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Nano Research 2021, 14(2): 355-368 https://doi.org/10.1007/s12274-020-2953-z
Review Article | Open Access | Issue | Published: 20 July 2020

Hierarchical assemblies of molecular frameworks—MOF-on-MOF epitaxial heterostructures

Show Author's Information Ritesh Haldar,  Christof Wöll( )
Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz, 176344 Eggenstein-Leopoldshafen, Germany
Keywords:
epitaxy, metal-organic framework (MOF) heterostructure, hierarchical assembly, layer-by-layer growth, surface-anchored MOFs
Topics:
Nanocrystalline materials OrganometallicsPore sizePorous materials
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Haldar R, Wöll C. Hierarchical assemblies of molecular frameworks—MOF-on-MOF epitaxial heterostructures. Nano Research, 2021, 14(2): 355-368. https://doi.org/10.1007/s12274-020-2953-z
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Abstract Full text About this article

Functional, porous metal-organic frameworks (MOFs) have attracted much attention as a very flexible class of crystalline, porous materials. For more advanced applications that exploit photophysical properties, the fabrication of hierarchical assemblies, including the creation of MOF/MOF heterointerfaces, is important. For the manufacturing of superstructures with length scales well beyond that of the MOF pore size, layer-by-layer (lbl) methods are particularly attractive. These allow the isoreticular approach to be extended to superstructures with micrometer length scales, a range that is not accessible using conventional MOF design. The lbl approach further substantially extends the compositional diversity in MOFs. At the same time, the favorable elastic properties of MOFs allow for heteroepitaxial growth, even in the case of lattice misfits as large as 20%. While the MOF-on-MOF approach to designing multicomponent superstructures with synergistic multifunctionality can also be realized with sophisticated solvothermal synthesis schemes, the lbl (or liquid-phase epitaxy) approach carries substantial advantages, in particular when it comes to the integration of such MOF superstructures into optical or electronic devices. While the structure vertical to the substrate can be adjusted using the lbl method, photolithographic methods can be used for lateral structuring. In this review, we will discuss the lbl liquid-phase epitaxy approach to growing surface-anchored MOF thins films (SURMOFs) as well as other relevant one-pot synthesis methods for constructing such hierarchically designed structures and their emerging applications.


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About this article

Hierarchical assemblies of molecular frameworks—MOF-on-MOF epitaxial heterostructures

Show Author's information Ritesh Haldar, Christof Wöll( )
Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology (KIT), Hermann-von-Helmholtz-Platz, 176344 Eggenstein-Leopoldshafen, Germany

Abstract

Functional, porous metal-organic frameworks (MOFs) have attracted much attention as a very flexible class of crystalline, porous materials. For more advanced applications that exploit photophysical properties, the fabrication of hierarchical assemblies, including the creation of MOF/MOF heterointerfaces, is important. For the manufacturing of superstructures with length scales well beyond that of the MOF pore size, layer-by-layer (lbl) methods are particularly attractive. These allow the isoreticular approach to be extended to superstructures with micrometer length scales, a range that is not accessible using conventional MOF design. The lbl approach further substantially extends the compositional diversity in MOFs. At the same time, the favorable elastic properties of MOFs allow for heteroepitaxial growth, even in the case of lattice misfits as large as 20%. While the MOF-on-MOF approach to designing multicomponent superstructures with synergistic multifunctionality can also be realized with sophisticated solvothermal synthesis schemes, the lbl (or liquid-phase epitaxy) approach carries substantial advantages, in particular when it comes to the integration of such MOF superstructures into optical or electronic devices. While the structure vertical to the substrate can be adjusted using the lbl method, photolithographic methods can be used for lateral structuring. In this review, we will discuss the lbl liquid-phase epitaxy approach to growing surface-anchored MOF thins films (SURMOFs) as well as other relevant one-pot synthesis methods for constructing such hierarchically designed structures and their emerging applications.

Keywords: epitaxy, metal-organic framework (MOF) heterostructure, hierarchical assembly, layer-by-layer growth, surface-anchored MOFs

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Received: 04 March 2020
Revised: 31 May 2020
Accepted: 26 June 2020
Published: 20 July 2020
Issue date: February 2021

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© The Author(s) 2020

Acknowledgements

The authors acknowledge support from Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany’s Excellence Strategy—2082/1—390761711 and SPP 1928 "COORNETS." We thank Xiaojing Liu for comments on the manuscript.

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