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3-dimensional linker-based metal–organic frameworks for sub-angstrom control and enhanced thermal stability

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Abstract

Metal–organic frameworks (MOFs) are some of the best materials for energy-efficient separations, like membranes and adsorption processes, due to their nanoporosity and tunability. To tune a MOF for optimum separation of molecules with sub-angstrom differences in size, which is a common challenge in industrial separations, precise control of the local pore environment is required. Here, we explore the concept of “3-dimensional” linkers, i.e., linkers that contain sterically bulky non-planar cores, as a means to attain sub-angstrom control over MOF pore size and to control structural flexibility. In particular, the introduction of 3-dimensional linkers (3DLs) is shown to hinder global breathing transitions in MOFs. Because these linkers occupy a consistent volume regardless of their orientation, they also allow for precise size-based separation of very similar molecules, such as hexane isomers. Furthermore, we discuss the thermal stability of a subset of these materials, characterized through variable temperature X-ray diffraction and porosity measurements.

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Acknowledgments

O.K.F. and R.Q.S. gratefully acknowledge support from the Separation Science program of the U.S. Department of Energy (DE-FG02-08ER15967). C.S.S. thanks the International Institute of Nanotechnology at Northwestern University for support under the Ryan Fellowship.

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Authors and Affiliations

  1. Department of Chemical and Biological Engineering, Northwestern University, Evanston, IL, 60208, USA

    Courtney S. Smoljan, Randall Q. Snurr & Omar K. Farha

  2. Department of Chemistry and International Institute for Nanotechnology, Northwestern University, Evanston, IL, 60208, USA

    Omar K. Farha

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  1. Courtney S. Smoljan
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C.S.S. wrote the manuscript under the supervision of R.Q.S. and O.K.F.

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Correspondence to Omar K. Farha.

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OKF and RQS have a financial interest in NuMat Technologies, a startup company that is seeking to commercialize MOFs. CSS declares no competing interests.

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Smoljan, C.S., Snurr, R.Q. & Farha, O.K. 3-dimensional linker-based metal–organic frameworks for sub-angstrom control and enhanced thermal stability. Journal of Materials Research 39, 1047–1056 (2024). https://doi.org/10.1557/s43578-024-01309-5

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