Time-Resolved in Situ Polymorphic Transformation from One 12-Connected Zr-MOF to Another

Seung Joon Lee; Jenna L. Mancuso; Khoa N. Le; Christos D. Malliakas; Youn Sang Bae; Christopher H. Hendon; Timur Islamoglu; Omar K. Farha

doi:10.1021/acsmaterialslett.0c00012

Time-Resolved in Situ Polymorphic Transformation from One 12-Connected Zr-MOF to Another

Seung Joon Lee, Jenna L. Mancuso, Khoa N. Le, Christos D. Malliakas, Youn Sang Bae, Christopher H. Hendon, Timur Islamoglu, Omar K. Farha

Department of Chemical and Biomolecular Engineering

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

10 Citations (Scopus)

Abstract

Understanding polymorphism in metal-organic frameworks (MOFs) provides opportunities to unravel the process of MOF crystallization, and it enables the elucidation of structure-property relationships of compositionally identical crystals. Here, we present the modulator- and temperature-mediated polymorphic transformation of the kinetic product from Zr₆-based MOF synthesis, EHU-30, to the thermodynamic product, UiO-66. The partial dissolution-recrystallization process was demonstrated by a combination of in situ powder X-ray diffraction (PXRD) and in situ ¹H NMR spectroscopy where EHU-30 was heated in the presence of a monotopic acid modulator, acetic acid. Density functional theory (DFT) calculations show that the EHU-30 polymorph is less stable because the bent linkers have higher Gibbs free energy compared to linear linkers in the thermodynamic product, UiO-66.

Original language	English
Pages (from-to)	499-504
Number of pages	6
Journal	ACS Materials Letters
Volume	2
Issue number	5
DOIs	https://doi.org/10.1021/acsmaterialslett.0c00012
Publication status	Published - 2020 May 4

Bibliographical note

Funding Information:
O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). This research was supported in part by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1A6A3A01011909). This work was also supported in part by the Yonsei University Research Fund (Yonsei Frontier Lab, Young Researcher Supporting Program) of 2018. PXRD and NMR studies 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); SEM study made use of EPIC facility of Northwestern University’s NU ANCE Center, which has received support from the SHyNE, the MRSEC program (NSF DMR-1720139) at the Materials Research Center, IIN, and the Keck Foundation. Computational works were performed using the High-Performance Computing cluster at the University of Oregon (Talapas), the Extreme Science and Engineering Discovery Environment (XSEDE) which is supported by National Science Foundation grant number ACI-1548562, and the Portland State University machine, Coeus, which is supported by the NSF (DMS1624776).

Publisher Copyright:
© 2020 American Chemical Society.

All Science Journal Classification (ASJC) codes

Chemical Engineering(all)
Materials Science(all)
Biomedical Engineering

Access to Document

10.1021/acsmaterialslett.0c00012

Cite this

@article{90ce87fd83d64c83a8810131fbf1842a,

title = "Time-Resolved in Situ Polymorphic Transformation from One 12-Connected Zr-MOF to Another",

abstract = "Understanding polymorphism in metal-organic frameworks (MOFs) provides opportunities to unravel the process of MOF crystallization, and it enables the elucidation of structure-property relationships of compositionally identical crystals. Here, we present the modulator- and temperature-mediated polymorphic transformation of the kinetic product from Zr6-based MOF synthesis, EHU-30, to the thermodynamic product, UiO-66. The partial dissolution-recrystallization process was demonstrated by a combination of in situ powder X-ray diffraction (PXRD) and in situ 1H NMR spectroscopy where EHU-30 was heated in the presence of a monotopic acid modulator, acetic acid. Density functional theory (DFT) calculations show that the EHU-30 polymorph is less stable because the bent linkers have higher Gibbs free energy compared to linear linkers in the thermodynamic product, UiO-66.",

author = "Lee, {Seung Joon} and Mancuso, {Jenna L.} and Le, {Khoa N.} and Malliakas, {Christos D.} and Bae, {Youn Sang} and Hendon, {Christopher H.} and Timur Islamoglu and Farha, {Omar K.}",

