A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia

Yuanyuan Zhang; Xuan Zhang; Zhijie Chen; Ken ichi Otake; Gregory W. Peterson; Yongwei Chen; Xingjie Wang; Louis R. Redfern; Subhadip Goswami; Peng Li; Timur Islamoglu; Bo Wang; Omar K. Farha

doi:10.1002/cssc.202000306

A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia

Yuanyuan Zhang, Xuan Zhang, Zhijie Chen, Ken ichi Otake, Gregory W. Peterson, Yongwei Chen, Xingjie Wang, Louis R. Redfern, Subhadip Goswami, Peng Li, Timur Islamoglu, Bo Wang, Omar K. Farha^*

^*Corresponding author for this work

Chemistry

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

28 Scopus citations

Abstract

Flexible metal–organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, a flexible interpenetrated Zr-MOF, NU-1401, composed of rare 4-connected Zr₆ nodes and tetratopic naphthalenediimide (NDI)-based carboxylate linkers, was designed. The intra-framework pore opening deformation and inter-framework motions, when subjected to different solvent molecules, were investigated by single-crystal XRD. The distance and overlap angle between the stacked NDI pairs in the entangled structure could be finely tuned, and the interactions between NDI and solvent molecules led to solvochromism. Furthermore, the presence of electron-deficient NDI units in the linker and acid sites on the node of the interpenetrated porous structure offered high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.

Original language	English (US)
Pages (from-to)	1710-1714
Number of pages	5
Journal	ChemSusChem
Volume	13
Issue number	7
DOIs	https://doi.org/10.1002/cssc.202000306
State	Published - Apr 7 2020

Keywords

ammonia capture
flexible MOF
interpenetrated structure
metal–organic frameworks
microporous materials

ASJC Scopus subject areas

Environmental Chemistry
Chemical Engineering(all)
Materials Science(all)
Energy(all)

Access to Document

10.1002/cssc.202000306

Cite this

@article{6bbf42b7cda74e1ca47502a4a8700415,

title = "A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia",

abstract = "Flexible metal–organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, a flexible interpenetrated Zr-MOF, NU-1401, composed of rare 4-connected Zr6 nodes and tetratopic naphthalenediimide (NDI)-based carboxylate linkers, was designed. The intra-framework pore opening deformation and inter-framework motions, when subjected to different solvent molecules, were investigated by single-crystal XRD. The distance and overlap angle between the stacked NDI pairs in the entangled structure could be finely tuned, and the interactions between NDI and solvent molecules led to solvochromism. Furthermore, the presence of electron-deficient NDI units in the linker and acid sites on the node of the interpenetrated porous structure offered high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.",

keywords = "ammonia capture, flexible MOF, interpenetrated structure, metal–organic frameworks, microporous materials",

author = "Yuanyuan Zhang and Xuan Zhang and Zhijie Chen and Otake, {Ken ichi} and Peterson, {Gregory W.} and Yongwei Chen and Xingjie Wang and Redfern, {Louis R.} and Subhadip Goswami and Peng Li and Timur Islamoglu and Bo Wang and Farha, {Omar K.}",

note = "Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1‐19‐1‐0007). Y.Z. acknowledges support from China Scholarship Council (CSC) during her visit to Northwestern University, and Fundamental Research Funds for the Central Universities and Beijing Institute of Technology Research Fund Program. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). 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 ECCS‐1542205); the MRSEC program (NSF DMR‐1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program (DE‐FG02‐03ER15457) used for the purchase of the Nicolet 6700 FT‐IR System. G.W.P. thanks the Defense Threat Reduction Agency (CB3934) for funding the ammonia work and Matthew Browe for running ammonia breakthrough experiments. Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). Y.Z. acknowledges support from China Scholarship Council (CSC) during her visit to Northwestern University, and Fundamental Research Funds for the Central Universities and Beijing Institute of Technology Research Fund Program. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). 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 ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program (DE-FG02-03ER15457) used for the purchase of the Nicolet 6700 FT-IR System. G.W.P. thanks the Defense Threat Reduction Agency (CB3934) for funding the ammonia work and Matthew Browe for running ammonia breakthrough experiments. Publisher Copyright: {\textcopyright} 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim",

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doi = "10.1002/cssc.202000306",

language = "English (US)",

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T1 - A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia

AU - Zhang, Yuanyuan

AU - Zhang, Xuan

AU - Chen, Zhijie

AU - Otake, Ken ichi

AU - Peterson, Gregory W.

