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Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture

Joshua M. Tuffnell Orcid Logo, Jędrzej K. Morzy Orcid Logo, Nicola D. Kelly Orcid Logo, Rui Tan Orcid Logo, Qilei Song Orcid Logo, Caterina Ducati Orcid Logo, Thomas D. Bennett Orcid Logo, Siân E. Dutton Orcid Logo

Dalton Transactions, Volume: 49, Issue: 44, Pages: 15914 - 15924

Swansea University Author: Rui Tan Orcid Logo

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DOI (Published version): 10.1039/d0dt02576c

Abstract

IL@MOF (IL: ionic liquid; MOF: metal–organic framework) materials have been proposed as a candidate for solid-state electrolytes, combining the inherent non-flammability and high thermal and chemical stability of the ionic liquid with the host–guest interactions of the MOF. In this work, we compare...

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Published in: Dalton Transactions
ISSN: 1477-9226 1477-9234
Published: Royal Society of Chemistry (RSC) 2020
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URI: https://cronfa.swan.ac.uk/Record/cronfa67812
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In this work, we compare the structure and ionic conductivity of a sodium ion containing IL@MOF composite formed from a microcrystalline powder of the zeolitic imidazolate framework (ZIF), ZIF-8 with a hierarchically porous sample of ZIF-8 containing both micro- and mesopores from a sol&#x2013;gel synthesis. Although the crystallographic structures were shown to be the same by X-ray diffraction, significant differences in particle size, packing and morphology were identified by electron microscopy techniques which highlight the origins of the hierarchical porosity. After incorporation of Na0.1EMIM0.9TFSI (abbreviated to NaIL; EMIM = 1-ethyl-3-methylimidazolium; TFSI = bis(trifluoromethylsulfonyl)imide), the hierarchically porous composite exhibited a 40% greater filling capacity than the purely microporous sample which was confirmed by elemental analysis and digestive proton NMR. Finally, the ionic conductivity properties of the composite materials were probed by electrochemical impedance spectroscopy. The results showed that despite the 40% increased loading of NaIL in the NaIL@ZIF-8micro sample, the ionic conductivities at 25 &#xB0;C were 8.4 &#xD7; 10&#x2212;6 and 1.6 &#xD7; 10&#x2212;5 S cm&#x2212;1 for NaIL@ZIF-8meso and NaIL@ZIF-8micro respectively. These results exemplify the importance of the long range, continuous ion pathways contributed by the microcrystalline pores, as well as the limited contribution from the discontinuous mesopores to the overall ionic conductivity.</abstract><type>Journal Article</type><journal>Dalton Transactions</journal><volume>49</volume><journalNumber>44</journalNumber><paginationStart>15914</paginationStart><paginationEnd>15924</paginationEnd><publisher>Royal Society of Chemistry (RSC)</publisher><placeOfPublication/><isbnPrint/><isbnElectronic/><issnPrint>1477-9226</issnPrint><issnElectronic>1477-9234</issnElectronic><keywords/><publishedDay>3</publishedDay><publishedMonth>11</publishedMonth><publishedYear>2020</publishedYear><publishedDate>2020-11-03</publishedDate><doi>10.1039/d0dt02576c</doi><url/><notes/><college>COLLEGE NANME</college><department>Engineering and Applied Sciences School</department><CollegeCode>COLLEGE CODE</CollegeCode><DepartmentCode>EAAS</DepartmentCode><institution>Swansea University</institution><apcterm>Another institution paid the OA fee</apcterm><funders>T. D. B. thanks the Royal Society for both a University Research Fellowship (UF150021) and a research grant (RSG\R1\180395). T. D. B. also gratefully acknowledges the University of Canterbury Te Whare W&#x101;nanga o Waitaha, New Zealand, for a University of Cambridge Visiting Canterbury Fellowship, and the Leverhulme Trust for a Philip Leverhulme Prize. J. M. T, C. D. and J. K. M. acknowledge funding from NanoDTC EPSRC Grant EP/L015978/1. J. K. M. also acknowledges funding from the Cambridge Trust. S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability. R. T. acknowledges the funding from China Scholarship Council. Q. S. acknowledges the funding from EPSRC Centre CAM-IES and ERC (NanoMMES, 851272). N. D. K. acknowledges PhD funding from the EPSRC Grant EP/R513180/1. J. M. T. would also like to thank Jack Hodkinson and Adam Lovett for their helpful discussions on the fitting of the electrochemical impedance spectra as well as Vahid Nozari and Lothar Wondraczek for further helpful discussions. J. K. M. would like to thank S. M. 