note = "Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). This research was supported in part by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1A6A3A01011909). This work was also supported in part by the Yonsei University Research Fund (Yonsei Frontier Lab, Young Researcher Supporting Program) of 2018. PXRD and NMR studies 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); SEM study made use of EPIC facility of Northwestern University{\textquoteright}s NU ANCE Center, which has received support from the SHyNE, the MRSEC program (NSF DMR-1720139) at the Materials Research Center, IIN, and the Keck Foundation. Computational works were performed using the High-Performance Computing cluster at the University of Oregon (Talapas), the Extreme Science and Engineering Discovery Environment (XSEDE) which is supported by National Science Foundation grant number ACI-1548562, and the Portland State University machine, Coeus, which is supported by the NSF (DMS1624776). Publisher Copyright: {\textcopyright} 2020 American Chemical Society.",

year = "2020",

month = may,

day = "4",

doi = "10.1021/acsmaterialslett.0c00012",

language = "English",

volume = "2",

pages = "499--504",

journal = "ACS Materials Letters",

issn = "2639-4979",

publisher = "American Chemical Society",

number = "5",

}

TY - JOUR

T1 - Time-Resolved in Situ Polymorphic Transformation from One 12-Connected Zr-MOF to Another

AU - Lee, Seung Joon

AU - Mancuso, Jenna L.

AU - Le, Khoa N.

AU - Malliakas, Christos D.

AU - Bae, Youn Sang

AU - Hendon, Christopher H.

AU - Islamoglu, Timur

AU - Farha, Omar K.

N1 - Funding Information: O.K.F. gratefully acknowledges support from the Defense Threat Reduction Agency (HDTRA1-19-1-0007). This research was supported in part by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2018R1A6A3A01011909). This work was also supported in part by the Yonsei University Research Fund (Yonsei Frontier Lab, Young Researcher Supporting Program) of 2018. PXRD and NMR studies 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); SEM study made use of EPIC facility of Northwestern University’s NU ANCE Center, which has received support from the SHyNE, the MRSEC program (NSF DMR-1720139) at the Materials Research Center, IIN, and the Keck Foundation. Computational works were performed using the High-Performance Computing cluster at the University of Oregon (Talapas), the Extreme Science and Engineering Discovery Environment (XSEDE) which is supported by National Science Foundation grant number ACI-1548562, and the Portland State University machine, Coeus, which is supported by the NSF (DMS1624776). Publisher Copyright: © 2020 American Chemical Society.

PY - 2020/5/4

Y1 - 2020/5/4

N2 - Understanding polymorphism in metal-organic frameworks (MOFs) provides opportunities to unravel the process of MOF crystallization, and it enables the elucidation of structure-property relationships of compositionally identical crystals. Here, we present the modulator- and temperature-mediated polymorphic transformation of the kinetic product from Zr6-based MOF synthesis, EHU-30, to the thermodynamic product, UiO-66. The partial dissolution-recrystallization process was demonstrated by a combination of in situ powder X-ray diffraction (PXRD) and in situ 1H NMR spectroscopy where EHU-30 was heated in the presence of a monotopic acid modulator, acetic acid. Density functional theory (DFT) calculations show that the EHU-30 polymorph is less stable because the bent linkers have higher Gibbs free energy compared to linear linkers in the thermodynamic product, UiO-66.

AB - Understanding polymorphism in metal-organic frameworks (MOFs) provides opportunities to unravel the process of MOF crystallization, and it enables the elucidation of structure-property relationships of compositionally identical crystals. Here, we present the modulator- and temperature-mediated polymorphic transformation of the kinetic product from Zr6-based MOF synthesis, EHU-30, to the thermodynamic product, UiO-66. The partial dissolution-recrystallization process was demonstrated by a combination of in situ powder X-ray diffraction (PXRD) and in situ 1H NMR spectroscopy where EHU-30 was heated in the presence of a monotopic acid modulator, acetic acid. Density functional theory (DFT) calculations show that the EHU-30 polymorph is less stable because the bent linkers have higher Gibbs free energy compared to linear linkers in the thermodynamic product, UiO-66.

UR - http://www.scopus.com/inward/record.url?scp=85083285722&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85083285722&partnerID=8YFLogxK

U2 - 10.1021/acsmaterialslett.0c00012

DO - 10.1021/acsmaterialslett.0c00012

M3 - Article

AN - SCOPUS:85083285722

SN - 2639-4979

VL - 2

SP - 499

EP - 504

JO - ACS Materials Letters

JF - ACS Materials Letters

IS - 5

ER -

Time-Resolved in Situ Polymorphic Transformation from One 12-Connected Zr-MOF to Another

Abstract

Bibliographical note

All Science Journal Classification (ASJC) codes

Access to Document

Other files and links

Fingerprint

Cite this