A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework
Abstract
Engendering electrical conductivity in high-porosity metal–organic frameworks (MOFs) promises to unlock the full potential of MOFs for electrical energy storage, electrocatalysis, or integration of MOFs with conventional electronic materials. Here we report that a porous zirconium-node-containing MOF, NU-901, can be rendered electronically conductive by physically encapsulating C60, an excellent electron acceptor, within a fraction (ca. 60%) of the diamond-shaped cavities of the MOF. The cavities are defined by node-connected tetra-phenyl-carboxylated pyrene linkers, i.e. species that are excellent electron donors. The bulk electrical conductivity of the MOF is shown to increase from immeasurably low to 10-3 S cm-1, following fullerene incorporation. The observed conductivity originates from electron donor–acceptor interactions, i.e. charge-transfer interactions – a conclusion that is supported by density functional theory calculations and by the observation of a charge-transfer-derived band in the electronic absorption spectrum of the hybrid material. Notably, the conductive version of the MOF retains substantial nanoscale porosity and continues to display a sizable internal surface area, suggesting potential future applications that capitalize on the ability of the material to sorb molecular species.
- Authors:
-
[1];
[2];
[1];
[1];
[1];
[1];
[1];
[2];
[3];
[1]
- Department of Chemistry, Northwestern University, Evanston, USA
- Department of Chemistry, Chemical Theory Center, Minnesota Supercomputing Institute, University of Minnesota, Minneapolis
- Department of Chemistry, Northwestern University, Evanston, USA, Department of Chemistry
- Publication Date:
- Research Org.:
- Univ. of Minnesota, Minneapolis, MN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
- OSTI Identifier:
- 1433741
- Alternate Identifier(s):
- OSTI ID: 1506652
- Grant/Contract Number:
- FG02-17ER16362; SC0008688
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 19; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Goswami, Subhadip, Ray, Debmalya, Otake, Ken-ichi, Kung, Chung-Wei, Garibay, Sergio J., Islamoglu, Timur, Atilgan, Ahmet, Cui, Yuexing, Cramer, Christopher J., Farha, Omar K., and Hupp, Joseph T. A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework. United Kingdom: N. p., 2018.
Web. doi:10.1039/C8SC00961A.
Goswami, Subhadip, Ray, Debmalya, Otake, Ken-ichi, Kung, Chung-Wei, Garibay, Sergio J., Islamoglu, Timur, Atilgan, Ahmet, Cui, Yuexing, Cramer, Christopher J., Farha, Omar K., & Hupp, Joseph T. A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework. United Kingdom. https://doi.org/10.1039/C8SC00961A
Goswami, Subhadip, Ray, Debmalya, Otake, Ken-ichi, Kung, Chung-Wei, Garibay, Sergio J., Islamoglu, Timur, Atilgan, Ahmet, Cui, Yuexing, Cramer, Christopher J., Farha, Omar K., and Hupp, Joseph T. Mon .
"A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework". United Kingdom. https://doi.org/10.1039/C8SC00961A.
@article{osti_1433741,
title = {A porous, electrically conductive hexa-zirconium( iv ) metal–organic framework},
author = {Goswami, Subhadip and Ray, Debmalya and Otake, Ken-ichi and Kung, Chung-Wei and Garibay, Sergio J. and Islamoglu, Timur and Atilgan, Ahmet and Cui, Yuexing and Cramer, Christopher J. and Farha, Omar K. and Hupp, Joseph T.},
abstractNote = {Engendering electrical conductivity in high-porosity metal–organic frameworks (MOFs) promises to unlock the full potential of MOFs for electrical energy storage, electrocatalysis, or integration of MOFs with conventional electronic materials. Here we report that a porous zirconium-node-containing MOF, NU-901, can be rendered electronically conductive by physically encapsulating C60, an excellent electron acceptor, within a fraction (ca. 60%) of the diamond-shaped cavities of the MOF. The cavities are defined by node-connected tetra-phenyl-carboxylated pyrene linkers, i.e. species that are excellent electron donors. The bulk electrical conductivity of the MOF is shown to increase from immeasurably low to 10-3 S cm-1, following fullerene incorporation. The observed conductivity originates from electron donor–acceptor interactions, i.e. charge-transfer interactions – a conclusion that is supported by density functional theory calculations and by the observation of a charge-transfer-derived band in the electronic absorption spectrum of the hybrid material. Notably, the conductive version of the MOF retains substantial nanoscale porosity and continues to display a sizable internal surface area, suggesting potential future applications that capitalize on the ability of the material to sorb molecular species.},
doi = {10.1039/C8SC00961A},
journal = {Chemical Science},
number = 19,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {1}
}
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