AU - Chen, Yongwei

AU - Wang, Xingjie

AU - Redfern, Louis R.

AU - Goswami, Subhadip

AU - Li, Peng

AU - Islamoglu, Timur

AU - Wang, Bo

AU - Farha, Omar K.

N1 - Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1‐19‐1‐0007). Y.Z. acknowledges support from China Scholarship Council (CSC) during her visit to Northwestern University, and Fundamental Research Funds for the Central Universities and Beijing Institute of Technology Research Fund Program. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS‐1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). 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 ECCS‐1542205); the MRSEC program (NSF DMR‐1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program (DE‐FG02‐03ER15457) used for the purchase of the Nicolet 6700 FT‐IR System. G.W.P. thanks the Defense Threat Reduction Agency (CB3934) for funding the ammonia work and Matthew Browe for running ammonia breakthrough experiments. Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). Y.Z. acknowledges support from China Scholarship Council (CSC) during her visit to Northwestern University, and Fundamental Research Funds for the Central Universities and Beijing Institute of Technology Research Fund Program. This work made use of the IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, and the International Institute for Nanotechnology (IIN). 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 ECCS-1542205); the MRSEC program (NSF DMR-1720139) at the Materials Research Center; the International Institute for Nanotechnology (IIN); the Keck Foundation; and the State of Illinois, through the IIN. The REACT Core facility acknowledges funding from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Catalysis Science program (DE-FG02-03ER15457) used for the purchase of the Nicolet 6700 FT-IR System. G.W.P. thanks the Defense Threat Reduction Agency (CB3934) for funding the ammonia work and Matthew Browe for running ammonia breakthrough experiments. Publisher Copyright: © 2020 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

PY - 2020/4/7

Y1 - 2020/4/7

N2 - Flexible metal–organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, a flexible interpenetrated Zr-MOF, NU-1401, composed of rare 4-connected Zr6 nodes and tetratopic naphthalenediimide (NDI)-based carboxylate linkers, was designed. The intra-framework pore opening deformation and inter-framework motions, when subjected to different solvent molecules, were investigated by single-crystal XRD. The distance and overlap angle between the stacked NDI pairs in the entangled structure could be finely tuned, and the interactions between NDI and solvent molecules led to solvochromism. Furthermore, the presence of electron-deficient NDI units in the linker and acid sites on the node of the interpenetrated porous structure offered high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.

AB - Flexible metal–organic frameworks (MOFs) are highly attractive porous crystalline materials presenting structural changes when exposed to external stimuli, the mechanism of which is often difficult to glean, owing to their complex and dynamic nature. Herein, a flexible interpenetrated Zr-MOF, NU-1401, composed of rare 4-connected Zr6 nodes and tetratopic naphthalenediimide (NDI)-based carboxylate linkers, was designed. The intra-framework pore opening deformation and inter-framework motions, when subjected to different solvent molecules, were investigated by single-crystal XRD. The distance and overlap angle between the stacked NDI pairs in the entangled structure could be finely tuned, and the interactions between NDI and solvent molecules led to solvochromism. Furthermore, the presence of electron-deficient NDI units in the linker and acid sites on the node of the interpenetrated porous structure offered high density of adsorption sites for ammonia molecules, resulting in high uptake at low pressures.

KW - ammonia capture

KW - flexible MOF

KW - interpenetrated structure

KW - metal–organic frameworks

KW - microporous materials

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ER -

A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia

Abstract

Keywords

ASJC Scopus subject areas

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CCDC 1956217: Experimental Crystal Structure Determination

CCDC 1956220: Experimental Crystal Structure Determination

CCDC 1956219: Experimental Crystal Structure Determination

Cite this

A Flexible Interpenetrated Zirconium-Based Metal–Organic Framework with High Affinity toward Ammonia

Abstract

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Datasets

CCDC 1956217: Experimental Crystal Structure Determination

CCDC 1956220: Experimental Crystal Structure Determination

CCDC 1956219: Experimental Crystal Structure Determination

Cite this