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Applications of
Elaboration and
Metal-Organic Frameworks
Series on Chemistry, Energy and the Environment
3/11/17 10:54 AM
ISSN: 2529-7716
Series Editors: Karl M. Kadish (University of Houston, USA)

Roger Guilard (University of Bourgogne, France)
The aim of this series on “Chemistry, Energy and the Environment” is to bring
together authoritative contributions where the multidisciplinary character of

Chemistry and its relationship to energy and the environment can be illustrated.
In each volume, the latest advances in bio-, energy- and environmentally-
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Published
Vol. 4 Prospects for Li-ion Batteries and Emerging Energy

Electrochemical Systems
edited by Laure Monconduit and Laurence Croguennec
Vol. 3 Advanced Green Chemistry

Part 1: Greener Organic Reactions and Processes
edited by István T. Horváth and Max Malacria
Vol. 2 Elaboration and Applications of Metal-Organic Frameworks

edited by Shengqian Ma and Jason A. Perman
Vol. 1 Perovskite Solar Cells: Principle, Materials and Devices

edited by Eric Wei-Guang Diau and Peter Chao-Yu Chen
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 Volume 2
Elaboration and
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Edited by
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Jason A. Perman
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University of Houston, USA
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b2980 Elaboration and Applications of Metal-Organic Frameworks
Preface
The materials known as metal-organic frameworks (MOFs) are experienc-

ing a shift from earlier design- and discovery-related research endeavors
into an accelerated revolution to apply these materials in technologies that
are useful in addressing the needs in energy, environment, and applied
research. These materials are coming from all around the world where the
novice and the expert are on equal standing and only their imaginations
can take these readily simple materials, to design and synthesize, and put
them into practical use. Many scientific researchers in the field can relate
their discoveries to childhood toys they have grown up with — myself
included. You could hold these toys in your hands as a child, which you
now manipulate in a reaction vessel. These toys with different shapes,
sizes, or colors of building blocks are befitting and correlate well with the
building blocks of MOFs that use metal–ligand coordination principles
from the field of inorganic chemistry to control the material’s physical and
chemical properties. Likewise, the countless possibilities in preparing
MOFs are expressed in this book to develop a deeper insight into the pos-
sible properties that can be manipulated to further advance this amazing
discipline. Many leaders and innovators in the MOF community have
contributed to this volume to cover important topics which begins with a
pressing issue concerning the stability of MOFs by Zhou’s group in
Chapter 1. This precedent c oncern in stability is considered by the authors
in the following chapters, where Humphrey’s group discusses phospho-
rus- and sulfur-containing building blocks in MOFs and their applications
in Chapter 2; and later in Chapter 3, Lee and Choe examine the postsyn-
thetic linker exchange reactions to modify existing MOFs. Next, porous
properties of MOFs are examined for their gas storage capabilities of
hydrogen in Chapter 4, and methane in Chapter 5, which are followed by
hydrocarbon separations in Chapter 6, from the groups of Ma, Eddaoudi,
and Zhao, respectively. The previous and following three c hapters have
b2980_FM.indd 5 05-Jan-18 9:55:32 AM

vi Preface
both energy and environmental applications where MOFs have partici-

pated as membranes in Chapter 7, are used for removing toxic anions in
Chapter 8, and heavy metals in Chapter 9, by the groups of Xue, Ghosh,
and Xu, respectively. The next block of four chapters by the groups of
Zhang, Chang, Zhao, and Zhang discusses the use of MOF as catalysts
whereby asymmetric catalysis in Chapter 10, MOFs as solid acid catalysts
in Chapter 11, biomass conversion in Chapter 12, and photocatalysis in

Chapter 13 show the development of these inspiring materials that harness
both their metal and organic constituents. These constituents also show
interesting phenomena allowing energy transfer within MOFs in Chapter
14 by Morris’s group, electronic conductivity in Chapter 15 by Saha’s
group, and finally the development of magnetic MOFs by Wriedt’s group.
This title hopes to inspire the next generation of MOF pioneers to forge
ahead and take a chance to make the next great breakthrough in MOF
research.
Shengqian Ma
Jason A. Perman
b2980_FM.indd 6 05-Jan-18 9:55:32 AM

Acknowledgments
The editors thank specifically the hard work done by Briana Aguila, Kia
Williams, Chavis Stackhouse, and Gaurav Verma for their hard work and
outstanding dedication in checking over all of the chapters, and they
acknowledge NSF (DMR-1352065) for their financial support because
without funding entities, research stands still.
vii
b2980_FM.indd 7 05-Jan-18 9:55:32 AM

b2530_FM.indd 6
This page intentionally left blank
b2530 International Strategic Relations and China’s National Security: World at the Crossroads
01-Sep-16 11:03:06 AM
Contents
Prefacev
Acknowledgmentsvii
1/D esign and Construction of Chemically Stable

Metal-Organic Frameworks 1
Hao Li, Mario Cosio, Kecheng Wang, William Burtner
and Hong-Cai Zhou
List of Abbreviations�� 2
I. Introduction�� 3
II. Metals and Ligands�� 5
A. High Valent Metal Nodes and O-Donor Linkers�� 5
B. Low Valent Metal Nodes and N-Donor Linkers�� 15
III. Other Structural Characteristics�� 20
A. High Connectivity of Metal Nodes and Ligands�� 20
B. Short Length of Ligands�� 21
C. Hydrophobic Groups�� 22
IV. Synthetic Methods�� 25
A. De Novo Synthesis�� 25
B. Kinetically Tuned Dimensional Augmentation�� 26
C. Metal and Ligand Exchange�� 28
D. Surface Modification�� 30
V. Acknowledgment�� 32
VI. References�� 32
ix
b2980_FM.indd 9 05-Jan-18 9:55:32 AM

x Contents
2 / A Survey of Metal-Organic Frameworks Based on

Phosphorus- and Sulfur-Containing Building Blocks 37
Joseph E. Reynolds III, Samuel G. Dunning,
Calla M. McCulley and Simon M. Humphrey
A. Designing MOFs with Programmable

Solid-State Reactivity�� 42
B. Ligand-Induced MOF Dimensionality�� 44
C. Chemical versus Thermal MOF Stability�� 48
II. MOFs with Phosphorus�� 50
A. Phosphorus(III)-Containing MOFs�� 50
1. Phosphine MOFs and Their Applications�� 51
B. Phosphorus(V)-Containing MOFs�� 60
1. Phosphonate MOFs�� 60
a. Gas Adsorption�� 61
2. Magnetism of Phosphonate MOFs�� 66
a. One-Dimensional Magnetic
Phosphonates��66
b. Two-Dimensional Magnetic
c. Three-Dimensional Magnetic
Phosphonates�� 69
3. Luminescence in Phosphonate MOFs�� 70
a. Luminescent Lanthanide Phosphonates�� 70
b. Luminescent Transition Metal
4. Catalysis of Phosphonate MOFs�� 71
a. Metal Phosphonates as Catalysts�� 72
b. Metal Phosphonates Incorporating
Catalytically Active Sites�� 73
5. Proton Conduction of Phosphonate MOFs�� 74
b2980_FM.indd 10 05-Jan-18 9:55:32 AM

Contents xi
a. Metal Phosphonates as Proton

Conductors�� 74
b. Metal Phosphonates Incorporating
Proton Conducting Sites�� 76
6. P(V) Derivatives of Phosphines:
Phosphine Oxide and Phosphonium MOFs

(O = PR3, R′-PR3)�� 77
b. Magnetism�� 82
c. Luminescence�� 84
7. Phosphinates�� 85
b. Magnetism�� 87
c. Luminescence�� 90
d. Catalysis�� 91
III. MOFs and Porous Coordination Polymers
with Sulfur-Based Ligands�� 91
A. Sulfur(VI)-Containing MOFs�� 91
1. Sulfonate MOFs�� 91
a. Structural Development/Stability
of Arylsulfonate Frameworks�� 92
b. Proton Conduction in Sulfonate
Frameworks�� 93
c. Gas Storage with Sulfonate
Frameworks�� 95
2. Luminescence Found in Sulfonate
Frameworks�� 97
a. Nonlanthanide-Based Framework
Luminescence�� 97
b. Luminescence of Lanthanide-Based
Sulfonate MOFs�� 98
3. Magnetism within Sulfonate Frameworks�� 98
b2980_FM.indd 11 05-Jan-18 9:55:32 AM

xii Contents
a. Magnetism within 2-D Sulfonate

Frameworks�� 99
b. Magnetism within 3-D Sulfonate
Frameworks�� 100
4. Sulfones�� 103
a. Structural Development of Sulfone

b. Proton Conduction in Sulfonyl
c. Gas Sorption of Sulfonyl Frameworks�� 107
d. Luminescent Properties of Sulfonyl
e. Magnetism in Sulfonyl Frameworks�� 109
B. Sulfur(II)-Containing MOFs�� 112
1. Thiophenes�� 112
a. Structural Studies of Thiophene
b. Luminescence of Thiophene Frameworks�� 116
c. Magnetism in Thiophene Frameworks�� 117
2. Thioethers�� 118
a. Structural Examples of Thioether
Frameworks��119
b. Luminescent Thioether Frameworks�� 120
c. Magnetic Thioether Frameworks�� 123
3. Thiolates�� 124
a. Bonding Properties of Thiolate-Based
b. Thiolate Coordination Polymers with
Magnetic Properties�� 126
4. Dithiolates�� 128
a. Dithiocarbamate�� 128
b. Dithiocarboxylate�� 130
IV. Outlook and Conclusions�� 130
V. References�� 131
b2980_FM.indd 12 05-Jan-18 9:55:32 AM

Contents xiii
3/P ostsynthetic Linker Exchange in Metal-Organic

Frameworks143
Soochan Lee and Wonyoung Choe
II. Postsynthetic Linker Exchange in Pillared MOFs�� 147
A. Control of Pore Size�� 148

B. Interpenetration Control�� 151
C. Isolation of Functional Sites�� 151
III. Postsynthetic Linker Exchange in Zeolitic
Imidazolate Frameworks�� 154
A. Isostructural Transformation in ZIFs�� 154
B. Topological Transformation via Linker Exchange
in ZIFs�� 157
C. Crystal Size Control in ZIFs�� 158
IV. Postsynthetic Linker Exchange in UiO-Series�� 158
A. Enhancement of CO2 Separation�� 160
B. Chemical Route for Introducing Catalytic Sites�� 160
C. MOF-Based Sensors�� 161
V. Postsynthetic Linker Exchange in Other MOFs�� 164
A. Enhancement of Proton Conduction�� 165
B. Introduction of Functionality�� 165
VI. Sequential Self-Assembly of MOFs via Postsynthetic
Linker Exchange�� 166
VII. Linker Exchange on MOF Surface�� 173
VIII. Mechanism and Thermodynamics in Linker Exchange��173
IX. Beyond Postsynthetic Linker Exchange: Site-Specific
Metal and Linker Replacement Within Ordered
Vacancies�� 176
X. Conclusion and Future Outlook�� 177
XI. References�� 178
4 / Hydrogen Storage in Metal-Organic Frameworks 183

Gaurav Verma, Jason A. Perman and Shengqian Ma
A. Hydrogen: Production and Storage Goals�� 185
b2980_FM.indd 13 05-Jan-18 9:55:32 AM

xiv Contents
B. MOFs as Hydrogen Storage Materials�� 187

II. Factors Influencing Hydrogen Storage�� 189
A. Open Metal Sites�� 189
B. Interpenetration�� 193
C. Guest Metal Ions�� 194
D. Decoration with Metal Nanoparticles�� 197
E. Ligands and Ligand Functionalization�� 199

