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Title: Hierarchically porous metal–organic frameworks: synthetic strategies and applications

Journal Article · · National Science Review
DOI:https://doi.org/10.1093/nsr/nwz170· OSTI ID:1712817
 [1];  [1];  [1];  [1];  [1]
  1. Department of Chemistry, Texas A&M University, College Station, TX 77843, USA

Abstract Despite numerous advantages, applications of conventional microporous metal–organic frameworks (MOFs) are hampered by their limited pore sizes, such as in heterogeneous catalysis and guest delivery, which usually involve large molecules. Construction of hierarchically porous MOFs (HP-MOFs) is vital to achieve the controllable augmentation of MOF pore size to mesopores or even macropores, which can enhance the diffusion kinetics of guests and improve the storage capacity. This review article focuses on recent advances in the methodology of HP-MOF synthesis, covering preparation of HP-MOFs with intrinsic hierarchical pores, and modulated, templated and template-free synthetic strategies for HP-MOFs. The key factors which affect the formation of HP-MOF architectures are summarized and discussed, followed by a brief review of their applications in heterogeneous catalysis and guest encapsulation. Overall, this review presents a roadmap that will guide the future design and development of HP-MOF materials with molecular precision and mesoscopic complexity.

Research Organization:
Univ. of California, Oakland, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Center for Gas Separations; Robert A. Welch Foundation
Grant/Contract Number:
SC0001015; A-0030
OSTI ID:
1712817
Alternate ID(s):
OSTI ID: 1573110; OSTI ID: 1850687
Journal Information:
National Science Review, Journal Name: National Science Review Vol. 7 Journal Issue: 11; ISSN 2095-5138
Publisher:
Oxford University PressCopyright Statement
Country of Publication:
China
Language:
English

References (114)

Piezofluorochromic Metal–Organic Framework: A Microscissor Lift journal August 2015
The effect of water adsorption on the structure of the carboxylate containing metal–organic frameworks Cu-BTC, Mg-MOF-74, and UiO-66 journal January 2013
Synthesis, Structure, and Metalation of Two New Highly Porous Zirconium Metal–Organic Frameworks journal June 2012
Stable Metal-Organic Frameworks: Design, Synthesis, and Applications journal February 2018
Isotherms of individual pores by gas adsorption crystallography journal May 2019
Synthesis and Integration of Fe-soc-MOF Cubes into Colloidosomes via a Single-Step Emulsion-Based Approach journal May 2013
Advanced fabrication of metal–organic frameworks: template-directed formation of polystyrene@ZIF-8 core–shell and hollow ZIF-8 microspheres journal January 2012
Flexible and Hierarchical Metal-Organic Framework Composites for High-Performance Catalysis journal June 2018
Metal–organic framework materials as catalysts journal January 2009
An Isoreticular Series of Metal-Organic Frameworks with Dendritic Hexacarboxylate Ligands and Exceptionally High Gas-Uptake Capacity journal June 2010
Observing the Growth of Metal–Organic Frameworks by in Situ Liquid Cell Transmission Electron Microscopy journal June 2015
Controlled Multiscale Synthesis of Porous Coordination Polymer in Nano/Micro Regimes journal August 2010
Uncovering Two Principles of Multivariate Hierarchical Metal–Organic Framework Synthesis via Retrosynthetic Design journal December 2018
Successful implementation of the stepwise layer-by-layer growth of MOF thin films on confined surfaces: mesoporous silica foam as a first case study journal January 2012
Yolk–Shell Nanocrystal@ZIF-8 Nanostructures for Gas-Phase Heterogeneous Catalysis with Selectivity Control journal August 2012
Structural Complexity in Metal–Organic Frameworks: Simultaneous Modification of Open Metal Sites and Hierarchical Porosity by Systematic Doping with Defective Linkers journal June 2014
Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation : Adding to the Arsenal of Zirconium-Based Metal-Organic Frameworks: the Topology as a Platform for Solvent-Assisted Metal Incorporation journal July 2016
A Highly Stable Zeotype Mesoporous Zirconium Metal-Organic Framework with Ultralarge Pores journal November 2014
Unusual and Highly Tunable Missing-Linker Defects in Zirconium Metal–Organic Framework UiO-66 and Their Important Effects on Gas Adsorption journal May 2013
Extended and functionalized porous iron(iii) tri- or dicarboxylates with MIL-100/101 topologies journal January 2014
Introduction of Functionalized Mesopores to Metal–Organic Frameworks via Metal–Ligand–Fragment Coassembly journal December 2012
3D-Printed MOF-Derived Hierarchically Porous Frameworks for Practical High-Energy Density Li-O 2 Batteries journal November 2018
An alternative synthetic approach for macro–meso–microporous metal–organic frameworks via a “domain growth” mechanism journal January 2016
Tuning the structure and function of metal–organic frameworks via linker design journal January 2014
Controllable Modular Growth of Hierarchical MOF-on-MOF Architectures journal November 2017
Hierarchical Structure with Highly Ordered Macroporous-Mesoporous Metal-Organic Frameworks as Dual Function for CO2 Fixation journal May 2019
Stable metal-organic frameworks containing single-molecule traps for enzyme encapsulation journal January 2015
Exploring the Role of Hexanuclear Clusters as Lewis Acidic Sites in Isostructural Metal–Organic Frameworks journal May 2019
Adsorption of a Catalytically Accessible Polyoxometalate in a Mesoporous Channel-type Metal–Organic Framework journal May 2017
A Single-Crystal Open-Capsule Metal–Organic Framework journal April 2019
Hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design journal January 2008
Metal-Organic Framework Nanospheres with Well-Ordered Mesopores Synthesized in an Ionic Liquid/CO2/Surfactant System journal December 2010
A spray-drying strategy for synthesis of nanoscale metal–organic frameworks and their assembly into hollow superstructures journal February 2013
Hierarchical Porous Zr-Based MOFs Synthesized by a Facile Monocarboxylic Acid Etching Strategy journal February 2018
Heterogeneity within Order in Crystals of a Porous Metal–Organic Framework journal August 2011
Cooperative Template-Directed Assembly of Mesoporous Metal–Organic Frameworks journal December 2011
Creating Hierarchical Pores by Controlled Linker Thermolysis in Multivariate Metal–Organic Frameworks journal January 2018
An in situ self-assembly template strategy for the preparation of hierarchical-pore metal-organic frameworks journal November 2015
Hybrid Polyoxotungstate/MIL-101 Materials: Synthesis, Characterization, and Catalysis of H 2 O 2 -Based Alkene Epoxidation journal March 2010
Nano-Biohybrids: In Vivo Synthesis of Metal-Organic Frameworks inside Living Plants journal November 2017
Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage journal January 2002
Carbon Dioxide Capture in Metal–Organic Frameworks journal September 2011
Nanosizing a Metal–Organic Framework Enzyme Carrier for Accelerating Nerve Agent Hydrolysis journal October 2016
Aqueous-Phase Synthesis of Mesoporous Zr-Based MOFs Templated by Amphoteric Surfactants journal February 2018
A Chromium Terephthalate-Based Solid with Unusually Large Pore Volumes and Surface Area journal September 2005
Tuned to Perfection: Ironing Out the Defects in Metal–Organic Framework UiO-66 journal July 2014
Highly Stable Zr(IV)-Based Metal–Organic Frameworks for the Detection and Removal of Antibiotics and Organic Explosives in Water journal May 2016
Template-Free Synthesis of Hierarchical Porous Metal–Organic Frameworks journal June 2013
Synthesis of Hierarchically Structured Hybrid Materials by Controlled Self-Assembly of Metal–Organic Framework with Mesoporous Silica for CO 2 Adsorption journal June 2017
One-Step Synthesis of Hybrid Core-Shell Metal-Organic Frameworks journal March 2018
Zirconium-Metalloporphyrin PCN-222: Mesoporous Metal-Organic Frameworks with Ultrahigh Stability as Biomimetic Catalysts journal August 2012
