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Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000

Nature Protocols volume 11, pages 149–162 (2016)Cite this article

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Abstract

The synthesis of NU-1000, a highly robust mesoporous (containing pores >2 nm) metal-organic framework (MOF), can be conducted efficiently on a multigram scale from inexpensive starting materials. Tetrabromopyrene and (4-(ethoxycarbonyl)phenyl)boronic acid can easily be coupled to prepare the requisite organic strut with four metal-binding sites in the form of four carboxylic acids, while zirconyl chloride octahydrate is used as a precursor for the well-defined metal oxide clusters. NU-1000 has been reported as an excellent candidate for the separation of gases, and it is a versatile scaffold for heterogeneous catalysis. In particular, it is ideal for the catalytic deactivation of nerve agents, and it shows great promise as a new generic platform for a wide range of applications. Multiple post-synthetic modification protocols have been developed using NU-1000 as the parent material, making it a potentially useful scaffold for several catalytic applications. The procedure for the preparation of NU-1000 can be scaled up reliably, and it is suitable for the production of 50 g of the tetracarboxylic acid containing organic linker and 200 mg–2.5 g of NU-1000. The entire synthesis is performed without purification by column chromatography and can be completed within 10 d.

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Figure 1: Structure of NU-1000 and developed post-synthetic modification methods on this platform.
Figure 2: The two-step synthesis of the tetra acid ligand for NU-1000 can be accomplished in 3 d with an overall yield of 55% to produce 36 g of H4TBAPy (2) without the need for chromatographic purification.
Figure 3: Synthesis of NU-1000 from 2 and ZrOCl2 with benzoic acid as modulator.
Figure 4: Equipment setup for a 50-g-scale synthesis of H4TBAPy (2).
Figure 5
Figure 6
Figure 7: Equipment setup for 250-mg-scale AIM modification for Al-AIM (4).
Figure 8
Figure 9: 1H NMR spectrum of dissolved F3G-SALI.
Figure 10: Powder X-ray diffraction data for NU-1000.
Figure 11: 1H NMR spectrum of dissolved NU-1000.
Figure 12: Scanning electron microscopy (SEM) images of NU-1000.
Figure 13: Powder X-ray diffraction data of Al-AIM.
Figure 14
Figure 15: Powder X-ray diffraction data of F3G-SALI.

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Acknowledgements

This work (MOF assembly, experimental characterization and AIM) was supported as part of the Inorganometallic Catalyst Design Center, an Energy Frontier Research Center, funded by the US Department of Energy, Office of Science, Basic Energy Sciences, under Award no. DESC0012702 (to O.K.F., A.B.F.M. and J.T.H.). This research is part (project 34-944) of the Joint Center of Excellence in Integrated Nano-Systems (JCIN) at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU; to J.F.S.). The authors thank both KACST and NU for their continued support of this research.

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Authors and Affiliations

  1. Department of Chemistry, Northwestern University, Evanston, Illinois, USA

    Timothy C Wang, Nicolaas A Vermeulen, J Fraser Stoddart, Joseph T Hupp & Omar K Farha

  2. Material Science Division, Argonne National Laboratory, Argonne, Illinois, USA

    In Soo Kim & Alex B F Martinson

  3. Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah, Saudi Arabia

    Omar K Farha

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Contributions

T.C.W., N.A.V. and O.K.F. designed the experiments; T.C.W. and N.A.V. performed the synthesis of the strut and analyzed the collected data, and T.C.W. designed and performed the synthesis of NU-1000 with guidance from O.K.F.; I.S.K. performed the ALD experiments with guidance from A.B.F.M.; and T.C.W., N.A.V., I.S.K., A.B.F.M., J.F.S., J.T.H. and O.K.F. wrote the manuscript.

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Correspondence to Omar K Farha.

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Competing interests

J.T.H. and O.K.F. have a financial interest in the startup company NuMat Technologies, which is seeking to commercialize metal-organic frameworks.

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Wang, T., Vermeulen, N., Kim, I. et al. Scalable synthesis and post-modification of a mesoporous metal-organic framework called NU-1000. Nat Protoc 11, 149–162 (2016). https://doi.org/10.1038/nprot.2016.001

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