III. Evaluation of High-Pressure Storage
at Room Temperature�� 200
IV. Conclusions and Future Outlook�� 201
V. Acknowledgments�� 201
5/M ethane Storage in Metal-Organic Frameworks: Insights

into the Storage Performance and the Intrinsic Property
Relationships for Enhanced Adsorbed Natural Gas
Storage207
Dalal Alezi, Youssef Belmabkhout and Mohamed Eddaoudi
II. Onboard Natural Gas Storage Technologies�� 211
A. Compressed Natural Gas�� 211
B. Liquefied Natural Gas�� 211
C. Adsorbed Natural Gas�� 212
III. Porous Materials for Methane Storage and Delivery�� 213
IV. High-Pressure Methane Storage Principles
and Terminology�� 214
A. Excess, Absolute and Total Adsorption�� 214
B. Gravimetric and Volumetric Capacity�� 215
C. Deliverable/Working Capacity�� 216
V. MOFs for Methane Storage�� 217
VI. Metrics Influencing Methane Storage Capacity
in MOFs�� 219
A. Surface Area and Pore Volume�� 219
B. Pore Shape and Size�� 223
b2980_FM.indd 14 05-Jan-18 9:55:32 AM

Contents xv
C. Open Metal Sites�� 225

D. Ligand Design and Functionality�� 225
VII. Evaluating MOFs for Methane Storage and Delivery�� 226
A. At Ambient Temperature (298 K) and Relatively
Low Pressure (35 and 65 bar), (ARPA-E
Operation Conditions)�� 226
1. Copper Based Tricarboxylic Ligand,

HKUST-1 (tbo MOF-1)�� 228
2. Copper Based Tetracarboxylic Ligands,
nbo MOFs�� 230
3. Other MOFs�� 232
B. At Ambient Temperature (298 K) and Relatively
High Pressure (80 bar)�� 232
1. Aluminum-Based Tetracarboxylic Ligands,
soc-MOF Platform�� 233
2. Expanded HKUST-1-like tbo-MOF Platform�� 237
3. Zinc-MOF Based on Acrylate Links�� 238
C. At Low Temperature (270, 258 K) and Different
Pressure of 65 and 80 bar�� 240
VIII. Summary and Outlook�� 241
IX. Acknowledgments�� 242
X. References�� 242
6 / S eparation of Light Hydrocarbons by Metal-Organic

Frameworks247
Jia Liu, Ruqiang Zou and Yanli Zhao
II. Paraffin Separation of C1/C2/C3�� 249
III. Paraffin/Olefin Separations�� 261
IV. Acetylene/Ethylene Separations�� 271
V. Paraffin of C4+ Separation�� 276
VI. Summary�� 277
VII. Acknowledgment�� 278
VIII. References�� 278
b2980_FM.indd 15 05-Jan-18 9:55:32 AM

xvi Contents
7/M etal-Organic Framework Membrane Synthesis

and Applications 281
Ming Xue and Shilun Qiu
II. MOF Membrane Fabrication Methods�� 285
A. In Situ Growth Method�� 286

B. Secondary Growth Method�� 291
C. Other Methods�� 297
III. MOF Membrane for Separations��300
A. Gas Separation�� 302
1. Hydrogen Separation�� 303
2. Carbon Dioxide Separation�� 311
3. C2 and C3 Hydrocarbon Separation�� 312
B. Liquid Separation�� 316
IV. Conclusions and Outlook�� 319
8/M etal-Organic Frameworks: An Advanced Class

of Anion-Exchange Materials 325
Shivani Sharma, Avishek Karmakar and Sujit K. Ghosh
II. MOFs for Anion-Exchange�� 330
A. Introduction to MOFs�� 330
B. Design Principles and Fabrication of
Cationic MOFs�� 330
C. Advantages of Cationic MOFs�� 332
D. Anion-Exchange in Cationic MOFs: State
of the Art�� 333
III. Anion-Exchange in MOFs: Potential Applications�� 340
A. Capture of Toxic Inorganic Anions�� 340
B. Capture of Organic Anionic Pollutants�� 349
C. Anion Sensing in MOFs�� 350
1. Luminescent-Based Sensors�� 352
2. Colorimetric Sensors�� 358
D. Anion-Dependent Sorption Behavior�� 362
b2980_FM.indd 16 05-Jan-18 9:55:33 AM

Contents xvii
E. Cationic MOFs for Drug Delivery�� 366

F. Anion-Exchange-Based Tunable Magnetism�� 366
IV. Summary and Future Outlook�� 368
V. Acknowledgments�� 370
9 / Metal-Organic Frameworks for Heavy Metal Removal 377

Yan-Lung Wong, Yunlong Hou and Zhengtao Xu

II. Metal-Organic Frameworks: A Promising Class
of Solid Materials for Heavy Metal Removal�� 380
A. Hard-and-Soft Strategy as Exemplified by the
Carboxyl-Thioether and Thiol Combination�� 383
III. Postsynthetically Installed Binding Sites for Heavy
Metal Removal�� 395
IV. Charged MOF Hosts for Ion Exchange with Heavy
Metal Solutes�� 399
V. Conclusion and Outlook�� 405
10 / S ynthesis and Applications of Homochiral

Metal-OrganicFrameworks411
Zhi-Gang Gu and Jian Zhang
II. Synthetic Strategies for Homochiral MOFs�� 413
III. Special Structures of Homochiral MOFs�� 421
IV. Applications of Homochiral MOFs�� 430
V. Conclusions and Outlook�� 436
11 / M
etal-Organic Frameworks as Solid Acid Catalysts
for Heterogeneous Catalysis 441
Sanil E. Sivan, Young Kyu Hwang and Jong-San Chang
b2980_FM.indd 17 05-Jan-18 9:55:33 AM

xviii Contents
II. Lewis Acidic MOFs and Catalysis�� 444

A. MOFs with CUM Sites Generated by the
Removal of Coordinated Solvent Molecules�� 445
1. Microporous MOFs�� 445
2. Mesoporous MOFs�� 453
3. Chiral MOFs�� 456
B. MOFs with CUM Sites of Defective Origin�� 459

III. Brønsted Acidic MOFs and Catalysis�� 464
A. MOFs with Brønsted Acid-Functionalized
Organic Linkers�� 468
B. MOFs as a Host Matrix for the Incorporation
of Brønsted Acidic Molecules�� 476
C. MOFs with Engineered Brønsted Acidic
Defect Sites�� 484
IV. Summary�� 485
12 / M
etal-Organic Frameworks-Based Heterogeneous
Catalysts for Biomass Conversion 495
Zhigang Hu and Dan Zhao
II. Metal-Organic Frameworks-Based Catalysts
for Biomass Conversion�� 500
A. MOF Catalysts with Lewis Acidity�� 500
B. MOF Catalysts with Brønsted Acidity�� 500
1. Postsynthetic Modification�� 501
2. Incorporation of External Brønsted Acids�� 503
3. Direct Synthesis of MOFs with Intrinsic
Brønsted Acidity�� 503
C. MOFs Loaded with MNPs�� 505
1. Hydrogenation�� 506
2. Hydrodeoxygenation�� 508
3. Oxidation�� 510
4. Esterification�� 511
III. Summary and Outlook�� 512
b2980_FM.indd 18 05-Jan-18 9:55:33 AM

Contents xix
A. MOF Catalysts with Hybrid Lewis/Brønsted

Acidity�� 513
B. Other Catalytic Reactions�� 514
IV. Acknowledgments�� 515
13 / Metal-Organic Frameworks for Photocatalysis 519

Xin Zhang and Jian Zhang

II. Photoactivity in MOFs�� 523
A. Ligand Design�� 523
B. Ligand-to-Metal Charge Transfer�� 524
C. Homogeneous Photosensitizer�� 525
D. Semiconductor�� 525
III. MOFs as Photocatalysts for Artificial Photosynthesis�� 526
A. Hydrogen Evolution Reaction�� 526
1. Metal-Oxo Clusters as the Cocatalyst�� 526
2. Pt NPs as the Cocatalyst�� 527
3. Molecular Pt Complex-Based Cocatalyst�� 535
4. Diiron Complex-Based Cocatalyst�� 537
5. Cobalt Molecular Complex-Based
Cocatalyst�� 540
6. Polyoxometalates-Based Cocatalyst�� 542
7. Other Types of Cocatalysts�� 545
B. CO2 Reduction�� 545
1. Metal-Oxo Clusters as the Cocatalyst�� 545
2. Noble Metal as the Cocatalyst�� 552
3. 3d Transition Metal Complexes
as the Cocatalyst�� 556
C. Water Oxidation Reaction�� 558
IV. Photocatalytic Organic Transformation�� 560
A. Net Oxidative Reactions�� 560
1. Alcohol Oxidation�� 560
2. Oxidative Generation of Iminium Ions�� 562
b2980_FM.indd 19 05-Jan-18 9:55:33 AM

xx Contents
3. Other Types of Oxidation Reactions�� 564

B. Net Reductive Reactions�� 565
C. Redox Neutral Reactions�� 567
D. Photocatalysis via Energy Transfer�� 568
V. Conclusions and Further Perspectives�� 573

14 / Energy Transfer in Metal-Organic Frameworks 581

Jie Zhu, Shaunak Shaikh, Nicholas J. Mayhall
and Amanda J. Morris
A. Background Information About Energy Transfer�� 583
1. Coupling Regimes�� 584
a. Strong Coupling�� 584
b. Weak Coupling�� 585
B. Coupling Mechanisms�� 586
1. Distance Dependence of Coupling
Mechanisms�� 587
2. Dexter-Type Integral, (ab|ji)) �� 587
3. Förster-Type Integral, (ai|jb)�� 588
C. Why MOFs�� 592
II. Lanthanide-Based Luminescent MOFs�� 593
A. ET in Ln-Node-Based MOFs�� 599
B. Ln@MOF�� 613
C. Summary�� 615
III. Ru/Os-Based MOFs�� 616
A. Ru/Os in Zn-Node-Based MOFs�� 616
B. Ru(bpy)32+-Doped Zirconium(IV) MOFs�� 624
C. Summary�� 628
IV. Porphyrin- and Metalloporphyrin-Based
MOF Materials�� 629
A. Porphyrin-Based MOFs as Crystalline Powders�� 629
B. Porphyrin-Based MOFs as Thin Films�� 639
A. Summary�� 642
b2980_FM.indd 20 05-Jan-18 9:55:33 AM

Contents xxi
V. Nonporphyrinic, Organic Chromophore-Based

MOFs�� 642
A. Summary�� 650
VI. Conclusions�� 651
VII. Acknowledgment�� 651
VIII. References�� 652
15 / Electrically Conductive Metal-Organic Frameworks 655

Nagapradeep Nidamanuri, Krishnendu Maity and Sourav Saha
II. MOFs with Intrinsic Conductivity�� 660
A. Through-Bond Charge Movement in
Intrinsically Conducting MOFs�� 660
B. Conducting MOFs Based on Metal Ions
Providing Mobile Charge Carriers�� 660
C. In-Plane Charge Transport in 2D Graphitic MOFs��666
D. Through-Space Charge Transport in Intrinsically
Conducting MOFs�� 672
III. Guest-Induced Conductivity in MOFs�� 674
A. Iodine-Induced MOF Conductivity�� 676
B. Li+ Ion-Induced MOF Conductivity�� 678
C. Through-Bond Charge Transport Through
Coordinated Cross-Linking Guests�� 679
D. Through-Space Charge Transport Activated
by π-Intercalated Guests�� 679
IV. Summary and Outlook�� 682
16 / M
etal-Organic Frameworks as Platforms for the
Nanostructuring of Molecular Magnets 687
Darpandeep Aulakh and Mario Wriedt
II. Single-Molecule Magnets@MOF Composites�� 690
b2980_FM.indd 21 05-Jan-18 9:55:33 AM

xxii Contents
III. Polyoxometalates@MOF Composites�� 692

IV. Paramagnetic Endohedral Fullerenes@MOF
Composites�� 695
V. Single-Ion Magnets@MOF Composites�� 697
VI. Future Perspectives�� 698
VII. Conclusions�� 699
VIII. Acknowledgments�� 700

IX. References�� 700
Index703
b2980_FM.indd 22 05-Jan-18 9:55:33 AM

1 Design and Construction

of Chemically Stable
by 65.130.49.243 on 02/05/18. For personal use only.
Hao Li, Mario Cosio, Kecheng Wang,

William Burtner and Hong-Cai Zhou*
Department of Chemistry, Texas A&M University,