Hierarchical bicontinuous porosity in metal–organic frameworks templated from functional block co-oligomer micelles journal January 2013
Void Engineering in Metal-Organic Frameworks via Synergistic Etching and Surface Functionalization journal June 2016
A Chemically Functionalizable Nanoporous Material [Cu3(TMA)2(H2O)3]n journal February 1999
Hollowing out MOFs: hierarchical micro- and mesoporous MOFs with tailorable porosity via selective acid etching journal January 2017
MIL-53(Al) mesostructured metal-organic frameworks journal May 2011
Ultrahigh Porosity in Metal-Organic Frameworks journal July 2010
Ligand Symmetry Modulation for Designing a Mesoporous Metal-Organic Framework: Dual Reactivity to Transition and Lanthanide Metals for Enhanced Functionalization journal May 2015
Hollow Zn/Co ZIF Particles Derived from Core-Shell ZIF-67@ZIF-8 as Selective Catalyst for the Semi-Hydrogenation of Acetylene journal August 2015
Tackling the Defect Conundrum in UiO-66: A Mixed-Linker Approach to Engineering Missing Linker Defects journal November 2017
Bioactive MIL-88A Framework Hollow Spheres via Interfacial Reaction In-Droplet Microfluidics for Enzyme and Nanoparticle Encapsulation journal November 2015
Correlated defect nanoregions in a metal–organic framework journal June 2014
Modulation versus Templating: Fine‐Tuning of Hierarchally Porous PCN‐250 Using Fatty Acids To Engineer Guest Adsorption journal September 2019
A Hybrid Solid with Giant Pores Prepared by a Combination of Targeted Chemistry, Simulation, and Powder Diffraction journal August 2004
Hierarchically mesostructured MIL-101 metal–organic frameworks: supramolecular template-directed synthesis and accelerated adsorption kinetics for dye removal journal January 2012
Hierarchically porous metal–organic frameworks: rapid synthesis and enhanced gas storage journal January 2018
Linking defects, hierarchical porosity generation and desalination performance in metal–organic frameworks journal January 2018
Introduction to Metal–Organic Frameworks journal September 2011
Porphyrinic Metal–Organic Frameworks Installed with Brønsted Acid Sites for Efficient Tandem Semisynthesis of Artemisinin journal March 2019
The chemistry of multi-component and hierarchical framework compounds journal January 2019
Engineering of Pore Geometry for Ultrahigh Capacity Methane Storage in Mesoporous Metal–Organic Frameworks journal September 2017
Flexible and Porous Nanocellulose Aerogels with High Loadings of Metal-Organic-Framework Particles for Separations Applications journal June 2016
Hydrogen Storage in Microporous Metal-Organic Frameworks journal May 2003
Selective gas adsorption and separation in metal–organic frameworks journal January 2009
Impact of Synthesis Parameters on the Formation of Defects in HKUST-1: Impact of Synthesis Parameters on the Formation of Defects in HKUST-1 journal February 2017
Enantioselective catalysis with homochiral metal–organic frameworks journal January 2009
The Organic Secondary Building Unit: Strong Intermolecular π Interactions Define Topology in MIT-25, a Mesoporous MOF with Proton-Replete Channels journal March 2017
Adsorption/desorption kinetics and breakthrough of gaseous toluene for modified microporous-mesoporous UiO-66 metal organic framework journal March 2019
Hydrolytic Transformation of Microporous Metal-Organic Frameworks to Hierarchical Micro- and Mesoporous MOFs journal September 2015
Formation of trigons in a metal–organic framework: The role of metal–organic polyhedron subunits as meta-atoms journal January 2019
Vapor-Phase Metalation by Atomic Layer Deposition in a Metal–Organic Framework
  • Mondloch, Joseph E.; Bury, Wojciech; Fairen-Jimenez, David
  • Journal of the American Chemical Society, Vol. 135, Issue 28, p. 10294-10297 https://doi.org/10.1021/ja4050828
journal May 2013
Lattice Expansion and Contraction in Metal-Organic Frameworks by Sequential Linker Reinstallation journal July 2019
