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Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing

Aykanat, Aylin and Jones, Christopher G. and Cline, Evan and Stolz, Robert M. and Meng, Zheng and Nelson, Hosea M. and Mirica, Katherine A. (2021) Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing. ACS Applied Materials & Interfaces, 13 (50). pp. 60306-60318. ISSN 1944-8244. doi:10.1021/acsami.1c14453.

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This paper describes the design, synthesis, characterization, and performance of a novel semiconductive crystalline coordination network, synthesized using 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP) ligands interconnected with bismuth ions, toward chemiresistive gas sensing. Bi(HHTP) exhibits two distinct structures upon hydration and dehydration of the pores within the network, Bi(HHTP)-α and Bi(HHTP)-β, respectively, both with unprecedented network topology (2,3-c and 3,4,4,5-c nodal net stoichiometry, respectively) and unique corrugated coordination geometries of HHTP molecules held together by bismuth ions, as revealed by a crystal structure resolved via microelectron diffraction (MicroED) (1.00 Å resolution). Good electrical conductivity (5.3 × 10⁻³ S·cm⁻¹) promotes the utility of this material in the chemical sensing of gases (NH₃ and NO) and volatile organic compounds (VOCs: acetone, ethanol, methanol, and isopropanol). The chemiresistive sensing of NO and NH₃ using Bi(HHTP) exhibits limits of detection 0.15 and 0.29 parts per million (ppm), respectively, at low driving voltages (0.1–1.0 V) and operation at room temperature. This material is also capable of exhibiting unique and distinct responses to VOCs at ppm concentrations. Spectroscopic assessment via X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopic methods (i.e., attenuated total reflectance-infrared spectroscopy (ATR-IR) and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS)), suggests that the sensing mechanisms of Bi(HHTP) to VOCs, NO, and NH₃ comprise a complex combination of steric, electronic, and protic properties of the targeted analytes.

Item Type:Article
Related URLs:
URLURL TypeDescription
Aykanat, Aylin0000-0002-1721-772X
Jones, Christopher G.0000-0003-4308-1368
Cline, Evan0000-0001-7709-2650
Stolz, Robert M.0000-0002-9291-0794
Meng, Zheng0000-0002-6775-3213
Nelson, Hosea M.0000-0002-4666-2793
Mirica, Katherine A.0000-0002-1779-7568
Additional Information:© 2021 American Chemical Society. Received 30 July 2021. Accepted 16 November 2021. Published online 13 December 2021. K.A.M., A.A., E.C., Z.M., and R.M.S. acknowledge support from startup funds provided by Dartmouth College, Walter and Constance Burke Research Initiation Award, Irving Institute for Energy and Society, Maximizing Investigators’ Research Award from the National Institutes of Health (R35GM138318), National Science Foundation CAREER Award (No. 1945218), National Science Foundation EPSCoR award (No. #1757371), Army Research Office Young Investigator Program Grant no. W911NF-17-1-0398, US Army Cold Regions Research & Engineering Lab (No. W913E519C0008), Sloan Research Fellowship (No. FG-2018-10561), the Cottrell Scholars Award (No. 26019) from the Research Corporation for Science Advancement, and Camille Dreyfus Teacher-Scholar Award. H.M.N. would like to acknowledge the Packard Foundation for generous support. C.G.J. would like to acknowledge the National Science Foundation Graduate Research Fellowship Program (DGE-1650604) for funding. The authors would like to thank the University Instrumentation Center at the University of New Hampshire (Durham, NH) for the access to XPS and Charles Daghlian and Maxime J. Guinel for their help with SEM. The authors also acknowledge beamline 11-BM of the Advanced Photon Source for the synchrotron pXRD measurement. The authors declare no competing financial interest.
Funding AgencyGrant Number
Dartmouth CollegeUNSPECIFIED
Army Research Office (ARO)W911NF-17-1-0398
Army Cold Regions Research and Engineering LabW913E519C0008
Alfred P. Sloan FoundationFG-2018-10561
Cottrell Scholar of Research Corporation26019
Camille and Henry Dreyfus FoundationUNSPECIFIED
David and Lucile Packard FoundationUNSPECIFIED
NSF Graduate Research FellowshipDGE-1650604
Subject Keywords:bismuth, coordination network, chemiresistor, crystalline, gas sensor, microelectron diffraction, semiconductive
Issue or Number:50
Record Number:CaltechAUTHORS:20211213-518524000
Persistent URL:
Official Citation:Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing. Aylin Aykanat, Christopher G. Jones, Evan Cline, Robert M. Stolz, Zheng Meng, Hosea M. Nelson, and Katherine A. Mirica. ACS Applied Materials & Interfaces 2021 13 (50), 60306-60318; DOI: 10.1021/acsami.1c14453
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112377
Deposited By: George Porter
Deposited On:13 Dec 2021 23:35
Last Modified:03 Jan 2022 18:36

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