College Station, Texas 77842-3012, United States
*zhou@chem.tamu.edu
Table of Contents
List of Abbreviations 2
I. Introduction 3
II. Metals and Ligands 5
A. High Valent Metal Nodes and O-Donor Linkers 5
B. Low Valent Metal Nodes and N-Donor Linkers 15
III. Other Structural Characteristics 20
A. High Connectivity of Metal Nodes and Ligands 20
B. Short Length of Ligands 21
C. Hydrophobic Groups 22
IV. Synthetic Methods 25
A. De Novo Synthesis 25
B. Kinetically Tuned Dimensional Augmentation 26
1
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2 Li et al.
C. Metal and Ligand Exchange 28

D. Surface Modification 30
V. Acknowledgment 32
VI. References 32
List of Abbreviations
1,3-H2BDP 1,3-benzenedi(4-pyrazolyl)
1,4-H2BDP 1,4-benzenedi(4-pyrazolyl)
1D one-dimensional
3D three-dimensional
ABTC 3,3′,5,5′-azobenzene tetracarboxylate
-AMn amide with an n carbon chain

BDC 1,4-benzenedicarboxylate
bIm benzimidazole
Boc tert-butoxycarbonyl
BTC 1,3,5-benzenetricarboxylate
BUT Beijing University of Technology
cbIm 5-chlorobenzimidazole
DEF N,N-diethylformamide
DMF N,N-dimethylformamide
en ethylenediamine
FMOF fluorinated metal-organic framework
H3BTP 1,3,5-tris(1H-pyrazol-4-yl)benzene
H3BTTri 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene
H4TBAPy 1,3,6,8-tetrakis( p-benzoic acid)pyrene
H4TPP 5,10,15,20-tetra(1H-pyrazol-4-yl)-porphyrin
HKUST Hong Kong University of Science and Technology
HMeIm 2-methylimidazole
HSAB hard and soft acid and base
IRMOF isoreticular metal-organic framework
KAUST King Abdullah University of Science and Technology
KDTA kinetically tuned dimensional augmentation
MIL Materials Institute Lavoisier
MOF metal-organic framework
nIm 2-nitroimidazole
NU Northwestern University
b2980_Ch-01.indd 2 05-Jan-18 6:40:07 AM

Design and Construction of Chemically Stable MOFs 3
PBS phosphate buffer saline

PCN porous coordination network
PDMS polydimethysiloxane
PECVD plasma-enhanced chemical vapor deposition
PSMO postsynthetic metathesis and oxidation
PXRD powder X-ray diffraction
RH relative humidity
SBU secondary building unit
SEM scanning electron microscopy
TATB 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate
TCPP tetrakis(4-carboxyphenyl)porphyrin
TzGal 5,5′-(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triolate)
UiO Universitetet i Oslo

ZIF zeolitic imidazolate framework
I. Introduction
Metal-organic frameworks (MOFs) are an emerging class of highly
porous materials, which are constructed from inorganic nodes and organic
linkers. By designing inorganic and organic components, various infinite
three-dimensional (3D) networks can be achieved with high porosity, high
surface area, and low density.1 Because of the diversity and tunability of
their structures, MOFs have been extensively explored, especially their
potential applications in gas storage and separation,2 catalysis,3 chemical
sensing,4 biomedicine,5 and so on. To have good performances and recy-
clability in these applications, the most important property of MOFs is
their robustness, because of which they can survive at various conditions
involved in real applications, such as water exposure, immersion in chem-
icals, or in an in vivo environment. Generally, the stability of MOFs can
be categorized into three aspects: chemical stability, thermal stability, and
mechanical stability.6 They refer to the ability of MOFs to maintain their
structural intactness when they are exposed to chemicals, high tempera-
ture, and mechanical force, respectively.6 This chapter mainly focuses on
the chemical stability of MOFs. In addition, there is also a type of stability
called hydrothermal stability, which refers to the scenario when a MOF is
exposed to water or water vapor at a temperature higher than room tem-
perature. Hydrothermal stability is classified into chemical stability in this
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4 Li et al.
book chapter. For readers who are interested in the discussion of thermal
stability and mechanical stability, a comprehensive review by Howarth
et al. is recommended here.6
Due to its abundance on the earth, water is the most readily applied
solvent in industrial and biological activities. Great concerns of the chem-
ical stability of MOFs have been mainly focused on their stability in aque-
ous solution or water vapor. MOFs are constructed by coordination bonds

between inorganic nodes and organic linkers. Fundamentally, MOF struc-
tures can be divided into two parts: building units (metal nodes and organic
linkers) and linkages (coordination bonds). The linkages are the weak parts
that are most likely to be attacked by water, generating protonated organic
linkers and metal hydroxide. Therefore, bond strength between metal
nodes and organic linkers is one of the main criteria that determines the
stability of MOFs.7 In acidic or basic solutions, the decomposition of
MOFs will become even faster owing to the existence of highly concen-
trated protons or hydroxide ions in the solution. Because of this, research
attention has been focused on synthesizing acid- or base-stable MOFs.
Though numerous papers have already been published on robust
MOFs, there are no concurred standards to assess their chemical stability.
This is mainly because plenty of variables are involved in the process,
such as the type of chemicals (H+, OH−, H2S, or PO43−), the concentration
of the chemical, the temperature of the solution, the time that MOFs are
immersed in the solution, and so on. Often a different set of parameters
are chosen for the stability test of each MOF, making it quite challenging
to compare the robustness of two MOFs.
Two techniques have been widely used to corroborate the stability of
MOFs: powder X-ray diffraction (PXRD) and porosity analysis with
inert gas. Usually, the PXRD pattern and inert gas uptake are measured
before and after a batch of MOF samples are immersed in a solution for
a period of time. If there is an obvious decrease in the gas uptake and the
intensity of PXRD peaks of the MOF sample, it indicates that the crys-
talline MOF is totally or partly degraded and is not quite stable under the
applied condition.
In this chapter, some representative stable MOFs with impressive robust-
ness in aqueous solutions will be exhibited. Their structural features and the
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chemistry accounting for their stability will also be revealed. Finally, some
typical methods to construct chemically robust MOFs will be discussed.
II. Metals and Ligands

A. High Valent Metal Nodes and O-Donor Linkers
According to the hard and soft acid and base (HSAB) theory, hard Lewis
acids, like high valent metal ions, interact strongly with hard Lewis bases,
such as oxygen-anion-terminated linkers, to form strong bonds. Therefore,
if MOFs are constructed by trivalent or tetravalent metal ions and carbox-
ylate-based ligands, strong coordination bonds between inorganic nodes
and organic linkers will endow the resulting materials with high stability to
survive in harsh conditions. Early successful examples of such robust

MOFs are the Materials Institute Lavoisier (MIL)-101 and MIL-100 series.
In the MIL-101 series, there are two typical examples, MIL-101(Cr)
and MIL-101(Fe), which are constructed by 1,4-benzenedicarboxylate
(BDC) and CrIII/FeIII clusters.8 The structure of MIL-101 is unique and
very intriguing. Six linear BDC linkers and four trimeric metal clusters
construct a supertetrahedral cage, functioning as edges and vertices,
respectively. These supertetrahedra are further connected by their corner-
sharing vertices of metal clusters to establish a 3D network of mtn topol-
ogy, which delimits two types of mesoporous cages with internal free
diameters of 29 Å and 34 Å, respectively (Figure 1). Though, to the best
of our knowledge, there is no experimental evidence about the stability of
MIL-101(Fe) in the literature, MIL-101(Cr) is tested to be highly robust,
as supported by HSAB theory.9 MIL-101(Cr) can be kept in air over
months. Its crystalline structure is also maintained after being immersed
in various organic solvents at raised temperature. Most importantly, the
Cr-MOF can even remain intact after being soaked in boiling water for 7
days, as indicated by its PXRD pattern and N2 uptake at 77 K.9 Apart from
the strong coordination bond generated between the trivalent chromium
ion and oxygen-terminated ligand, the ultrastability of MIL-101(Cr) is
also largely driven by the kinetic inertness of CrIII, which will be dis-
cussed thoroughly later in the case of porous coordination network
(PCN)-333. Because of its stability under harsh conditions, MIL-101(Cr)
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6 Li et al.
Figure 1. (a) Pentagonal and hexagonal windows, and (b) mesoporous cages with
radii of 14.5 and 17 Å, respectively, in MIL-101(Cr). Taken from Ref. 10e with per-
mission of the American Chemical Society.
and its derivatives, such as MIL-101(Cr)-NH2, MIL-101(Cr)-NO2, MIL-

101(Cr)-SO3H, have become some of the most favored MOF candidates
for various applications, including but not limited to, gas sorption, water
sorption, catalysis, and heat transformation.10
Similar to MIL-101, MIL-100 is also constructed by vertex-sharing
supertetrahedra to form a framework with two types of mesopores, which
are accessible through microporous windows of 5.5 Å and 8.6 Å.11 The
difference lies in the components of the supertetrahedra. In MIL-100, each
supertetrahedron is comprised of four 1,3,5-benzenetricarboxylate (BTC),
instead of six BDC, and four trimeric metal clusters (Figure 2); BTC
serves as the face of the supertetrahedron. Like MIL-101, MIL-100 series
is quite chemically robust, among which three MOFs have become the
focus of research, namely MIL-100(Cr),11a MIL-100(Fe),11b and MIL-
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100(Al).11c Their stabilities are mostly evaluated through the cycling

experiment of water adsorption–desorption.12 For MIL-100(Cr), its three
cycling isotherms overlap with each other, indicating its stability in water
vapor with relative humidity (RH) as high as 95% at 25 °C.12b In the cases
of MIL-100(Fe) and MIL-100(Al), both samples are exposed to humidi-
fied argon with a partial water vapor pressure of 5.6 kPa (RH 76% at 40
°C). The samples are put through temperature swings between 40 °C and
140 °C for 40 cycles with 5 h per cycle. Judging from the small decreases
of water capacities and porosities and no discernible changes in the PXRD
patterns, both MIL-100(Fe) and MIL-100(Al) are relatively water-
Figure 2. (a) Secondary building unit (SBU), (b) supertetrahedron, (c) small mesopore,
and (d) large mesopore in MIL-100(Fe). Hydrogen atoms are omitted for clarity.
Different objects are not drawn to scale. Taken from Ref. 12a with permission of the
Royal Society of Chemistry.
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8 Li et al.
stable.12a There is also a compelling experiment to corroborate the stabil-

ity of ML-100(Cr), in which the MOF is placed in pure water for 12
months and still retains its crystalline structure.13 All these examples ver-
ify the good chemical stability of the MIL-100 series and substantiate the
guiding role of HSAB theory in the design and synthesis of robust MOFs.
PCN-333 is an elongated version of MIL-100, in which each face of
the supertetrahedron is a 4,4′,4″-s-triazine-2,4,6-triyl-tribenzoate ligand

