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Metal-Organic Frameworks
Author(s):
- Lars ÖhrströmProfessor, Chemistry & Chemical EngineeringChalmers University of TechnologyEmail: [email protected]More by Lars Öhrström
- Francoise M. Amombo NoaResearcherChalmers University of TechnologyEmail: [email protected]More by Francoise M. Amombo Noa
Publication Date:
March 25, 2021
Copyright ©
2020 American Chemical Society
eISBN:
9780841299047
DOI:
10.1021/acs.infocus.7e4004
Read Time:
six to seven hours
Collection:
Inaugural
Publisher:
American Chemical Society
Some 80,000 metal-organic frameworks (MOFs) have been reported as of 2020. With intriguing structures and fascinating properties, MOFs are poised to be a defining material of the 21st century with a great deal of commercial potential from methane fuel automobile tanks to carbon capturing.
Metal-Organic Frameworks provides an introduction to the complex world of MOFs. Researchers new to MOFs can use this work as a jumping-off point for theoretical study or applied research. The work is broad and expansive in scope, but inclusive and comprehensive in detail. The authors provide a personal perspective of MOF research that provides a strong foundation in the basic methods and themes as well as directs the reader in how to think about MOFs.
Sixteen MOF structures are animated, providing more clarity into the dimensionality of MOFs. Accompanying links take the reader to additional 3-D structures provided by The Cambridge Crystallographic Data Centre (CCDC).
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Detailed Table of Contents
About the Series
Preface
1.
Metal–Organic Frameworks in Perspective
1.1
Why MOFs?
1.2
The Chemistry of MOFs
1.3
What Kinds of Solids Are MOFs?
1.4
A Brief History of MOFs
1.4.1
Proving the Porosity by Gas Sorption in 1998
1.4.2
The Story Continues
1.5
Insider Q&A
1.6
MOFs versus Other Currently Commercially Used Porous Materials
1.6.1
Zeolites
1.6.2
Mesoporous Silica
1.6.3
Mesoporous Carbon
1.6.4
Other Emerging Porous Materials
1.7
Current Commercial MOF Applications
1.7.1
Companies Stretch from Multinationals to Tiny Startups
1.7.2
Patent Situation
1.8
Some Well-Known MOFs
1.9
Insider Q&A
1.10
That’s a Wrap
1.11
Read These Next
2.
How To Talk about MOFs
2.1
Talking about MOFs
2.2
Five Pillars of MOFs
2.2.1
Coordination Chemistry
2.2.2
Reticular Chemistry
2.2.3
Crystallography and Structure Elucidation
2.2.4
Gas Sorption Measurements of the Inside Space
2.2.5
Organic Synthesis
2.3
Why We Need Nomenclature and Terminology
2.3.1
IUPAC Terminology
2.3.2
IUPAC Nomenclature
2.3.3
Trivial Names
2.4
That’s a Wrap
2.5
Read These Next
3.
Reticular Chemistry
3.1
Reticular Chemistry: Network Chemistry
3.2
The Synthon
3.3
The Secondary Building Unit Approach
3.3.1
Geometry of Organic SBUs
3.3.2
Metal SBU Geometry
3.3.3
Rod and Sheet SBUs
3.4
Network Topology
3.4.1
Topology Descriptors: The Point Symbol
3.4.2
Topology Descriptors: The Coordination Sequence
3.4.3
Dual Nets and Interpenetration
3.4.4
Flexible Topologies
3.4.5
The Ambiguity of Vertex Assignment
3.5
Insider Q&A
3.6
That’s a Wrap
3.7
Read These Next
4.
Synthesis
4.1
Chemistry and Creativity
4.2
Design and General Comments
4.3
Insider Q&A
4.4
Coordination Chemistry Effects
4.5
Crystal Growth
4.6
Traditional Synthesis Methods
4.6.1
Classical Solution Chemistry
4.6.2
Solvothermal
4.6.3
Microwave
4.6.4
Mechanochemistry
4.7
Newer Synthesis Methods
4.7.1
Electrochemical
4.7.2
Sonochemistry
4.7.3
Spray-Drying
4.8
Final remarks on Synthesis Methods
4.9
Insider Q&A
4.10
Tools and Materials
4.10.1
Dry Baths
4.10.2
Convection Ovens
4.10.3
Microwave Ovens
4.11
Activation of MOFs
4.11.1
Conventional Activation
4.11.2
Solvent Exchange Activation
4.11.3
Supercritical Carbon Dioxide (CO2) Activation
4.11.4
Chemical Treatment Activation
4.11.5
Freeze-Drying Activation
4.12
That’s a Wrap
4.13
Read These Next
5.
Structure and Structure Determination
5.1
Thinking and Talking about Structures
5.2
Illustrating Molecular Structures
5.2.1
Illustrating Flexibility Is Hard
5.2.2
Ball-and-Spoke Models Are Deceiving
5.2.3
Hard Sphere Models Have Limitations
5.2.4
Crystal Structure Data Models Seldom Include Disorder and Defects
5.2.5
The Polyhedron Paradox
5.3
MOF Structure Overview
5.4
Example Structures
5.4.1
MOF-5 and MIL-101
5.4.2
HKUST-1
5.4.3
MOFs with bdc Derivatives
5.4.4
Zr-MOFs: UiO-66
5.5
Single Crystal X-ray Diffraction
5.5.1
Single Crystals—Crystallization
5.5.2
Crystal Selection and Mounting
5.5.3
Data Collection
5.5.4
Summary of Strengths and Weaknesses
5.6
Powder X-ray Diffraction
5.6.1
PXRD: Advantages and Disadvantages
5.7
What Can You Learn from a Published Structure?
