Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/Xenon Separation

Karam B. Idrees; Zhijie Chen; Xuan Zhang; Mohammad Rasel Mian; Riki J. Drout; Timur Islamoglu; Omar K. Farha

doi:10.1021/acs.chemmater.9b05048

Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/Xenon Separation

Karam B. Idrees, Zhijie Chen, Xuan Zhang, Mohammad Rasel Mian, Riki J. Drout, Timur Islamoglu, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

89 Scopus citations

Abstract

Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly energy-intensive; however, adsorption-based separation processes provide an alternative strategy for isolating gases in high purity. The absence of strong interactions between these molecules and porous adsorbents has impeded the advancement of adsorptive separation of krypton and xenon. Herein, we capitalized on the modular nature of metal-organic frameworks (MOFs) to design a porous material which relies on gas confinement to separate krypton/xenon (Kr/Xe) mixtures. We solvothermally synthesized a new zirconium-based MOF, NU-403, which comprises a three-dimensional linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid. Comprehensive gas adsorption measurements revealed that the linker dimensionality and MOF pore aperture dramatically affect the separation of xenon from krypton owing to the confinement of gas molecules inside the framework. Moreover, Kr/Xe selectivity increased significantly after postsynthetic defect healing, which further enhanced gas-framework interactions, demonstrating an effective strategy for enhancing krypton and xenon separation.

Original language	English (US)
Pages (from-to)	3776-3782
Number of pages	7
Journal	Chemistry of Materials
Volume	32
Issue number	9
DOIs	https://doi.org/10.1021/acs.chemmater.9b05048
State	Published - May 12 2020

Funding

The authors gratefully acknowledge support from the U.S. Department of Energy (DOE) Office of Science, Basic Energy Sciences Program for separation (DE-FG02-08ER15967) and the Defense Threat Reduction Agency for MOF synthesis (HDTRA1-19-1-0007). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF NNCI-1542205), the MRSEC program (NSF DMR1720139) at the Materials Research Center, the Keck Foundation, the International Institute for Nanotechnology (IIN), and the State of Illinois through the IIN. This work made use of the IMSERC at Northwestern University, which has received support from the NSF (CHE-1048773 and DMR0521267), the SHyNE Resource (NSF NNCI-1542205), the State of Illinois, and the IIN.

ASJC Scopus subject areas

General Chemistry
General Chemical Engineering
Materials Chemistry

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10.1021/acs.chemmater.9b05048

Cite this

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title = "Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/Xenon Separation",

abstract = "Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly energy-intensive; however, adsorption-based separation processes provide an alternative strategy for isolating gases in high purity. The absence of strong interactions between these molecules and porous adsorbents has impeded the advancement of adsorptive separation of krypton and xenon. Herein, we capitalized on the modular nature of metal-organic frameworks (MOFs) to design a porous material which relies on gas confinement to separate krypton/xenon (Kr/Xe) mixtures. We solvothermally synthesized a new zirconium-based MOF, NU-403, which comprises a three-dimensional linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid. Comprehensive gas adsorption measurements revealed that the linker dimensionality and MOF pore aperture dramatically affect the separation of xenon from krypton owing to the confinement of gas molecules inside the framework. Moreover, Kr/Xe selectivity increased significantly after postsynthetic defect healing, which further enhanced gas-framework interactions, demonstrating an effective strategy for enhancing krypton and xenon separation.",

author = "Idrees, {Karam B.} and Zhijie Chen and Xuan Zhang and Mian, {Mohammad Rasel} and Drout, {Riki J.} and Timur Islamoglu and Farha, {Omar K.}",

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AU - Idrees, Karam B.

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AU - Zhang, Xuan

AU - Mian, Mohammad Rasel

AU - Drout, Riki J.

AU - Islamoglu, Timur

AU - Farha, Omar K.

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N2 - Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly energy-intensive; however, adsorption-based separation processes provide an alternative strategy for isolating gases in high purity. The absence of strong interactions between these molecules and porous adsorbents has impeded the advancement of adsorptive separation of krypton and xenon. Herein, we capitalized on the modular nature of metal-organic frameworks (MOFs) to design a porous material which relies on gas confinement to separate krypton/xenon (Kr/Xe) mixtures. We solvothermally synthesized a new zirconium-based MOF, NU-403, which comprises a three-dimensional linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid. Comprehensive gas adsorption measurements revealed that the linker dimensionality and MOF pore aperture dramatically affect the separation of xenon from krypton owing to the confinement of gas molecules inside the framework. Moreover, Kr/Xe selectivity increased significantly after postsynthetic defect healing, which further enhanced gas-framework interactions, demonstrating an effective strategy for enhancing krypton and xenon separation.

AB - Krypton and xenon are important gases in many applications, including, but not limited to, electronics, lighting, and medicine. Separation of these two gases by cryogenic distillation is highly energy-intensive; however, adsorption-based separation processes provide an alternative strategy for isolating gases in high purity. The absence of strong interactions between these molecules and porous adsorbents has impeded the advancement of adsorptive separation of krypton and xenon. Herein, we capitalized on the modular nature of metal-organic frameworks (MOFs) to design a porous material which relies on gas confinement to separate krypton/xenon (Kr/Xe) mixtures. We solvothermally synthesized a new zirconium-based MOF, NU-403, which comprises a three-dimensional linker, bicyclo[2.2.2]octane-1,4-dicarboxylic acid. Comprehensive gas adsorption measurements revealed that the linker dimensionality and MOF pore aperture dramatically affect the separation of xenon from krypton owing to the confinement of gas molecules inside the framework. Moreover, Kr/Xe selectivity increased significantly after postsynthetic defect healing, which further enhanced gas-framework interactions, demonstrating an effective strategy for enhancing krypton and xenon separation.

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Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/Xenon Separation

Abstract

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CCDC 1970352: Experimental Crystal Structure Determination

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Tailoring Pore Aperture and Structural Defects in Zirconium-Based Metal-Organic Frameworks for Krypton/Xenon Separation

Abstract

Funding

ASJC Scopus subject areas

Access to Document

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CCDC 1970352: Experimental Crystal Structure Determination

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