Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers

Courtney S. Smoljan; Zhao Li; Haomiao Xie; Caitlin J. Setter; Karam B. Idrees; Florencia A. Son; Filip Formalik; Saman Shafaie; Timur Islamoglu; Lauren K. Macreadie; Randall Q. Snurr; Omar K. Farha

doi:10.1021/jacs.2c13715

Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers

Courtney S. Smoljan, Zhao Li, Haomiao Xie, Caitlin J. Setter, Karam B. Idrees, Florencia A. Son, Filip Formalik, Saman Shafaie, Timur Islamoglu, Lauren K. Macreadie^*, Randall Q. Snurr^*, Omar K. Farha^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

28 Scopus citations

Abstract

Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.

Original language	English (US)
Pages (from-to)	6434-6441
Number of pages	8
Journal	Journal of the American Chemical Society
Volume	145
Issue number	11
DOIs	https://doi.org/10.1021/jacs.2c13715
State	Published - Mar 22 2023

Funding

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). L.K.M. gratefully acknowledges ARC DE210101627. This work made use of the IMSERC X-RAY facility at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), and Northwestern University and the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the SHyNE Resource (NSF ECCS-2025633), the IIN, and Northwestern’s MRSEC program (NSF DMR-1720139). Z.L. acknowledges support from a Data Science Fellowship via the Northwestern Institute on Complex Systems (NICO). This research was partly supported through the computational resources provided for the Quest High-Performance Computing Facility at Northwestern University, which is jointly supported by the Office of the Provost, the Office for Research, and Northwestern University Information Technology. We also gratefully acknowledge the resources provided by the National Energy Research Scientific Computing Center (NERSC), a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under contract no. DE-AC02-05CH11231. F.F. is supported by the Polish National Agency for Academic Exchange (decision no. BPN/BEK/2021/1/00184/DEC/). F.A.S. is supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate (NDSEG) Fellowship Program and the Ryan Fellowship through the International Institute for Nanotechnology at Northwestern University.

ASJC Scopus subject areas

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/jacs.2c13715

Cite this

Smoljan, C. S., Li, Z., Xie, H., Setter, C. J., Idrees, K. B., Son, F. A., Formalik, F., Shafaie, S., Islamoglu, T., Macreadie, L. K., Snurr, R. Q., & Farha, O. K. (2023). Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers. Journal of the American Chemical Society, 145(11), 6434-6441. https://doi.org/10.1021/jacs.2c13715

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abstract = "Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.",

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AB - Metal-organic frameworks (MOFs) are highly tunable materials with potential for use as porous media in non-thermal adsorption or membrane-based separations. However, many separations target molecules with sub-angstrom differences in size, requiring precise control over the pore size. Herein, we demonstrate that this precise control can be achieved by installing a three-dimensional linker in an MOF with one-dimensional channels. Specifically, we synthesized single crystals and bulk powder of NU-2002, an isostructural framework to MIL-53 with bicyclo[1.1.1]pentane-1,3-dicarboxylic acid as the organic linker component. Using variable-temperature X-ray diffraction studies, we show that increasing linker dimensionality limits structural breathing relative to MIL-53. Furthermore, single-component adsorption isotherms demonstrate the efficacy of this material for separating hexane isomers based on the different sizes and shapes of these isomers.

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Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers

Abstract

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CCDC 2234122: Experimental Crystal Structure Determination

CCDC 2234123: Experimental Crystal Structure Determination

CCDC 2234124: Experimental Crystal Structure Determination

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Engineering Metal-Organic Frameworks for Selective Separation of Hexane Isomers Using 3-Dimensional Linkers

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ASJC Scopus subject areas

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Datasets

CCDC 2234122: Experimental Crystal Structure Determination

CCDC 2234123: Experimental Crystal Structure Determination

CCDC 2234124: Experimental Crystal Structure Determination

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