(TATB) instead of BTC in MIL-100 (Figure 3).14 PCN-333(Fe) and PCN-
333(Al) remain intact after immersion in aqueous solutions with pH of 3
and 9 for 12 h,14a and the functionalized PCN-333(Cr) is even able to sur-
vive in 10 mM NaOH or 1M HCl for 24 h.14b Though Fe, Al and Cr all
present in their trivalent state in PCN-333, PCN-333(Cr) exhibits evidently
stronger resistance to harsh conditions, which can be attributed to the

kinetic inertness of CrIII. As is well known, the degradation of MOFs can
Figure 3. (a) Comparison of the ligands in MIL-100 (BTC) and PCN-333 (TATB),
(b) large mesopore, and (c) supertetrahedron in PCN-333. Hydrogen atoms are omit-
ted for clarity. Taken from Ref. 14b with permission of the American Chemical Society.
b2980_Ch-01.indd 8 05-Jan-18 6:40:09 AM

be modeled as stepwise substitutions of bridging ligands with attacking

species, such as H2O.15 They often undergo a dissociative mechanism due
to the saturated coordination environment around the metal ions. If the dis-
sociative pathway is represented in a reaction coordinate diagram, the ini-
tial release of a ligand would be the rate-determining step and have a much
larger activation energy than the other steps in the reaction. Based on
experimental data (Figure 4), the ligand exchange rate constant of CrIII is
much smaller than those of other trivalent metal ions, which indicates a far
larger activation energy for ligand dissociation on CrIII, making structural
damages more difficult to occur in CrIII-MOFs than other trivalent MOFs.
Apart from the aforementioned mtn-topology MOFs, robust frame-
works, still based on trivalent metal ions and carboxylate ligands, but
adopting other topological patterns, have also been created with HSAB
theory, such as the PCN-250 series.17 It consists of 6-connected [Fe2M(µ3-O)]
(M = FeIII, MnII, CoII, NiII, ZnII) building units and rectangular tetratopic
Figure 4. Characteristic rate constants for the substitution of coordinated water

molecules on various metal ions. Taken from Ref. 16 with permission of Elsevier.
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10 Li et al.
Figure 5. (a) M3O metal cluster, (b) 3,3′,5,5′-azobenzene tetracarboxylate (ABTC)

ligand, (c) PCN-250 structure expressed in building blocks. Taken from Ref. 17 with
permission of Nature Publishing Group.
carboxylate ligands (Figure 5). Even with the introduction of relatively

softer Lewis acid MII in the metal cluster, the PCN-250 series still exhibits
good chemical stability. For instance, PCN-250(Fe2Co) remains intact
under water for 6 months. It can also sustain aqueous solution with pH
ranging from 1 to 11 for 24 h. Because of its chemical stability and appro-
priate pore sizes, PCN-250 is utilized as an extraordinary methane storage
material.
Compared with trivalent metal ions, tetravalent species (such as TiIV,
Zr , and HfIV) can form stronger bonds with oxyanion ligands and lead to
IV
another group of stable MOFs. Universitetet i Oslo (UiO)-66 is the first ZrIV-
based stable MOF,18 which is ideally comprised of 12-connected Zr6 clusters
and BDC ligands (Figure 6). Because the strength of Zr-oxyanion bond is
very high and the length of BDC ligand is short, the rate of ligand dissocia-
tion (reverse reaction of crystal growth) is very low.15 This leads to a limited
rate of structural reparation in the crystal growth of UiO-66 and makes UiO-
66 often come with a high ratio of deficiency. However, structural defects
have little impact on the chemical stability of UiO-66. It is reported that
UiO-66 is stable in water or moderately acidic solutions (pH = 1).19
After the incipient exploration of synthesizing robust MOFs with
tetravalent metal ions, various stable ZrIV-MOFs have been made subse-
quently.20 Among them, one outstanding example is PCN-222(Fe). (The
metal in the parentheses indicates the element in the porphyrin center
rather than the metal in the constructing inorganic nodes of the MOF.)
PCN-222(Fe) is synthesized through the solvothermal reaction of ZrCl4
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Figure 6. Structure of UiO-66. Taken from Ref. 19b with permission of the American
Chemical Society.
and Fe-TCPP (TCPP, tetrakis(4-carboxyphenyl)porphyrin). One porphyrin

ligand is linked to four 8-connected Zr6 clusters, generating a 3D network
containing very large one-dimensional (1D) channels with a diameter of
37 Å (Figure 7). The PXRD pattern and N2 uptake of PCN-222(Fe) have
no apparent changes after being soaked in boiling water or even in concen-
trated HCl for 24 h. Its ultrastability mainly comes from the high charge
density on ZrIV, making the ZrIV–O bond exceedingly strong. The ultrast-
ability of the framework as well as the high density of porphyrin active
centers make PCN-222(Fe) an excellent platform to perform biomimetic
catalysis. Follow-up works include a series of robust Zr-MOFs in different
topologies (PCN-22X, X = 3, 4, 5, 8, 9, and PCN-230), which are also
prepared from ZrIV and porphyrin linkers but under altered conditions.
These MOFs show good chemical stability in acidic or basic solutions as
well and constitute a useful library of robust Zr-porphyrin MOFs.20
An isoreticular MOF of PCN-222, namely Northwestern University
(NU)-1000, is also proposed to be hydrolytically stable.21 The primary
structural difference between NU-1000 and PCN-222 is that the tetratopic
ligand in NU-1000 is not TCPP but 1,3,6,8-tetrakis( p-benzoic acid)pyrene
(H4TBAPy) (Figure 8). Though there is no detailed experimental data,
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12 Li et al.
Figure 7. (a) 4-connected Fe-TCPP (blue square), (b) 8-connected Zr6 cluster
(orange cuboid), (c) 1D channel with radius of 3.7 nm (green pillar), (d, e) crystal
structure and underlying network topology of PCN-222(Fe). Atom color legend: Zr
(black), C (gray), O (red), N (blue), and Fe (orange). H atoms are omitted for clarity.
Taken from Ref. 20a with permission of John Wiley and Sons.
NU-1000 is still presumed to be chemically stable and has been studied for
metalation and catalysis.21
It is worth mentioning that not all chemically stable MOFs are discov-
ered by deliberately soaking the material in certain solutions. Sometimes,
they are found along the process of postsynthetic modification of pristine
MOFs. MOF-808 is a typical example to illustrate this point.22 MOF-808
is a Zr-MOF prepared from ZrOCl2·8H2O and H3BTC, in the form of a
6,3-connected 3D network with a spn topology (Figure 9). In 2014, a
sulfated MOF-808 was achieved from the pristine MOF-808 for catalytic
purposes, by submerging the material in aqueous sulfuric acid (0.005–0.1
M) for 1 day. The crystal appearance, PXRD pattern, and porosity of the
sulfated MOF-808 are all remarkably almost identical to those of the pris-
tine MOF, suggesting the strikingly acid tolerance of MOF-808.
All the above examples are related to the stability of MOFs in aqueous
solutions containing H+ or OH−, which may serve as good evaluations of
their structural robustness and performances in acid- or base-involved
b2980_Ch-01.indd 12 05-Jan-18 6:40:11 AM


Figure 8. H4TBAPy ligand and structural representation of NU-1000. H atoms are

omitted for simplicity. Taken from Ref. 21 with permission of the American
Chemical Society.
Figure 9. Zr6O4(OH)4(-CO2)6(HCOO)6 SBUs and BTC ligands are combined to

form MOF-808, which contains large adamantane-shaped cages (open space) and
small tetrahedral cages (green spheres). Atom labeling legend: formate C atom
(black), formate O atom (red), other C atom (gray), other O atom (pink), Zr coordina-
tion polyhedral (blue). H atoms are omitted for clarity. Taken from Ref. 22b with
permission of the American Chemical Society.
b2980_Ch-01.indd 13 05-Jan-18 6:40:12 AM

14 Li et al.
Figure 10. Chemical structure of 5,5′-(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-

triol) or H6-TzGal.
catalytic reactions. Some interest has been further directed to the bioap-
plications of MOFs, rendering more study on their stability in bioenviron-
ment, for instance, in phosphate buffer saline (PBS). In 2015, Mouchaham
et al. published a paper of a Zr-MOF, MIL-163, using a phenolate ligand
5,5′-(1,2,4,5-tetrazine-3,6-diyl)bis(benzene-1,2,3-triolate) (TzGal) as the
linker (Figure 10).7a Each TzGal molecule chelates four ZrIV ions, which
affords edge-sharing ZrO8 polyhedra that delineates chains aligned along
the [001] direction.7a Each ZrIV ion is chelated by two pairs of TzGal link-
ers that extend along the [100] and [010] directions, respectively.
Therefore, the Zr-O chains are connected by two groups of orthogonally-
oriented ligands, generating a 3D network with large square-shaped chan-
nels. MIL-163 exhibits extraordinary chemical stability not only in boiling
water but also in a PBS solution (pH = 7.4) at 37 °C. No apparent differ-
ences can be discerned between the PXRD patterns of the sample before
and after immersion in the media for 2 weeks. Usually Zr-MOF are robust
enough to resist boiling water due to the strength of Zr-carboxylate bond,
but rarely can they survive phosphates, which are known to have higher
affinity with ZrIV than carboxylates. To rationalize this peculiar phenom-
enon, two attempted explanations are proposed. Firstly, the strength of
ZrIV-ligand interaction might follow the exact order of 1,2,3-trioxoben-
zene > phosphate > carboxylate > H2O, as suggested by the experimental
results. Secondly, unlike many other Zr-MOFs, there are no μ3-oxo and
-hydroxo bridges in MIL-163, which could act as the weak points to be
attacked by phosphates. Lack of these bridging moieties in the structure
could also serve as a beneficial factor for the ultrastability of MIL-163 in
PBS. Though there are not sufficient experimental or calculated results to
substantiate these explanations, they are still inspiring to design more
chemically stable MOFs in the future.
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B. Low Valent Metal Nodes and N-Donor Linkers
Similar to the cases of hard Lewis acids and bases, soft Lewis acids and
bases, on the other end of HSAB spectrum, also have strong interactions
in between and can be utilized as metal ions and ligands for construction
of robust MOFs. Typical soft bases are anion N-donor ligands, such as
imidazolate, pyrazolate, triazolate, and are paired with soft acids like CuII,
ZnII, NiII to form strong coordination bonds.

A representative example of stable MOF with N-donor ligand is
zeolitic imidazolate framework (ZIF)-8 published by Park et al. in 2006.23
ZIF-8 is synthesized from zinc nitrate tetrahydrate Zn(NO3)2·4H2O and
2-methylimidazole (HMeIm). Imidazole ligand loses one proton to form
imidazolate and coordinates to metal ions by N atoms. The structure of
ZIF-8 is based on nets of connected ZnN4 tetrahedra linked by imida-

zolate ligands. The bridged imidazolate generates Zn-In-Zn angle close to
145°, which is coincident with the Si-O-Si angle in zeolite. ZIF-8, with
sod topology, possesses large pore with a diameter of 11.6 Å, which are
connected by small apertures. The chemical stability of ZIF-8 is tested by
suspending the sample in boiling benzene, methanol, water, and sodium
hydroxide aqueous solution. Based on the PXRD patterns collected at
designated intervals, ZIF-8 is immune to boiling organic solvent for 7
days. It can also retain the crystallinity in 8 M NaOH aqueous solution at
100 °C for 24 h.23
In addition to ZIF-8, a series of imidazolate-based MOFs have been
synthesized afterwards. Among them, ZIF-68, -69, -70 show good chemi-
cal stability.24 These three MOFs are all synthesized from two different
functionalized imidazolate ligands and share the same topology of gme
(Figure 11). Evaluation of their chemical stability is conducted by
immersing the samples in boiling benzene, methanol, and water for 7
days. All these MOFs survive under these conditions, as indicated by the
unshifted and sharp peaks in their PXRD patterns.24
Attempts have also been made to construct MOFs with other soft N
ligands, such as tetrazolate ligands25 and triazolate ligands.26 Because
tetrazolates have a higher number of N atoms in the aromatic hetero
rings, their ligands in the form of acids have low pKa values (~4.9, which
is as low as that of acetic acid 4.76), and coordination abilities of the
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16 Li et al.
Figure 11. Reaction of 2-nitroimidazole (nIm) and a specific imidazolate-based

ligand generates ZIF-68, -69, -70, respectively. Taken from Ref. 24b with permission
of the American Chemical Society.
corresponding deprotonated ligands are weak. As a consequence, M–N

bonds are not strong enough to resist the attack of water or other solvent
molecules, making tetrazolate-based frameworks less chemically stable

than their triazolate or diazolate counterparts.27 Therefore, to obtain
robust MOFs with azolate-based ligands bearing more than two N atoms,
efforts have been focused on triazolate ligands. In 2009, Demessence
et al. reported a CuII-MOF, Cu-BTTri, which is composed of CuII and a
triazolate-based ligand, 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene
(H3BTTri) (Figure 12). Cu-BTTri is stable in boiling water for 3 days
and in 1 mM HCl solution (pH = 3) for 1 day. Moreover, Cu-BTTri is
utilized to immobilize ethylenediamine (en) for CO2 capture, suggesting
its resistance to some basic conditions as well (Figure 12). All the above
evidence substantiates the strong bond formed between BTTri and CuII
and the chemical robustness of Cu-BTTri.26
It has been analyzed that the remarkable chemical stability of imidazolate-
bridged frameworks is due to the high basicity of imidazolate ligand, as
reflected in the high pKa values of imidazoles. Considering that pyrazoles
have similar or even higher pKa values than imidazoles, MOFs based on
pyrazolate ligands are also anticipated to be stable.28 In 2010, Choi et al.
reported two robust MOFs constructed from ZnII and two pyrazolate-
based ligands, respectively: 1,4-benzenedi(4-pyrazolyl) (1,4-H2BDP) and
its meta isomer 1,3-benzenedi(4-pyrazolyl) (1,3-H2BDP). ZnII ions adopt
a tetrahedral coordination geometry and are linked by 1,4- or 1,3-BDP.
To investigate the water stability of the resulting MOFs, as-synthesized
sample, Zn(1,4-BDP)·2DEF·H2O (DEF, N,N-diethylformamide) is soaked
b2980_Ch-01.indd 16 05-Jan-18 6:40:12 AM


