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Title: Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate) 2] by Gas Adsorption

Abstract

The development of new chemiresistive materials for use in chemical sensors that operate near ambient conditions could potentially reduce the costs of implementation, encouraging their use in new areas. Conductive metal–organic frameworks represent one intriguing class of materials for further investigation in this area, given their vast structural diversity and the specificity of adsorbate interactions afforded by their crystallinity. Here, we re-examine the electronic conductivity of the desolvated and acetonitrile-solvated microporous framework Cu[Ni(pdt) 2] (pdt 2]= 2,3-pyrazinedithiolate), and find that the conductivity in the pristine material is 200-fold greater than in the solvated state, highlighting the sensitivity of sample conductivity to guest inclusion. Additionally, the desolvated material is demonstrated to selectively adsorb the gaseous hydrocarbons ethane, ethylene, acetylene, propane, propylene, and cis-2-butene at ambient temperature. Investigation of the effect of gas adsorption on conductivity using an in situ measurement cell reveals a chemiresistive response for each adsorbate, and the change in conductivity with adsorbate pressure closely follows an empirical model identical in form to the Langmuir–Freundlich equation. The relative sensitivity of the framework to each adsorbate is, surprisingly, not correlated with binding strength. Instead, the differences in chemiresistive response between adsorbates are found to correlate strongly with gas phase specificmore » heat capacity of the adsorbate. Nanoconfinement effects, manifesting as a relative deviation from the expected chemiresistive response, may influence charge transport in the case of the largest adsorbate considered, cis-2-butene. Finally, time-resolved conductance and adsorption measurements additionally show that the chemiresistive response of the sensor equilibrates on a shorter time scale than gas adsorption, suggesting that interparticle contacts limit conduction through the bulk material and that conductivity at the crystallite surfaces is most responsive to gas adsorption.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of Minnesota, Minneapolis, MN (United States). Dept. of Chemistry, Minnesota Supercomputing Inst., and Chemical Theory Center
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Univ. of Minnesota, Minneapolis, MN (United States). Nanoporous Materials Genome Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
Contributing Org.:
Minnesota Supercomputing Institute (MSI)
OSTI Identifier:
1507018
Grant/Contract Number:  
SC0008688; FG02-17ER16362; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 12; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Aubrey, Michael L., Kapelewski, Matthew T., Melville, Jonathan F., Oktawiec, Julia, Presti, Davide, Gagliardi, Laura, and Long, Jeffrey R.. Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate)2] by Gas Adsorption. United States: N. p., 2019. Web. doi:10.1021/jacs.9b00654.
Aubrey, Michael L., Kapelewski, Matthew T., Melville, Jonathan F., Oktawiec, Julia, Presti, Davide, Gagliardi, Laura, & Long, Jeffrey R.. Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate)2] by Gas Adsorption. United States. doi:10.1021/jacs.9b00654.
Aubrey, Michael L., Kapelewski, Matthew T., Melville, Jonathan F., Oktawiec, Julia, Presti, Davide, Gagliardi, Laura, and Long, Jeffrey R.. Mon . "Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate)2] by Gas Adsorption". United States. doi:10.1021/jacs.9b00654.
@article{osti_1507018,
title = {Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate)2] by Gas Adsorption},
author = {Aubrey, Michael L. and Kapelewski, Matthew T. and Melville, Jonathan F. and Oktawiec, Julia and Presti, Davide and Gagliardi, Laura and Long, Jeffrey R.},
abstractNote = {The development of new chemiresistive materials for use in chemical sensors that operate near ambient conditions could potentially reduce the costs of implementation, encouraging their use in new areas. Conductive metal–organic frameworks represent one intriguing class of materials for further investigation in this area, given their vast structural diversity and the specificity of adsorbate interactions afforded by their crystallinity. Here, we re-examine the electronic conductivity of the desolvated and acetonitrile-solvated microporous framework Cu[Ni(pdt)2] (pdt2]= 2,3-pyrazinedithiolate), and find that the conductivity in the pristine material is 200-fold greater than in the solvated state, highlighting the sensitivity of sample conductivity to guest inclusion. Additionally, the desolvated material is demonstrated to selectively adsorb the gaseous hydrocarbons ethane, ethylene, acetylene, propane, propylene, and cis-2-butene at ambient temperature. Investigation of the effect of gas adsorption on conductivity using an in situ measurement cell reveals a chemiresistive response for each adsorbate, and the change in conductivity with adsorbate pressure closely follows an empirical model identical in form to the Langmuir–Freundlich equation. The relative sensitivity of the framework to each adsorbate is, surprisingly, not correlated with binding strength. Instead, the differences in chemiresistive response between adsorbates are found to correlate strongly with gas phase specific heat capacity of the adsorbate. Nanoconfinement effects, manifesting as a relative deviation from the expected chemiresistive response, may influence charge transport in the case of the largest adsorbate considered, cis-2-butene. Finally, time-resolved conductance and adsorption measurements additionally show that the chemiresistive response of the sensor equilibrates on a shorter time scale than gas adsorption, suggesting that interparticle contacts limit conduction through the bulk material and that conductivity at the crystallite surfaces is most responsive to gas adsorption.},
doi = {10.1021/jacs.9b00654},
journal = {Journal of the American Chemical Society},
number = 12,
volume = 141,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 4, 2020
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