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

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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
Issue number12
StatePublished - Mar 27 2019

Bibliographical note

Funding Information:
This research was supported by NSF award DMR-1611525. M.T.K. and J.O. thank the NSF for graduate fellowship funding. Use of Beamline 17-BM-B of the Advanced Photon Source at Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The computational part of this research (D.P. and L.G.) was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences under Award DE-FG02-17ER16362. The authors acknowledge the Minnesota Supercomputing Institute (MSI) for providing computing resources. Dr. Katie R. Meihaus is acknowledged for editorial assistance.

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