Figure 12. A portion of Cu-BTTri structure, which shows functionalization of a

coordinatively unsaturated CuII site with en. H atoms are omitted for clarity. Taken
from Ref. 26 with permission of the American Chemical Society.
in water at raised temperatures. Though there are minor phase changes

when the MOF is immersed in water, the original phase is rapidly recov-
ered after reimmersion in DEF for 3 min. It has been observed that
Zn(1,4-BDP)·2DEF·H2O is able to survive in boiling water for 3 days.
Zn(1,3-BDP)·0.7DMF·0.5H2O “(DMF, N,N-dimethylformamide) exhib-
its even more marked stability in water and acidic solutions. Apart from
being able to retain its structure in boiling water for 3 days, it is also
reported to survive in an acidic solution with a pH value of 3 for up to 30
min at 90 °C, which serves as a good example to demonstrate the strong
bonds between soft Lewis acids and pyrazolate-based ligands.28 Similar
examples were published by Padial et al. in 2013 about a series of linear
pyrazolate-based ligands that form strong bonds with NiII. The resulting
NiII-dipyrazolate MOFs are also water stable.29
Later, some tritopic pyrazolate ligands are also synthesized to bond
with soft metal ions. An example was reported by Colombo et al. in
2011.30 The stable MOF is synthesized from Ni(AcO)2 and 1,3,5-tris(1H-
pyrazol-4-yl)benzene (H3BTP) (Figure 13). Remarkably, Ni3(BTP)2 is
stable in boiling water, boiling aqueous HCl or HNO3 solution with a pH
b2980_Ch-01.indd 17 05-Jan-18 6:40:13 AM

18 Li et al.
Figure 13. (a) Structure of H3BTP ligand, (b) a portion of Ni3(BTP)2 structure.
H atoms are omitted for clarity. Taken from Ref. 30 with permission of the Royal
Society of Chemistry.
value of 2, and boiling aqueous NaOH solution with a pH value of 14 for

14 days. The reason for its ultrastability is also analyzed. Based on the
previous research results, the bond strength of N–M is closely related to
the pKa value of the acid form of an azolate ligand. The higher the pKa
value, the stronger the N–M bond. The pKa values for tetrazole, 1,2,3-
triazole, imidazole, and pyrazole are 4.9, 13.9, 18.6, and 19.8, respec-
tively.30 Therefore, pyrazolate-based ligands are reasonable to generate
very chemically robust MOFs.
In 2016, Wang et al. reported a pyrazolate-based porphyrinic MOF
with ftw-a topology, namely PCN-601. It is constructed by Ni8 cluster and
5,10,15,20-tetra(1H-pyrazol-4-yl)-porphyrin (H4TPP) (Figure 14).15
PCN-601 is demonstrated to be extremely stable, especially in alkali
aqueous solutions. It can maintain sound crystallinity and porosity even
after being boiled in saturated NaOH aqueous solution (20 mol/L) at
100 °C for 24 h. The intactness of PCN-601 is also examined by UV-Vis
adsorption spectrum by submerging the treated MOF into DMF for 24 h
and comparing its spectrum with the standard solution of H4TPP in DMF.
The absolute zero absorbance indicates that there is no ligand decomposed
and leaked from the MOF which confirms the intactness of PCN-601 after
b2980_Ch-01.indd 18 05-Jan-18 6:40:13 AM


Figure 14. Topological and structural representation of PCN-601. Taken from

Ref. 15 with permission of the American Chemical Society.
the harsh treatment. This striking stability in saturated basic solution at

high temperature can be explained partially by the strong interaction
between soft Lewis acid NiII and soft pyrazolate-terminated ligand, which
makes the framework highly resistant to the attack of destructive species
in solutions. The robustness of PCN-601 can also be rationalized from the
perspective of crystal field theory. In basic solution, the decomposition of
PCN-601 can be regarded as a competition between pyrazolate and OH−
to bind NiII. It is well known that pyrazolate is a stronger field ligand than
OH− or H2O. Thus, the coordination between NiII and pyrazolate can
render a larger crystal field stabilization energy than that of between NiII
and OH− or H2O. This serves as a thermodynamic factor to enhance the
robustness of PCN-601 under harsh conditions. Because of its compelling
stability in extremely basic condition and the inherent inclusion of por-
phyrin moieties, PCN-601 is expected to have a lot of application in the
fields of pH sensing, catalysis, and photodynamic therapy.
Many efforts have also been made to synthesize MOFs with neutral
N-donor ligands, such as pyrazine. King Abdullah University of Science
and Technology (KAUST)-7 (also known as NbOFFIVE-1Ni), which is
b2980_Ch-01.indd 19 05-Jan-18 6:40:14 AM

20 Li et al.
built upon pyzazine, NiII, and inorganic block [NbOF5]2−.31 KAUST-7 is

assembled by square-shaped Ni-pyrazine (4,4′) square grid that is further
connected by (NbOF5)2− pillars. KAUST-7 is stable in aqueous solution
for more than 6 months and is also stable after being exposed in atmos-
phere with 95% humidity or 10% H2S. The strong bond between pyzazine
and NiII is one reason for its stability. It is also proposed that the strong
hydrogen interaction between the NiII-pyrazine square layers and
(NbOF5)2− pillars also enhances the robustness of the MOF. A similar

example of MOF synthesized from pyrazine is SIFSIX-2-Cu-i. Its stabil-
ity in water vapor was demonstrated by the unchanged PXRD pattern after
its water sorption experiment.32
It is worth mentioning that the N-donor ligands also have strong inter-
action with some trivalent metal ion, which is exemplified in the case of
Fe2(BDP)3.33 The MOF is built upon FeIII and a ditopic pyrazolate ligand
BDP2−. The strong FeIII-pyzazolate bonds and high connectivity between
the metal ions and ligands render Fe2(BDP)3 with exceptional stability. It
can survive in boiling aqueous solutions with pH ranging from 2–10 for 2
weeks, which acts as a highly inspiring example.
III. Other Structural Characteristics

Apart from the strength of coordination bonds in MOFs, there are also
other structural features that can affect the robustness of MOFs.
A. High Connectivity of Metal Nodes and Ligands

If the connectivity of ligands or metal nodes is higher, the reparation of
structural defects can take place at a higher rate to prevent further decom-
position and enhance the stability of MOFs.15 The idea is exemplified in
the case of PCN-601. The connectivity of both the Ni8 cluster (a 12-
connected node) and the pyrazolate-based porphyrinic ligand TPP4− (a
4-connected linker) is very high among the reported inorganic clusters and
organic ligands. From a kinetic perspective, the decomposition of MOFs
in solution could be regarded as successive substitution of coordination
moieties with small molecules or ions, during which structural defects
occur. With respect to the ligand, the coordination site might stay around
b2980_Ch-01.indd 20 05-Jan-18 6:40:14 AM

the metal nodes even after it is displaced due to the tethering from other
attached terminals of the ligand. This creates a very high “effective con-
centration” of the ligand terminal around the defect site. As a result, the
reverse reaction of ligand dissociation, that is, reattach of the ligand to
metal nodes, is extremely rapid, rendering fast structural reparation and
increased stability. If the connectivity of the ligand is higher, this enhanced
defect reparation effect (3D chelating effect) will be stronger because

higher connected ligands could tolerate a larger number of displaced
ligand coordination sites and have a higher rate of reparation. Similar
conclusions can be drawn for high-connected metal nodes as well.
Therefore, high-connected constructing fragments are greatly favored for
the generation of stable MOFs.
B. Short Length of Ligands

Apart from the 3D chelating effect, the length of a ligand is also crucial in
determining the robustness of the framework. In the work of PCN-601,
Wang et al. rationalized that the length of the ligand is related to the acti-
vation energy of ligand dissociation and thus affects the decomposition of
MOFs.15 In Scheme 1, two isoreticular frameworks are presented, which
are constructed by a long and a short ligand, respectively. Regardless of
the mechanism of substitution (dissociative or associative), ligands coor-
dinated to metal nodes are sure to be bent in transition states. If the dis-
placement of the ligand terminals in transition states are equal in the two
scenarios, that is ds = dl, the short ligand would be bent to a larger degree
(qs > ql). This makes the activation energy of decomposition higher for
MOFs with shorter ligands and leads to relatively higher inertness.
Scheme 1. Illustration of the kinetic stability of MOFs with different lengths of

ligands. Taken from Ref. 15 with permission of the American Chemical Society.
b2980_Ch-01.indd 21 05-Jan-18 6:40:14 AM

22 Li et al.
C. Hydrophobic Groups
Water stability of MOFs may also be improved through the addition of
hydrophobic groups in ligands. ZIF-8 is a good example to illustrate this
point.23 It is proposed that the methyl groups on imidazolates can assist in
blocking water molecules from attacking the ZnN4 units. Similarly, in
ZIF-68, -69, -70, the hydrophobic surfaces of these ZIFs also serve the
same function and increase their water resistance.

In 2013, Padial et al. published a work about using pyrazolate-based
ligands bearing inherent methyl groups for construction of stable MOFs.
The methyl groups were demonstrated to increase the partial pressure
corresponding to water vapor condensation into the framework (P/P0 >
0.6 compared to P/P0 > 0.65 for the linker with additional methyl
groups), substantiating the effect of methyl groups on the hydrophobic-

ity of frameworks.
The same strategy can be applied in MOFs constructed by hard Lewis
acids and bases as well. In 2016, Wang et al. reported two isostructural
Zr-MOFs, Beijing University of Technology (BUT)-12 and BUT-13
(Figure 15).34 Both MOFs demonstrate their stability in boiling water for
7 days, concentrated HCl for 24 h, and NaOH solution (pH = 10) for 24
h. It is purposed that the presence of methyl groups on the central phenyl
ring of the organic linker increases the hydrophobic character of the
frameworks and therefore raises their water stability.29 By examining the
contact angle of water with the material, the extent of hydrophobicity of
the framework and thus water stability can be anticipated. A hydrophobic
material exhibits a contact angle between 90° and 150° with water and a
material displaying a contact angle over 150° is considered superhydro-
Figure 15. Ligands and MOF structures of BUT-12 (left) and BUT-13 (right). Taken
from Ref. 34 with permission of the American Chemical Society.
b2980_Ch-01.indd 22 05-Jan-18 6:40:14 AM

phobic. In the cases of BUT-12 and BUT-13, the contact angle of the
frameworks with water are determined to be 138.7° and 118.3°, respec-
tively, classifying both materials as hydrophobic. Water isotherms for both
materials feature hysteresis loops, with low uptakes at low pressures fol-
lowed by large rises in uptakes at high pressures. At low pressures, the
water uptakes of the MOFs are 18.5% and 15.1% of the total water
uptakes for BUT-12 and BUT-13, respectively.34 This suggests strong
hydrophobicity on the surface of these materials and is likely to act as a

contributing factor for their water stability.
In addition to synthesizing MOFs with ligands that have methyl groups
inherently, alkyl groups can also be introduced into MOFs via postsyn-
thetic modification. In 2010, Nguyen et al. were able to increase the hydro-
phobic character of isoreticular metal-organic framework (IRMOF)-3 and

