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

Michael L. Aubrey, Matthew T. Kapelewski, Jonathan F. Melville, Julia Oktawiec, Davide Presti, Laura Gagliardi, Jeffrey R. Long

Research output: Contribution to journalArticle

2 Citations (Scopus)

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 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. 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.

Original languageEnglish (US)
Pages (from-to)5005-5013
Number of pages9
JournalJournal of the American Chemical Society
Volume141
Issue number12
DOIs
StatePublished - Mar 27 2019

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Gas adsorption
Adsorbates
Hydrocarbons
Adsorption
Charge transfer
Gases
Acetylene
Propane
Ethane
Butenes
Specific heat
Hot Temperature
Metals
Pressure
Costs and Cost Analysis
Temperature
Chemical sensors
Acetonitrile
Propylene
Ethylene

PubMed: MeSH publication types

  • Journal Article

Cite this

Chemiresistive Detection of Gaseous Hydrocarbons and Interrogation of Charge Transport in Cu[Ni(2,3-pyrazinedithiolate) 2 ] by Gas Adsorption . / Aubrey, Michael L.; Kapelewski, Matthew T.; Melville, Jonathan F.; Oktawiec, Julia; Presti, Davide; Gagliardi, Laura; Long, Jeffrey R.

In: Journal of the American Chemical Society, Vol. 141, No. 12, 27.03.2019, p. 5005-5013.

Research output: Contribution to journalArticle

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 In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 12. pp. 5005-5013.
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