Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework
Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-tempera...
| Main Authors: | , , , , , , |
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| Other Authors: | |
| Format: | Article |
| Language: | English |
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American Chemical Society (ACS)
2020
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| Online Access: | https://hdl.handle.net/1721.1/126154 |
| _version_ | 1811083578327433216 |
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| author | Xie, Lilia S. Sun, Lei Wan, Ruomeng Park, Sarah Sunah DeGayner, Jordan A. Hendon, Christopher H. Dinca, Mircea |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Xie, Lilia S. Sun, Lei Wan, Ruomeng Park, Sarah Sunah DeGayner, Jordan A. Hendon, Christopher H. Dinca, Mircea |
| author_sort | Xie, Lilia S. |
| collection | MIT |
| description | Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe[superscript 2+] and Fe[superscript 3+] centers. These findings are consistent with low-lying Fe[superscript 3+] defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs. |
| first_indexed | 2024-09-23T12:35:19Z |
| format | Article |
| id | mit-1721.1/126154 |
| institution | Massachusetts Institute of Technology |
| language | English |
| last_indexed | 2024-09-23T12:35:19Z |
| publishDate | 2020 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1261542022-10-01T09:56:33Z Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework Xie, Lilia S. Sun, Lei Wan, Ruomeng Park, Sarah Sunah DeGayner, Jordan A. Hendon, Christopher H. Dinca, Mircea Massachusetts Institute of Technology. Department of Chemistry Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe[superscript 2+] and Fe[superscript 3+] centers. These findings are consistent with low-lying Fe[superscript 3+] defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs. U.S. Department of Energy, Office of Basic Energy Sciences (grant no. DE-SC0018235) National Science Foundation Graduate Research Fellowship Program (grant no. 1122374) 2020-07-13T16:20:12Z 2020-07-13T16:20:12Z 2018-05 2019-12-17T14:28:53Z Article http://purl.org/eprint/type/JournalArticle 1520-5126 https://hdl.handle.net/1721.1/126154 Xie, Lilia S., et al. "Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework." Journal of the American Chemical Society 140, 24 (2018): p. 7411-14 doi 10.1021/JACS.8B03604 ©2018 Author(s) en 10.1021/JACS.8B03604 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) MIT web domain |
| spellingShingle | Xie, Lilia S. Sun, Lei Wan, Ruomeng Park, Sarah Sunah DeGayner, Jordan A. Hendon, Christopher H. Dinca, Mircea Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title_full | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title_fullStr | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title_full_unstemmed | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title_short | Tunable mixed-valence doping toward record electrical conductivity in a three-dimensional metal-organic framework |
| title_sort | tunable mixed valence doping toward record electrical conductivity in a three dimensional metal organic framework |
| url | https://hdl.handle.net/1721.1/126154 |
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