MIL-53(Al)-NH2 by conducting postsynthetic modifications on the amine
groups to add alkyl chains into the frameworks (Figure 16).35 In these
experiments, IRMOF-1 is used as the control group. The untreated
IRMOF-1 and -3, as well as IRMOF-3-AM1, -AM2, and -AM3 (-AMn =
amide with an n carbon chain) exhibit water contact angles close to 0°.
(Materials with contact angles less than 90° are considered as hydrophilic.)
When IRMOF-3 is treated with longer alkyl chains (n ≥ 4), the modified
MOFs display contact angles > 116°, classifying the materials as hydro-
phobic. It is also found that longer alkyl chains need lower percentages of
conversion to make the resulting MOFs hydrophobic. For instance, the
Figure 16. Schematic representation of the alkyl chain modified IRMOF-3 and
MIL-53(Al). Taken from Ref. 35 with permission of the American Chemical Society.
b2980_Ch-01.indd 23 05-Jan-18 6:40:15 AM

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CHAPTER III.
VARIOUS MATERIALS USED IN COACH-

BUILDING.
The materials employed in coach-building number a great many:
various kinds of wood—ash, beech, elm, oak, mahogany, cedar,
deal, pine, &c.; hides, skins, hair, wool, silk, glue, whalebone, ivory,
&c.; iron, steel, copper, brass, lead, tin, glass, &c.
The timber principally used in the construction of carriages is the
ash. This is not an elastic, but rather a tough and fibrous wood,
capable of altering its form by the application of pressure, and
therefore when not in large masses requires iron plates to secure it.
By boiling it becomes very pliable, and may be formed into almost
any shape, provided that it is not too thick. For this purpose it is
better to use steam than boiling water, as the latter is likely to
dissolve and carry off the gluten which unites the fibres, thus
rendering the timber useless. Some ash timber is white at heart, and
some red; the white is usually the strongest and best. Some trees
which have been grown on hillsides much exposed to constant winds
present a remarkably wrinkled appearance through their whole
length, and it is scarcely possible to plane their timber smooth; this is
the toughest of all ash timber. Parts of ash-trees are sometimes
found of a yellowish-brown colour, accompanied by a fetid acid
smell. This is sometimes attributed to the effect of lightning, but more
probably it is a putrid fermentation of the sap, owing to imperfect
drying. All other circumstances being equal, the timber is best which
is cut down when the circulation of the sap is slowest, as the pores
are then open. In the process of drying or seasoning the bulk
diminishes considerably. One of the qualities which render ash
peculiarly fit for carriage construction is the absence of elasticity, and
consequent indisposition to alter its form by warping or twisting. It is
not well adapted for boards or planks in which much width is
required, as in drying it cracks a great deal. The diameter of ash-
trees used by carriage-builders varies from 1 foot to 3 feet 6 inches.
It should be borne in mind in cutting ash, that the interior and the
outer casing under the bark are rather softer and less durable than
the parts between them.
Beech is sometimes used by carriage-builders and by
wheelwrights, on account of its cheapness; but it is very liable to
warp and rot, and consequently unworthy of the attention of the
conscientious manufacturer.
Elm is largely used for planking where strength is required. The
grain is wavy, hard to work, brittle, and apt to split without care. It is
not a good surface to paint on, as the grain shows through several
coats of colour. It is also used for the naves or stocks of wheels.
Oak is used for the spokes of wheels. The best kinds are made
from the timbers of saplings, which are not sawn but cleft, in order
that the grain may be not cut across and render the spoke unfit to
resist the strains it will be subject to. Spokes are also made from the
limbs of large trees.
Mahogany is largely used for panels, as when painted it shows a
very even surface. There are two kinds, the “Spanish” and the
“Honduras.” The former is unfit for the purposes of the carriage-
builder. It is heavy and very difficult to work, requiring special tools
for this purpose, as the edges of ordinary tools are rapidly destroyed
by it. The Honduras is very much lighter and cheaper than Spanish,
and the grain and colour more even. It takes the sweeps and curves
required for body-work very easily. It can be procured up to 4 feet in
width, straight-grained, and free from knots and blemishes.
A coarse-grained species of cedar is brought from the same
district as Honduras mahogany, and is sometimes used for panels
which have to be covered with leather, &c. Its extreme porosity
renders it unfit for the application of paint.
Deal is largely used for the flooring of carriages, and for covered
panels, and for any rough work that is not exposed to great wear and
tear.
The wide American pine is chiefly used in very thin boards to form
the covered panels and roofing of carriages.
Lancewood is a straight-grained, elastic wood, but very brittle
when its limit of elasticity is reached. It comes from the West Indies
in taper poles about 20 feet long and 6 or 8 inches diameter at the
largest end. It was formerly much used for shafts, but since curved
forms have been fashionable it has fallen into disuse. It can be bent
by boiling, but is a very unsafe material to trust to such an important
office as the shafts.
American birch is a very valuable wood for flat boarding, as it can
be procured up to 3 feet in width. It is of a perfectly homogeneous
substance, free from rents, and with scarcely a perceptible pore. It
works easily with the plane and yields a very smooth surface, and
the grain does not show through the most delicate coat of paint. Its
chief disadvantage is its brittleness, which will not permit of its being
used for any but plane surfaces, and some care is required in nailing
and screwing it.
Hides are used chiefly for coverings, but also in some parts strips
are used for the purposes of suspension. The hides are those of
horses and neat cattle. For covering they are converted into leather
by the action of oak and other bark. They are afterwards smoothed
and levelled by the currier, and sometimes split into two equal
thicknesses by machinery. They are then rendered pliable by the
action of oil and tallow, and finished to a clear black or brown colour
as may be required. This is called dressed leather. For some
purposes the hides are merely levelled, put on wet to the object they
are intended to cover, and left to shrink and dry. Others are covered
with a coat of elastic japan, which gives them a highly glazed
surface, impermeable to water; in this state they are called patent
leather. In a more perfectly elastic mode of japanning, which will
permit folding without cracking the surface, they are called
enamelled leather. They are generally black, but any colour desired
may be given to them. All this japanned leather has the japan
annealed, somewhat in the same mode as glass. The hides are laid
between blankets, and are subjected to the heat of an oven raised to
the proper temperature during several hours.
The skins used are those of the sheep and goat. The former are
converted into leather by the action of oak bark. In one form of
dressing them they are known as basil leather, which is of a light
brown colour and very soft. Sometimes they are blacked, and
occasionally japanned like the hides. In all these forms sheep skins
are only used for inferior purposes, as mere coverings, where no
strength is required.
Goat skins are used in the preparation of the leather known as
“Spanish” and “Morocco.” They are not tanned in oak bark like other
leather, but very slightly in the bark of the sumach-tree. They pass
through many processes previous to that of dyeing, for which
purpose they are sewn up with the grain outwards and blown out like
a bladder. This is to prevent the dye from getting access to the flesh
side. This beautiful leather was originally manufactured by the
Moors, who afterwards introduced the process into Spain, by which
means it came to be known under two names. The English have
greatly improved on the manufacture, so much so that few others
can vie with it. These skins are used for the inside linings of
carriages.
Hair is used as an article of stuffing. To give it the peculiar curl
which renders it elastic, it is forcibly twisted up in small locks, and in
that state baked in an oven to fix it. Horse-hair is the best, being the
strongest and longest; but various other kinds are used. Sometimes
it is adulterated with fibres of whalebone. Doe-hair is also much used
as an article for stuffing, but as it is very short it cannot be curled,
and there is not much elasticity in it.
Wool in its natural state is not used for carriage purposes. In the
form of “flocks,” which are the short combings and fibres produced in
the process of manufacturing it, it is very largely used for stuffing. In
its manufactured state wool is used in great quantities, as cloth, lace,
fringe, carpeting, &c.
The iron used is that known as wrought iron. To judge of its quality
break a piece over the anvil; if it breaks off brittle it is of no use for
the purposes it is required for. If it is good wrought iron the fracture
will present a bluish, fibrous, silky texture, without any crystalline
portions. Inferior iron will either appear bright and glistening (when it
partakes of the properties of cast iron) or dull and greyish in tone at
the fracture.
It may also be tested by bringing it to a red heat and bending it,
when any flaws, &c., will at once become apparent.
Cast iron is also used in the shape of axle-boxes.
Great quantities of wrought iron are used in the construction of
modern carriages. One of the best qualities is that known as the
“King and Queen,” so called from its brand. This iron is
manufactured from pieces of old iron, called scrap iron, which are
placed in furnaces and welded under a heavy tilt-hammer, after
which it is passed between rollers and converted into bars.
Steel also enters largely into carriage construction in the shape of
springs, &c. Axles are made of Bessemer steel, and are found to
wear very well. Steel consists of iron in which is combined a large
proportion of carbon; the more carbon the higher the elasticity of the
steel. If steel is over-heated, it gives up a portion of its carbon and
approaches once again its original form of iron.
CHAPTER IV.
POINTS TO BE CONSIDERED BEFORE

