Conductive Stimuli-Responsive Coordination Network Linked with Bismuth for Chemiresistive Gas Sensing
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.
© 2021 American Chemical Society. Attribution-NonCommercial-NoDerivatives 4.0 International (CC BY-NC-ND 4.0). 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.
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