Exploiting in situ NMR to monitor the formation of a metal–organic framework

Corey L Jones; Colan E.  Hughes; Hamish Yeung; Alison Paul; Kenneth D. M. Harris; Timothy Easun

doi:10.1039/D0SC04892E

Exploiting in situ NMR to monitor the formation of a metal–organic framework

Corey L Jones, Colan E. Hughes, Hamish Yeung, Alison Paul, Kenneth D. M. Harris, Timothy Easun

Chemistry

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

153 Downloads (Pure)

Abstract

The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase ¹H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol⁻¹) and growth (72.9 ± 8.6 kJ mol⁻¹) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.

Original language	English
Pages (from-to)	1486-1494
Number of pages	9
Journal	Chemical Science
Volume	12
Issue number	4
Early online date	20 Nov 2020
DOIs	https://doi.org/10.1039/D0SC04892E
Publication status	Published - 28 Jan 2021

Bibliographical note

Funding Information:
T. L. E. gratefully acknowledges the Royal Society for the award of a University Research Fellowship (6866). We thank Cardiff University and the EPSRC (grant reference EP/L504749/1) for funding. H. H.-M. Y. thanks the Samuel and Violette Glasstone Bequest for a Fellowship. We are grateful to the UK High-Field Solid-State NMR Facility for the award of spectrometer time. This facility was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick, including part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands and the European Regional Development Fund. The in situ powder XRD study on beamline I12 was supported by Diamond Light Source (beamtime EE16450). We thank Sebastian Henke, Roman Pallach, Niclas Heidenreich and Nghia Vo for assistance with in situ powder XRD measurements, and Dinu Iuga for assistance with NMR measurements.

Publisher Copyright:
© The Royal Society of Chemistry 2020.

Access to Document

10.1039/D0SC04892ELicence: Creative Commons: Attribution (CC BY)

JonesC2020ExploitingFinal published version, 1.07 MBLicence: Creative Commons: Attribution (CC BY)

Cite this

@article{53e8875bfe2949bf813484ce546b1e16,

title = "Exploiting in situ NMR to monitor the formation of a metal–organic framework",

abstract = "The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase 1H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol−1) and growth (72.9 ± 8.6 kJ mol−1) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.",

author = "Jones, {Corey L} and Hughes, {Colan E.} and Hamish Yeung and Alison Paul and Harris, {Kenneth D. M.} and Timothy Easun",

note = "Funding Information: T. L. E. gratefully acknowledges the Royal Society for the award of a University Research Fellowship (6866). We thank Cardiff University and the EPSRC (grant reference EP/L504749/1) for funding. H. H.-M. Y. thanks the Samuel and Violette Glasstone Bequest for a Fellowship. We are grateful to the UK High-Field Solid-State NMR Facility for the award of spectrometer time. This facility was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick, including part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands and the European Regional Development Fund. The in situ powder XRD study on beamline I12 was supported by Diamond Light Source (beamtime EE16450). We thank Sebastian Henke, Roman Pallach, Niclas Heidenreich and Nghia Vo for assistance with in situ powder XRD measurements, and Dinu Iuga for assistance with NMR measurements. Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2020.",

year = "2021",

month = jan,

day = "28",

doi = "10.1039/D0SC04892E",

language = "English",

volume = "12",

pages = "1486--1494",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "4",

}

TY - JOUR

T1 - Exploiting in situ NMR to monitor the formation of a metal–organic framework

AU - Jones, Corey L

AU - Hughes, Colan E.

AU - Yeung, Hamish

AU - Paul, Alison

AU - Harris, Kenneth D. M.

AU - Easun, Timothy

N1 - Funding Information: T. L. E. gratefully acknowledges the Royal Society for the award of a University Research Fellowship (6866). We thank Cardiff University and the EPSRC (grant reference EP/L504749/1) for funding. H. H.-M. Y. thanks the Samuel and Violette Glasstone Bequest for a Fellowship. We are grateful to the UK High-Field Solid-State NMR Facility for the award of spectrometer time. This facility was funded by EPSRC and BBSRC (contract reference PR140003), as well as the University of Warwick, including part funding through Birmingham Science City Advanced Materials Projects 1 and 2 supported by Advantage West Midlands and the European Regional Development Fund. The in situ powder XRD study on beamline I12 was supported by Diamond Light Source (beamtime EE16450). We thank Sebastian Henke, Roman Pallach, Niclas Heidenreich and Nghia Vo for assistance with in situ powder XRD measurements, and Dinu Iuga for assistance with NMR measurements. Publisher Copyright: © The Royal Society of Chemistry 2020.

PY - 2021/1/28

Y1 - 2021/1/28

N2 - The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase 1H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol−1) and growth (72.9 ± 8.6 kJ mol−1) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.

AB - The formation processes of metal–organic frameworks are becoming more widely researched using in situ techniques, although there remains a scarcity of NMR studies in this field. In this work, the synthesis of framework MFM-500(Ni) has been investigated using an in situ NMR strategy that provides information on the time-evolution of the reaction and crystallization process. In our in situ NMR study of MFM-500(Ni) formation, liquid-phase 1H NMR data recorded as a function of time at fixed temperatures (between 60 and 100 °C) afford qualitative information on the solution-phase processes and quantitative information on the kinetics of crystallization, allowing the activation energies for nucleation (61.4 ± 9.7 kJ mol−1) and growth (72.9 ± 8.6 kJ mol−1) to be determined. Ex situ small-angle X-ray scattering studies (at 80 °C) provide complementary nanoscale information on the rapid self-assembly prior to MOF crystallization and in situ powder X-ray diffraction confirms that the only crystalline phase present during the reaction (at 90 °C) is phase-pure MFM-500(Ni). This work demonstrates that in situ NMR experiments can shed new light on MOF synthesis, opening up the technique to provide better understanding of how MOFs are formed.

UR - http://www.scopus.com/inward/record.url?scp=85100513801&partnerID=8YFLogxK

U2 - 10.1039/D0SC04892E

DO - 10.1039/D0SC04892E

M3 - Article

SN - 2041-6520

VL - 12

SP - 1486

EP - 1494

JO - Chemical Science

JF - Chemical Science

IS - 4

ER -

Exploiting in situ NMR to monitor the formation of a metal–organic framework

Abstract

Bibliographical note

Access to Document

Fingerprint

Cite this