COMMENCING THE CONSTRUCTION OF A
CARRIAGE.—COMPONENT PARTS OF THE
BODY.—SMITH’S WORK.—GLUE.
As previously remarked the vehicle is divided into two parts—the
carriage and the body. After the drawing or draught is carefully
worked out to full-size on the black-board in the shop, with all the
curves and sweeps developed, and shown in elevation and plan,
patterns or templates are made from the draught, and from these the
construction of the body proceeds.
In commencing the construction of a vehicle there are several
things to be borne in mind; such as the purpose to which the vehicle
is to be applied, the size of horses to draw it, and other
considerations arising from these two. It is popularly believed that
the shorter the carriage the lighter it will run; in ascending an incline
this may be true, but on ordinary level ground a long carriage and
short one must be alike in friction, provided the total amount of
weight and other circumstances be equally balanced.
Another consideration is the height of the wheels. On level ground,
draught is easiest when the centre of the wheel is a little lower than
the point of draught, viz. the point where the traces are affixed to the
collar; but this in practice would be found rather inconvenient, as
very high wheels would be required, and consequently the height of
the whole vehicle would have to be increased, causing great trouble
and annoyance in getting in and out of the vehicle, and the driver’s
seat would have to be raised to a corresponding height. Under equal
circumstances a high wheel is more efficient than a low one, and
requires less power to draw it; though it may be mentioned that a low
wheel on a good and level road will do its work far better than a very
much higher wheel on a rougher road. The sizes of the wheels of
two-wheeled vehicles vary from 3 feet to 4 feet 6 inches.
It would be a very good thing if four-wheeled vehicles were to have
the wheels of equal size, in order that the friction and power might be
equal. But with the present mode of construction this is an
impossibility, as we have only one mode of making the lock or turn.
Therefore the height of the fore wheels must be regulated by the
height at which the body hangs, so that the wheels may pass
beneath it without striking, when the springs play. In practice this
height varies from 2 feet to 3 feet 8 inches, according to the kind of
carriage the wheels are intended for. The hind wheels vary from 3
feet to 4 feet 8 inches.
The next point is the dishing of the wheel, which is necessary for
strength to take the strain off the nuts, to throw off the mud and
prevent it clogging either the wheel or the body, and to give greater
room for the body between the wheels without increasing the track
on the ground. Whatever be the amount of dishing or coning, which
varies from 1½ to 2½ inches, one rule should always be observed,
viz. so to form the wheel that when running the lower spokes should
maintain a true vertical position both in the fore and hind wheels.
This is mainly accomplished by the dip of the axle, but if the fore and
hind wheels have the same dish, they will take the same track along
the ground. The dish of a wheel will be understood by referring to
Fig. 10, in which it will be seen that the extremities of the spokes are
not in the same plane, thus forming a dish or hollow in the surface of
the wheel.
Some ingenious persons have deduced from the foregoing that a
wheel runs best on an axle having a conical arm (the arm is the
extremity of the axle which fits into an axle-box in the nave or stock
of the wheel), in which case the axle would not dip, but the wheel
would be put on to a perfectly horizontal axle. The motion of a wheel
thus placed would be anything but artistic, though there would not be
so much friction on an arm of this sort as on an arm of the dipped
axle. Dipping the axle is shown at Fig. 10. It merely consists in
bending it so far out of the horizontal as to give the lower spokes a
vertical position. But in practice this theory of the conical arm will not
answer, inasmuch as curving the arm will reduce the front bearing
surface so much that the oil would be squeezed out, and it would run
dry, and the total amount of friction would be greatly increased. Long
practice has shown that a cylindrical or slightly conical arm is the
best that can be used.
Fig. 10.
We have now to settle the form, combination, and proportion of the
springs. Springs which are laid on the axle at right angles have to
carry the whole of the weight of the carriage, save only the wheels
and axles. Where other springs are used in addition it is not
necessary that the axle-springs should have much play. It will be
sufficient to give them just so much play as will intercept the
concussion caused by moving over a road. The strength of the
springs must of course be adjusted to the weight they have to carry,
for it is evident that if they be made sufficiently elastic to carry the
weight of six persons, they will be found hard if only three enter the
carriage. This is a disadvantage all carriages must labour under, for
it is ridiculous to suppose that if a carriage is constructed to hold six
that number will always want to use it at the same time. There would
seem to be room for some improvement in the way of introducing
springs adjustable to any weight, though, to give spring-makers their
due, they do turn out really a first-class article in this respect; this is
more noticeable because it is so recent. Light carriages are never so
easy to ride as heavy ones, even when the springs are well adjusted,
because on meeting with an obstacle there is not a sufficient
resistance to the bound or jerk upwards of the spring, which makes
riding in a light carriage over a rough road rather unpleasant.
The position of the front wheels next demands attention. As these
have to turn under the body it requires some skill to fix them, and the
play of the springs, the height of the axletree, and the height of the
arch (the portion of the body under which they turn) have all to be
considered. This will be more particularly described when dealing
with wheel-plates.
The rule for the height of the splinter-bar, to which the traces or
shafts are fixed, is that it should fall on a line drawn from the horse’s
shoulder to the centre of the hind wheel. This, however, is not always
convenient in practice, as the fore wheels regulate the height of the
framing of the under carriage, to which the splinter-bar is fixed. The
distance of the splinter-bar from the central pin, on which the wheel-
plate and fore carriage turn, is regulated by the size of the wheels
and the projection of the driving seat footboard.
All the above particulars are considered when setting out the full-
sized draught, and all points capable of delineation are put on the
board in some convenient part. In Fig. 9 the outline is simply given,
as to show everything would only confuse the reader. Such other
details as are required are filled in after the draught has reached the
stage shown in the figure.
It is most necessary for the safe conduct of a coach and carriage
builder’s business that there should be a goodly stack of well-
seasoned timber of the various kinds required, otherwise great
trouble and vexation will arise in the course of business from a good
piece of timber being perhaps spoilt in working, and there not being
another piece in the factory to replace it.
Where there is sufficient accommodation it is usual for makers to
season their own timber in specially constructed sheds, which are
kept from bad weather, but at the same time thoroughly well
ventilated. In these the timber is stacked, with small fillets between
each plank or board, to insure a free current of air circulating all
round. One year should be allowed for seasoning for every inch of
thickness in the timber, and none should be used in which this rule
has not been observed.
Thin portions of timber, such as panel stuff and the like, should be
treated in the same way, and in addition the ends should be secured
to prevent splitting. The panel stuff undergoes another process of
seasoning after it is planed up; in fact, all the thin timber required for
roofs, sides, &c., does. And about the first thing done in commencing
to build a carriage is for the body-maker to get his thin stuff ready, as
far as planing it up goes, and then to put it aside in some moderately
dry place, with slips of wood between each board to allow a
circulation of air round them. The other stuff that is likely to be
required should also be selected and put aside. If all these things be
strictly attended to, there is not likely to be much trouble about bad
joints; and it will be to the employer’s interest to look after such
workmen who have not enough scientific knowledge to see the
reason of things themselves, and put them in the right direction. But
an intelligent workman will soon appreciate the advantage of getting
his stuff ready at the commencement, instead of waiting till he wants
to use it.
The parts composing the body may be thus enumerated:—
The frame or case.
The doors.
The glasses, which are fixed in thin frames of wainscot, covered
with cloth or velvet. It is a very good thing to have india-rubber for
these to fall on, and little india-rubber buffers would prevent them
from rattling.
The blinds, which are sometimes panel, but more generally
Venetian, so adjusted with springs that the bars may stand open at
any required angle.
The curtains, of silk, which slide up and down on spring rollers.
The lining and cushions, of cloth, silk, or morocco, as the case
may be, ornamented with lace, &c. The cushions are sometimes
made elastic with small spiral springs.
The steps, which are made to fold up and fit into recesses in the
doors, or in the bottom, when they are not in use.
The lamps, which are fixed to the fore part of the body by means
of iron stays.
The boot, on which is carried the coachman’s seat.
In carriages suspended from C springs we have in addition:—
The check-brace rings, to which are attached leather braces from
the spring heads, to prevent the body from swinging too much
backwards and forwards.
The collar-brace rings, to which are attached leather braces from
the perch, to prevent the body swinging too much upwards or
sideways.
The curve or rounding given to the side of the body from end to
end is called the side-cant, and the rounding from the top to the
bottom the turn-under. Some makers arrive at this curve by framing
the skeleton of the body together with square timber, and then round
these off to the required curve after they are put together. It must be
evident to any one that this proceeding will greatly strain the joints,
and under any circumstances will never give thorough satisfaction or
good results, and the waste of time and material must be very
considerable.
The proper way is to set the curve out beforehand on a board
called the “cant” board, and the method of doing this is as follows:—
Take a clean pine board, plane it up to a smooth surface. Shoot
one edge perfectly true with a trying-plane. This straight edge may
be taken to represent the side of the carriage if it were a straight line.
Apply this edge to the full-sized draught, and mark along it the
various parts of the body (see Fig. 8, in which the numbered points
are those required to form the side-cant). By means of these points
the required sweep can be set up or drawn, as shown by the dotted
line C in the figure. Now, if you choose, you can cut away the portion
between A and B, and a template will be formed to which the
constructional timbers can be cut; and it possesses the advantage of
being easily applied to the carriage as it proceeds, to see that the
curve is true and uniform. As this template forms the pattern to which
the timber, &c., is cut, great care is requisite in forming it, so that it
shall be perfectly true.
In order to get the turn-under, the same process is gone through
on another board. This gives what is called the “standing” pillar
pattern, the standing pillar being the upright timber to which the door
is hinged.
There is no rule in particular for determining the amount of side-
cant or turn-under to be given to a vehicle, 2½ or 3 inches on each
side making the outside width of the body; 5 or 6 inches less at the
bottom than at the elbow line is a usual allowance, but this is entirely
dependent on the will or taste of the workman.
The cant-board described above is one having a “concave”
surface; but it quite as often has a convex surface, and it is just as
well to have one of each, and use the convex for cutting the timbers
to, and the concave for trying them when in place, though, if this be
done, it is imperative that the curves on the two boards should be
one and the same. The same remarks apply to the standing pillar
pattern.
The body is a species of box, fitted with doors and windows, and
lined and wadded for the purpose of comfort. As the greatest amount
of strain is put upon the bottom part, and the forces acting on the
other parts are transmitted to the bottom, it is necessary that it
should be very strongly put together. The two side bottom timbers
are bonded, or tied together, by two cross timbers called bottom
bars, which are firmly framed into them. To give depth to the floor,
without destroying the symmetry of the side, deep pieces of elm
plank are fixed to the inside of the side bottom pieces, and to these
the flooring-boards are nailed, being additionally secured by iron
strap plates, nailed or screwed beneath them. In the central portion
of the bottom sides are framed the door-posts, called standing
pillars. At the angles of the bottom framework are scarfed the corner
pillars. The cross framing pieces, which connect the pillars, are
called rails. Two of these rails stretch across the body inside, on
which the seats are formed; these are called seat rails. The doors
are framed double, to contain a hollow space for the glasses and
blinds, and they are fastened by means of a wedge lock, forced into
a groove by a lever handle. There is a window in each door and one
in front of an ordinary carriage, say a brougham. The doors are
hinged with secret or flush hinges.
Before cutting the timber to the various sizes required, patterns or
templates of all the parts are made in thin wood from the full-sized
draught; also of the various curves likely to be given to the different
parts of the body.
Before a workman could be trusted with the making of a body, he
must of course have considerably advanced in the knowledge of his
craft beyond the mere use of his tools, because the success of a
carriage depends very largely upon the individual skill of the
workman, more so than perhaps in any other trade.
The stuff is marked out from the thin patterns before mentioned by
means of chalk, and in doing so care should be taken to lay the
patterns on the timber so that the grain may run as nearly as
possible in a line with it, and thus obtaining the greatest possible
strength in the wood, which lies in the direction of the grain. Thus if
the pattern be straight, lay it down on a piece of straight-grained
timber; if the pattern sweep round, then get a piece of timber the
grain of which will follow, or nearly follow, the line of pattern.
The strongest timber that can be obtained is necessary for the
construction of the hind and front bottom sides; for the weight is
directly transmitted to these, more particularly the hind bottom sides,
where the pump-handles are fixed.
The body-maker, having marked and cut out the various pieces of
timber he will require, planes a flat side to each of them, from which
all the other sides, whether plain or curved, are formed and finished.
They are then framed and scarfed together, after which the various
grooves are formed for the panels and rebates, for the floor-boards
to fit on to. Then, if there is to be any carved or beaded work, it is
performed by the carver. Previous to being fitted in, some of the
panels have strong canvas glued firmly on their backs, and when
fitted in blocks are glued round the internal angles to give greater
security to the joints, and to fix the panels firmly in their places.
Before the upper panels are put in, the roof is nailed on, and all the
joints stuck over with glued blocks inside. The upper panels are then
put on, united at the corners, and blocked inside.
If the foreman who superintends all this be a thoroughly skilful
artisan, and the men under him possess equal intelligence and skill,
the work might be distributed amongst almost as many men as there
are parts in the framework of the body. These parts will be worked
up, the mortises and tenons, the rabbets and tongues, being all cut
to specified gauges; and when they are all ready it will be found that
they go together like a Chinese puzzle.
The woodwork being completed, the currier now takes the body in
hand, and a hide of undressed leather, specially prepared for it, is
strained over the roof, the back, and the top quarters of the body
whilst in a soft pulpy state, and carefully sleeked or flattened down till
it is perfectly flat. This sleeking down is a rather tedious process, and
takes a long time and a great amount of care to bring it to a
successful issue; when it is flattened down satisfactorily, it is nailed
round the edges and left to dry, which will take several days.
Such panels as require bending may be brought to the required
sweep by wetting one side and subjecting the other to heat, as of a
small furnace.
The doors are now made and hinged, and the hollow spaces
intended to hold the glasses and blinds are covered in with thin
boards, to prevent any foreign matter from getting down into the
space, and being a source of trouble to dislodge.
In constructing the body the aid of the smith is called in. His
services are required to strengthen the parts subjected to great
strain, more particularly the timbers forming the construction of the
lower portion. All along each side of the body should be plated with
iron; this should be of the best brand and toughest quality. It is
several inches wide, and varies from ¼ to ¾ of an inch in thickness.
This is called the “edge plate,” and is really the backbone of the
body, for everything depends on its stability. It should run from one
extremity to the other, commencing at the hind bottom bar, on to
which it should be cranked, and ending at the front part of the front
boot, bottom side. This plate should take a perfectly flat bearing at
every point. Great care must be taken in fitting it, for although the
plate may be of the requisite strength the absence of this perfect
fitting will render it comparatively weak, the result of which will be
found, when the carriage is completed and mounted on the wheels,
by the springing of the sides, which will cause the pillars of the body
to press on the doors, and it will be a matter of great difficulty to
open them.
In the application of smith’s work to coach-building, it is often
necessary to fit the iron to intricate parts while it is red hot, and if due
precaution be not taken the wood becomes charred and useless,
and in cases where there are glued joints it may cause the loosening
or breaking of these joints and other material defects. It is an easy
matter to have the means at hand to get over the difficulty. All that is
necessary is to have handy some heat neutraliser. One of the
commonest things that can be used is chalk, and no smith’s shop
should ever be without it. If chalk is rubbed over the surface to which
the hot iron is to be applied it will not char or burn. Plaster of Paris is
a still more powerful heat neutraliser, and it is freer from grit. A small
quantity of the plaster mixed with water, and worked up to the proper
consistency, will be ready for use in about two hours. Many smiths
will say that they never have any accidents in applying heated iron,
but on inquiry the reason is apparent, for it will generally be found
that such men use chalk, in order to see that the iron plate takes its
proper bearings, thus inadvertently using a proper heat neutraliser. If
it were more generally known that the difficulty could be met by such
simple means, there would be less material spoilt in the smith’s
shop.
It has been very common of late years for body-makers to use
glue instead of screws and nails for panel work, &c.; but it requires a
great deal of experience for a man to use glue with successful
results. It is useless for the tyro to try it; he will only spoil the work.
So, unless the artisan be well experienced in the treatment and
application of glue, he had better leave it alone. To render the
operation successful two considerations must be taken into account.
First: To do good gluing requires that the timber should be well
seasoned and the work well fitted. Second: In preparing for gluing
use a scratch plane or rasp to form a rough surface of the pieces to
be joined together, for the same purpose that a plasterer scores over
his first coat of plaster-work, in order to give a key or hold. The shop
in which the gluing is done should be at a pretty good temperature,
and so should the material, so that the glue may flow freely. Having
the glue properly prepared, spread it upon the parts, so as to fill up
the pores and grain of the wood, and put the pieces together; then
keep the joints tight by means of iron cramps where it is possible,
and if this cannot be done the joints must be pushed tightly up, and
held till the glue is a little set and there is no fear of its giving way. All
superfluous glue will be forced out by this pressure and can be
cleaned off.
A great cause of bad gluing is using inferior glue and laying it on
too thick. Before using a new quality of glue, the body-maker should
always test it by taking, say a piece of poplar and a piece of ash, and
glue them together, and if when dry the joints give way under
leverage caused by the insertion of the chisel, the glue is not fit for
the purposes of carriage-building and should be rejected. With good
glue, like good cement, the material should rather give way than the
substance promoting adhesion. This is a very severe test, but in
putting it into practice you will be repaid by the stability of your work.
Waterproof Glue.
It is often found that joints glued together will allow water to

