
small and large mesopores, and (d) pores size
distribution of the considered MOF (PCN-160-
34%) in the presence of acid in different amounts.
(Top) (a) Representation of one kind of MOF in
the presence of enzyme. (b) relative activity of the
considered MOFs in the oxidative reaction of ABTS
(2,2ʹ-azino-bis(3-ethylbenzothiazoline-6-sulphonic
acid)) and o-PDA (o-phenylenediamine). 40
Figure 3.6 O ne kind of mixed-valence RuII/III MOF with
mixed-linker. 42
Figure 3.7 Olefin hydrogenation mechanism. 42
Figure 3.8 Zeolite-like MOFs based on mixed linkers. 44
Figure 3.9 A mixed-ligand MOF with two ligands BTC
(benzene-1,3,5-tricarboxylate) and BTRE
(1,2-bis(1,2,4-triazol-4-yl)-ethane). 44
List of Illustrations ix
Figure 3.10 S tepwise preparation of {[Cu (CDC) (4,4ʹ-
4 4
bipy)(H O) ] } ·xS. Copper: aqua; oxygen: red;
2 2 3 n
nitrogen: blue; carbon; black. Hydrogen atoms
have not been shown (top). Synthesis of the
isostructural porphyrinic MOFs and obtained
crystals photographs (bottom). 46
Figure 3.11 A DES-1: (a) coordination environment around
Zn(II); (b) and (c) [Zn (COO) ] SBU in 1D
2 2
metal-carboxylate chain and double lined
2D network, respectively; (d) ABAB manner
interlayer with lattice H O. 47
2
Figure 3.12 A DES-2: (a) coordination environment around
Cd(II); (b) and (c) [Cd (COO) ] SBU in 1D
2 2
metal-carboxylate chain and double lined 2D
network, respectively; (d) Offset stacked 2D
layers with the lattice H2O and π···π stacked L. 47
Figure 3.13 D irect synthesis mixed-ligands MOF film, RuB-
RuTB-UiO-67/TiO /FTO through solvothermal
2
method. 50
Figure 4.1 Some of the tritopic linkers. 58
Figure 4.2 The symmetry in organic linker. Tetratopic
linkers with (a) symmetry C2 and (b)
h
symmetry C. 59
s
Figure 4.3 Some of the tetratopic linkers. 60
Figure 4.4 A mixed-ligand MOF with tetratopic organic
linkers. 61
Figure 4.5 Some of the multi-topic linkers. 62
Figure 4.6 A kind of MOF with multi-hetero topic organic
linker. 64
Figure 4.7 ( a) Cu(II) Coordination environment. Symmetric
nodes: (i) y, 1 - x, 1 - z; (ii) y, x, 1 – z; (iii) 1 - y, x,
1 – z; (iv) 1 – x, y, z; (v) x, 1 – y, z; (vi) -x, 1 – y,
z; (vii) -x, y, z; (viii) y, x, -z; (ix) -y, x, -z; (x) y,
-x, -z. (b) Distorted truncated octahedron cage:
(trinuclear + tetranuclear) SBUs. (c) Illustration
of three dimensional porous framework in the
considered MOF. 65
Figure 5.1 Two synthesis strategies to create MMʹ-MOFs. 72