5.7.1
Structure Correlations and Statistics
5.8
Crystalline Sponges—When the Framework Space Is in Focus
5.9
Beyond the Crystal—Amorphous MOFs
5.9.1
The Pair Distribution Function—Total X-Ray Scattering
5.10
That’s a Wrap
5.11
Read These Next
6.
Functionalized MOFs
6.1
Tinkering with MOFs and MOF Spaces
6.2
Functionalization Overview
6.3
In-Synthesis Modification
6.3.1
Multivariate MOFs
6.4
Postsynthetic Modification (PSM)
6.4.1
PSM-1: Ligand Exchange
6.4.2
PSM-2: Metal-Ion Exchange
6.4.3
PSM-3: Linker Exchange
6.4.4
PSM-4: Adding Linkers
6.4.5
PSM-5: Performing Reactions on the Linkers
6.4.6
PSM-6 Crystalline Sponges and More
6.5
Deliberate MOF Topology Transformations
6.5.1
Heating, Melting, and Quenching
6.5.2
Mechanochemical Transformations
6.5.3
Sol–Gel-Derived MOF Monoliths
6.5.4
Other Approaches to MOF Monoliths
6.6
Surfaces and MOFs—Wrapping Around or Being Wrapped Around
6.6.1
In Situ MOF Surface Modification
6.6.2
Postsynthesis MOF Surface Modification
6.6.3
MOFs on Solid Supports
6.7
That’s a Wrap
6.8
Read These Next
7.
Gas Sorption and Porosity
7.1
Introduction and Perspective on Gas Sorption Measurements
7.2
Sorption, Porosity, Surface Area, and Pore Volume
7.3
Gas Sorption Isotherms for Physisorption
7.3.1
Surface Area
7.3.2
Pore Volume and Size
7.3.3
Gas Sorption Isotherms: Eight Types
7.3.4
Gas Sorption Isotherm Hysteresis: Six Cases
7.4
Final Comments
7.5
That’s a Wrap
7.6
Read These Next
8.
Other Characterization Methods and Approaches
8.1
A Few Other General Techniques
8.2
Thermogravimetric Methods
8.3
Nuclear Magnetic Resonance (NMR) Methods
8.4
Elemental Analysis
8.5
Microscopy Techniques
8.6
Computational Methods
8.6.1
Quantum Chemistry and Molecular Mechanics
8.6.2
Databases and Machine Learning
8.7
That’s a Wrap
8.8
Read These Next
9.
Mechanical Properties
9.1
Macroscopic Models of the Solid State
9.2
General Mechanical Properties
9.2.1
Different Types of Mechanical Properties Often Measured and Discussed
9.3
Measuring MOF Mechanical Properties
9.3.1
Nanoindentation
9.3.2
High-Pressure Crystallography
9.3.3
Computational Methods
9.4
Unusal MOF Mechanical Properties
9.4.1
Negative Thermal Expansion (NTE)
9.4.2
Negative Poisson’s Ratios
9.5
That’s a Wrap
9.6
Read These Next
10.
Where to Now?
10.1
Read These Next
Appendix A
Appendix B
Bibliography
Glossary
Footnotes
Index
Reviewer quotes
Equip yourself to read more complex and cutting-edge works on MOFs
Metal-Organic Frameworks serves as a gateway to more technical literature. The text is thorough, yet easy to understand, and would be beneficial both to early researchers looking to explore the field further and scientists looking to learn more about a topic outside of their field.
Tour through the field of MOFs
This is an excellent tour through what is an otherwise extensive field of MOFs. It covers the most important intellectual and practical aspects of MOFs and in an understated manner communicates with great ease how MOFs have combined inorganic and organic chemistry and have changed the way we think about solid state structures and materials.
On-the-job MOF training
This is excellent for a newcomer to the field as it is a readable and approachable document. Moreover, it shares some common frustrations of practitioners that are less commonly reported papers but more on-the-job training. The buildup from basic coordination chemistry and supramolecular principles is valuable.
Dr. Lars Öhrström is Professor of Inorganic Chemistry at the Department of Chemistry and Chemical Engineering at Chalmers University of Technology in Gothenburg. He received his M.Sc. in Chemical Engineering, and Ph.D. in chemistry, from the Royal Institute of Technology in Stockholm 1988 and 1993 respectively. He completed postdoctoral training at the Alternative Energies and Atomic Energy Commission, CEA, in Grenoble prior to joining Chalmers in 1995. He co-authored Molecule Based Materials – The Structural Network Approach in 2005 and is also a prolific popular science writer. He received the Gunnar Starck medal from the Swedish Chemical Society in 2018. Photo: Johan Bodell, Kw Studios
Dr. Francoise M. Amombo Noa is a researcher with expertise in supramolecular chemistry, reticular chemistry and crystallography. She is currently working on synthesis and characterization of metal-organic frameworks with emphasis on host-guest aspects, environmental applications and structural chemistry. Prior to her present position at Chalmers University of Technology she did postdoctoral training at the Centre for Supramolecular Chemistry Research at the University of Cape Town, and has also held a position at Engen Petroleum. She received a Ph.D. in Chemistry from the University of Cape Town in 2017 following M.Sc. and B.Sc. degrees in Chemistry from the Cape Peninsula University of Technology in Cape Town 2014 and 2012 respectively. Photo: Johan Bodell, Kw Studios