dissolve the glue, and thereby destroy its adhesive power. It may
have been well painted and every care taken to make it impervious
to water, but owing to its exposed position water has managed to get
in. Often where screws are put in the glue around them will be
dissolved, caused by the screws sweating; and it is very often found,
where the screws are inserted in a panel, that the glue loses its
strength and allows the joint to open, and there is little or no
appearance of glue on the wood, which shows that it has been
absorbed by the moisture.
To render ordinary glue insoluble, the water with which it is mixed
should have a little bichromate of potash dissolved in it. Chromic
acid has the property of rendering glue or gelatine insoluble. And, as
the operation of heating the glue pot is conducted in the light, no
special exposure of the pieces joined is necessary.
Glue prepared in this manner is preferable in gluing the panels on
bodies, which are liable to the action of water or damp. The strength
of the glue is not affected by the addition of the potash.
In plugging screw holes glue the edge of the plug; put no glue into
the hole. By this means the surplus glue is left on the surface, and if
the plug does not hit the screw it will seldom show.
Where brads are used the heads should be well set in; then pass
a sponge well saturated with hot water over them, filling the holes
with water. This brings the wood more to its natural position, and it
closes by degrees over the brad heads. The brad must have a
chance to expand, when exposed to the heat of the sun, without
hitting the putty stopping; if it does it will force the putty out so as to
show, by disturbing the surface, after the work is finished.
CHAPTER V.
PARTS COMPOSING THE UNDER-CARRIAGE.

—FRAMING THEM TOGETHER.—WROUGHT-
IRON PERCHES.—BRAKES.
We have now to consider the construction of the lower framework, or
carriage.
The following is a list of the chief parts of a coach, as generally
known:—
Wheels.
Axles.
Springs.
Beds, or cross framing timbers, which are technically termed the
fore axle bed, the hind axle bed, fore spring bed or transom,
hind spring bed, and horn bar.
Perch, or central longitudinal timber connecting the axletrees.
Wings, which are spreading sides, hooped to the perch and
framed to the hind beds.
Nunters, or small framing pieces, which help to bind the hind
beds together.
Hooping-piece. A piece of timber scarped and hooped to the
fore end of the perch to secure it to the
Wheel plate, which is the circular iron beneath which the fore
carriage turns.
The fore carriage consists of the fore axle beds, into which are
framed the
Futchells (French, fourchil, a fork), which are the longitudinal
timbers supporting the
Splinter-bar and the
Pole, to which the horses are attached.
The hinder ends of the futchells support the
Sway-bar—a circular piece of timber working beneath the
wheel-plate.
A circular piece of timber of smaller size, supported on the fore
part of the futchells for a similar purpose, is called the
Felloe-piece (often made of iron).
On the splinter-bar are fixed the
Roller bolts, for fastening the traces.
On the pole is fixed the
Pole hook, to secure the harness.
The perch and beds are strengthened with iron plates, where
necessary, and the other ironwork consists of
Splinter-bar stays, to resist the action of the draught. Formerly
these were affixed to the ends of the axles and called
“wheel-irons.”
Tread-steps, for the coachman to mount by.
Footman’s step.
Spring-stays.
On the beds are placed
Blocks, to support the
C springs; to which are attached

Jacks, or small windlasses, and
Leathern suspension braces.
These parts fitted together would form what is generally known as
a coach, or a vehicle, the body of which is large, and suspended by
leathern braces from the ends of C springs. They enter into the
formation of all vehicles more or less, but for the other kinds some
part or parts are omitted, as in a brougham hung on elliptic springs,
the C springs, perch, leather braces, &c., would be omitted, and, of
course, elliptic springs and a pump-handle would be added. All the
woodwork is lightened as much as possible by the introduction of
beading, carving, chamfering, &c.
In starting the carriage part the workman first takes the perch and
planes a flat side to it, and then works it taper from front to back. The
top and bottom curves are then worked up, or at least some portion
of them, and then the front and hind spring beds are framed on. A
pair of spreading wings are then fitted to the sides of the perch;
these are simply circular iron stays, swelled and moulded to take off
their plainness. A pair is fitted at each end of the perch. The hind
axletree bed is then scarfed upon the top of the perch and wings,
and is connected with the hind spring bed by two small framing
pieces called nunters. At the front end of the perch a cross bed
called a horn-bar is scarfed on the perch, at the same distance from
the fore spring bed as the hind axle bed is from the hind spring bed,
viz. the length of the bearing of the spring, or about 15 inches. The
horn-bar is connected with the fore spring bed by the two spring
blocks, which are either framed into them or scarfed down on them,
and also by the hooping-piece, which is scarfed on the top of the
perch. The perch is then planed up to the curve it is to have when
finished, and it is then taken to the smith, who fits and rivets on the
side plates, which have ears at the ends for the purpose of bolting
them to the beds. The carver then does his work by beading the
perch and beds, having due regard to the finish of the parts, rounds
and curves all the ends. On the under side of the perch is riveted an
iron plate, and on this plate is an iron hook for hanging the drag shoe
and chain (if such be used). The hind framing is now put together, all
connections being by means of mortises and tenons secured by

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Elaboration and Applications of Metal

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Series Editors: Karl M. Kadish (University of Houston, USA)

together authoritative contributions where the multidisciplinary character of

Vol. 4 Prospects for Li-ion Batteries and Emerging Energy

Vol. 3 Advanced Green Chemistry

Vol. 2 Elaboration and Applications of Metal-Organic Frameworks

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Devi - 10616 - Elaboration and Applications of Metal-Organic Frameworks.indd 2 29-12-17 8:51:09 AM

The materials known as metal-organic frameworks (MOFs) are experienc-

b2980_FM.indd 5 05-Jan-18 9:55:32 AM

both energy and environmental applications where MOFs have partici-

in Chapter 11, biomass conversion in Chapter 12, and photocatalysis in

b2980_FM.indd 6 05-Jan-18 9:55:32 AM

b2980_FM.indd 7 05-Jan-18 9:55:32 AM

1/D esign and Construction of Chemically Stable

b2980_FM.indd 9 05-Jan-18 9:55:32 AM

2 / A Survey of Metal-Organic Frameworks Based on

A. Designing MOFs with Programmable

b2980_FM.indd 10 05-Jan-18 9:55:32 AM

a. Metal Phosphonates as Proton

Phosphine Oxide and Phosphonium MOFs

b2980_FM.indd 11 05-Jan-18 9:55:32 AM

a. Magnetism within 2-D Sulfonate

a. Structural Development of Sulfone

b2980_FM.indd 12 05-Jan-18 9:55:32 AM

3/P ostsynthetic Linker Exchange in Metal-Organic

A. Control of Pore Size���������������������������������������������� 148

4 / Hydrogen Storage in Metal-Organic Frameworks 183

b2980_FM.indd 13 05-Jan-18 9:55:32 AM

B. MOFs as Hydrogen Storage Materials������������������� 187

E. Ligands and Ligand Functionalization������������������� 199

5/M ethane Storage in Metal-Organic Frameworks: Insights

b2980_FM.indd 14 05-Jan-18 9:55:32 AM

C. Open Metal Sites�������������������������������������������������� 225

1. Copper Based Tricarboxylic Ligand,

6 / S eparation of Light Hydrocarbons by Metal-Organic

b2980_FM.indd 15 05-Jan-18 9:55:32 AM

7/M etal-Organic Framework Membrane Synthesis

A.  In Situ Growth Method����������������������������������������� 286

8/M etal-Organic Frameworks: An Advanced Class

b2980_FM.indd 16 05-Jan-18 9:55:33 AM

E. Cationic MOFs for Drug Delivery�������������������������� 366

9 / Metal-Organic Frameworks for Heavy Metal Removal 377

Yan-Lung Wong, Yunlong Hou and Zhengtao Xu

10 / S ynthesis and Applications of Homochiral

b2980_FM.indd 17 05-Jan-18 9:55:33 AM

1/D esign and Construction of Chemically Stable

2 / A Survey of Metal-Organic Frameworks Based on

A. Designing MOFs with Programmable

a. Metal Phosphonates as Proton

a. Magnetism within 2-D Sulfonate

a. Structural Development of Sulfone

3/P ostsynthetic Linker Exchange in Metal-Organic

A. Control of Pore Size�� 148

4 / Hydrogen Storage in Metal-Organic Frameworks 183

B. MOFs as Hydrogen Storage Materials�� 187

E. Ligands and Ligand Functionalization�� 199

5/M ethane Storage in Metal-Organic Frameworks: Insights

C. Open Metal Sites�� 225

1. Copper Based Tricarboxylic Ligand,

6 / S eparation of Light Hydrocarbons by Metal-Organic

7/M etal-Organic Framework Membrane Synthesis

A. In Situ Growth Method�� 286

8/M etal-Organic Frameworks: An Advanced Class

E. Cationic MOFs for Drug Delivery�� 366

9 / Metal-Organic Frameworks for Heavy Metal Removal 377

10 / S ynthesis and Applications of Homochiral

II. Lewis Acidic MOFs and Catalysis�� 444

B. MOFs with CUM Sites of Defective Origin�� 459

A. MOF Catalysts with Hybrid Lewis/Brønsted

13 / Metal-Organic Frameworks for Photocatalysis 519

3. Other Types of Oxidation Reactions�� 564

VI. References�� 574

14 / Energy Transfer in Metal-Organic Frameworks 581

V. Nonporphyrinic, Organic Chromophore-Based

15 / Electrically Conductive Metal-Organic Frameworks 655

III. Polyoxometalates@MOF Composites�� 692

VIII. Acknowledgments�� 700

C. Metal and Ligand Exchange 28