Hierarchically Engineered Mesoporous Metal-Organic Frameworks toward Cell-free Immobilized Enzyme Systems journal May 2018
Modular Programming of Hierarchy and Diversity in Multivariate Polymer/Metal–Organic Framework Hybrid Composites journal May 2019
Postsynthetic Selective Ligand Cleavage by Solid–Gas Phase Ozonolysis Fuses Micropores into Mesopores in Metal–Organic Frameworks journal October 2018
Mesoporous Metal-Organic Frameworks with Size-, Shape-, and Space-Distribution-Controlled Pore Structure journal March 2015
Facile Fabrication of Multifunctional Metal–Organic Framework Hollow Tubes To Trap Pollutants journal November 2017
A mesoporous NNN-pincer-based metal–organic framework scaffold for the preparation of noble-metal-free catalysts journal January 2019
High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture journal February 2008
Toward Design Rules for Enzyme Immobilization in Hierarchical Mesoporous Metal-Organic Frameworks journal July 2016
Topological Analysis of Metal–Organic Frameworks with Polytopic Linkers and/or Multiple Building Units and the Minimal Transitivity Principle journal November 2013
Bottom-up construction of a superstructure in a porous uranium-organic crystal journal April 2017
In Situ Growth of Metal–Organic Frameworks in Three-Dimensional Aligned Lumen Arrays of Wood for Rapid and Highly Efficient Organic Pollutant Removal journal February 2019
De novo synthesis of a metal–organic framework material featuring ultrahigh surface area and gas storage capacities journal September 2010
Ordered macro-microporous metal-organic framework single crystals journal January 2018
From fundamentals to applications: a toolbox for robust and multifunctional MOF materials journal January 2018
A Modulator-Induced Defect-Formation Strategy to Hierarchically Porous Metal-Organic Frameworks with High Stability journal December 2016
Nanoparticles of Metal-Organic Frameworks: On the Road to In Vivo Efficacy in Biomedicine journal June 2018
Mixed-Linker Hybrid Superpolyhedra for the Production of a Series of Large-Pore Iron(III) Carboxylate Metal-Organic Frameworks journal April 2013
Toward Topology Prediction in Zr-Based Microporous Coordination Polymers: The Role of Linker Geometry and Flexibility journal May 2016
A Mesoporous Indium Metal–Organic Framework: Remarkable Advances in Catalytic Activity for Strecker Reaction of Ketones journal July 2016
Synthesis and Enhanced H 2 Adsorption Properties of a Mesoporous Nanocrystal of MOF-5: Controlling Nano-/Mesostructures of MOFs To Improve Their H 2 Heat of Adsorption journal October 2010
Construction of hierarchically porous metal–organic frameworks through linker labilization journal May 2017
Hierarchically Micro- and Mesoporous Metal-Organic Frameworks with Tunable Porosity journal November 2008
Roll-to-Roll Production of Metal-Organic Framework Coatings for Particulate Matter Removal journal January 2017
Direct Imaging of Tunable Crystal Surface Structures of MOF MIL-101 Using High-Resolution Electron Microscopy journal July 2019
Control the Structure of Zr-Tetracarboxylate Frameworks through Steric Tuning journal November 2017
Copper Benzene Tricarboxylate Metal–Organic Framework with Wide Permanent Mesopores Stabilized by Keggin Polyoxometallate Ions journal June 2012
Design and synthesis of an exceptionally stable and highly porous metal-organic framework journal November 1999
Synthesis of Metal-Organic Frameworks (MOFs): Routes to Various MOF Topologies, Morphologies, and Composites journal September 2011
Temperature-Controlled Evolution of Nanoporous MOF Crystallites into Hierarchically Porous Superstructures journal May 2019
Highly mesoporous metal–organic framework assembled in a switchable solvent journal July 2014
Construction of Hierarchically Porous Nanoparticles@Metal-Organic Frameworks Composites by Inherent Defects for the Enhancement of Catalytic Efficiency journal October 2018
Mesoporous Cages in Chemically Robust MOFs Created by a Large Number of Vertices with Reduced Connectivity journal November 2018