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spelling 2024-10-18T12:05:28.6607808 v2 67812 2024-09-25 Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture 774c33a0a76a9152ca86a156b5ae26ff 0009-0001-9278-7327 Rui Tan Rui Tan true false 2024-09-25 EAAS IL@MOF (IL: ionic liquid; MOF: metal–organic framework) materials have been proposed as a candidate for solid-state electrolytes, combining the inherent non-flammability and high thermal and chemical stability of the ionic liquid with the host–guest interactions of the MOF. In this work, we compare the structure and ionic conductivity of a sodium ion containing IL@MOF composite formed from a microcrystalline powder of the zeolitic imidazolate framework (ZIF), ZIF-8 with a hierarchically porous sample of ZIF-8 containing both micro- and mesopores from a sol–gel synthesis. Although the crystallographic structures were shown to be the same by X-ray diffraction, significant differences in particle size, packing and morphology were identified by electron microscopy techniques which highlight the origins of the hierarchical porosity. After incorporation of Na0.1EMIM0.9TFSI (abbreviated to NaIL; EMIM = 1-ethyl-3-methylimidazolium; TFSI = bis(trifluoromethylsulfonyl)imide), the hierarchically porous composite exhibited a 40% greater filling capacity than the purely microporous sample which was confirmed by elemental analysis and digestive proton NMR. Finally, the ionic conductivity properties of the composite materials were probed by electrochemical impedance spectroscopy. The results showed that despite the 40% increased loading of NaIL in the NaIL@ZIF-8micro sample, the ionic conductivities at 25 °C were 8.4 × 10−6 and 1.6 × 10−5 S cm−1 for NaIL@ZIF-8meso and NaIL@ZIF-8micro respectively. These results exemplify the importance of the long range, continuous ion pathways contributed by the microcrystalline pores, as well as the limited contribution from the discontinuous mesopores to the overall ionic conductivity. Journal Article Dalton Transactions 49 44 15914 15924 Royal Society of Chemistry (RSC) 1477-9226 1477-9234 3 11 2020 2020-11-03 10.1039/d0dt02576c COLLEGE NANME Engineering and Applied Sciences School COLLEGE CODE EAAS Swansea University Another institution paid the OA fee T. D. B. thanks the Royal Society for both a University Research Fellowship (UF150021) and a research grant (RSG\R1\180395). T. D. B. also gratefully acknowledges the University of Canterbury Te Whare Wānanga o Waitaha, New Zealand, for a University of Cambridge Visiting Canterbury Fellowship, and the Leverhulme Trust for a Philip Leverhulme Prize. J. M. T, C. D. and J. K. M. acknowledge funding from NanoDTC EPSRC Grant EP/L015978/1. J. K. M. also acknowledges funding from the Cambridge Trust. S. E. D. acknowledges funding from the Winton Programme for the Physics of Sustainability. R. T. acknowledges the funding from China Scholarship Council. Q. S. acknowledges the funding from EPSRC Centre CAM-IES and ERC (NanoMMES, 851272). N. D. K. acknowledges PhD funding from the EPSRC Grant EP/R513180/1. J. M. T. would also like to thank Jack Hodkinson and Adam Lovett for their helpful discussions on the fitting of the electrochemical impedance spectra as well as Vahid Nozari and Lothar Wondraczek for further helpful discussions. J. K. M. would like to thank S. M. Collins for discussions on possible TEM approaches. 2024-10-18T12:05:28.6607808 2024-09-25T21:34:22.0283799 Faculty of Science and Engineering School of Engineering and Applied Sciences - Chemical Engineering Joshua M. Tuffnell 0000-0003-3069-1466 1 Jędrzej K. Morzy 0000-0003-0770-461x 2 Nicola D. Kelly 0000-0003-2861-1623 3 Rui Tan 0009-0001-9278-7327 4 Qilei Song 0000-0001-8570-3626 5 Caterina Ducati 0000-0003-3366-6442 6 Thomas D. Bennett 0000-0003-3717-3119 7 Siân E. Dutton 0000-0003-0984-5504 8 67812__32624__574a6a6c9523478eb5d8ffd39ef7c921.pdf 67812.VoR.pdf 2024-10-18T10:36:18.4691539 Output 2664108 application/pdf Version of Record true This article is licensed under a Creative Commons Attribution-NonCommercial 3.0 Unported Licence. true eng http://creativecommons.org/licenses/by-nc/3.0/
title Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
spellingShingle Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
Rui Tan
title_short Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
title_full Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
title_fullStr Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
title_full_unstemmed Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
title_sort Comparison of the ionic conductivity properties of microporous and mesoporous MOFs infiltrated with a Na-ion containing IL mixture
author_id_str_mv 774c33a0a76a9152ca86a156b5ae26ff
author_id_fullname_str_mv 774c33a0a76a9152ca86a156b5ae26ff_***_Rui Tan
author Rui Tan
author2 Joshua M. Tuffnell
Jędrzej K. Morzy
Nicola D. Kelly
Rui Tan
Qilei Song
Caterina Ducati
Thomas D. Bennett
Siân E. Dutton
format Journal article
container_title Dalton Transactions
container_volume 49
container_issue 44
container_start_page 15914
publishDate 2020
institution Swansea University
issn 1477-9226
1477-9234
doi_str_mv 10.1039/d0dt02576c
publisher Royal Society of Chemistry (RSC)
college_str Faculty of Science and Engineering
hierarchytype
hierarchy_top_id facultyofscienceandengineering
hierarchy_top_title Faculty of Science and Engineering
hierarchy_parent_id facultyofscienceandengineering
hierarchy_parent_title Faculty of Science and Engineering
department_str School of Engineering and Applied Sciences - Chemical Engineering{{{_:::_}}}Faculty of Science and Engineering{{{_:::_}}}School of Engineering and Applied Sciences - Chemical Engineering
document_store_str 1
active_str 0
description IL@MOF (IL: ionic liquid; MOF: metal–organic framework) materials have been proposed as a candidate for solid-state electrolytes, combining the inherent non-flammability and high thermal and chemical stability of the ionic liquid with the host–guest interactions of the MOF. In this work, we compare the structure and ionic conductivity of a sodium ion containing IL@MOF composite formed from a microcrystalline powder of the zeolitic imidazolate framework (ZIF), ZIF-8 with a hierarchically porous sample of ZIF-8 containing both micro- and mesopores from a sol–gel synthesis. Although the crystallographic structures were shown to be the same by X-ray diffraction, significant differences in particle size, packing and morphology were identified by electron microscopy techniques which highlight the origins of the hierarchical porosity. After incorporation of Na0.1EMIM0.9TFSI (abbreviated to NaIL; EMIM = 1-ethyl-3-methylimidazolium; TFSI = bis(trifluoromethylsulfonyl)imide), the hierarchically porous composite exhibited a 40% greater filling capacity than the purely microporous sample which was confirmed by elemental analysis and digestive proton NMR. Finally, the ionic conductivity properties of the composite materials were probed by electrochemical impedance spectroscopy. The results showed that despite the 40% increased loading of NaIL in the NaIL@ZIF-8micro sample, the ionic conductivities at 25 °C were 8.4 × 10−6 and 1.6 × 10−5 S cm−1 for NaIL@ZIF-8meso and NaIL@ZIF-8micro respectively. These results exemplify the importance of the long range, continuous ion pathways contributed by the microcrystalline pores, as well as the limited contribution from the discontinuous mesopores to the overall ionic conductivity.
published_date 2020-11-03T08:20:48Z
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score 11.058331

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