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

Abstract

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 (NH 3 and NO) and volatile organic compounds (VOCs: acetone, ethanol, methanol, and isopropanol). The chemiresistive sensing of NO and NH 3 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 NH 3 comprise a complex combination of steric, electronic, and protic properties of the targeted analytes.

Negative electrodes for supercapacitors with good performance using conductive bismuth-catecholate metal–organic frameworks

“…In addition, the calculated BET surface areas of our Bi (HHTP) nanobelts are much higher than the value of Bi (HHTP) in the reported literature. 29 As mentioned above, the TEM image shows the Bi(HHTP) nanobelts contain many small crystals (Fig. S3 †), and the small open interspaces between the crystals can allow more nitrogen molecules to be adsorbed during the nitrogen adsorption measurement, which could be attributed to the enhancement in specific surface areas.…”

“…S1a,† and the diffraction peaks of the samples agree well with the reported results of the Bi(HHTP) crystals. 29 In addition, a weak peak is observed at the 2 θ position of 6.74°, which corresponds to a very small amount of residual bismuth( iii ) acetate. The amount of residual bismuth( iii ) acetate is estimated to be very low, and its presence in Bi(HHTP) almost has no influence on the electrochemical performance of Bi(HHTP).…”

“…2c, displays two different peaks at 159.8 eV and 165.0 eV, which implies the low valence oxidation states of the Bi element. 29 It means that the Bi ions in the Bi(HHTP) electrode can be allowed to gain or lose electrons in the charge/discharge process. Thus, Bi ions are used as the active site of the faradaic reactions.…”

“…2c, displays two different peaks at 159.8 eV and 165.0 eV, which implies the low valence oxidation states of the Bi element. 29 It means that the Bi ions in the Bi(HHTP) electrode can be allowed to gain or lose electrons in the charge/discharge As is known, the specific surface area of active materials can affect their energy storage performance. 31 The nitrogen adsorption measurements are used to investigate the surface areas and pore size distributions of the Bi(HHTP) nanobelts (Fig.…”

Controllable Construction of Two-Dimensional Conductive M3(HHTP)2 Nanorods for Electrochemical Sensing of Malachite Green in Fish

“…It has been found that the same CMOF materials with physical forms have very different properties due to their different microstructures. − Moreover, the electrocatalytic and electrochemical sensing properties of the same series of conductive MOFs with different metal atomic centers also differ . For the linkers, a tricatecholate with a highly conjugated structure, 2,3,6,7,10,11-hexahydroxy­triphenylene (H 12 C 18 O 6 , HHTP), is redox-active and capable of reversible interconversions among catecholate, quinone, and semiquinonate, − making it have a variety of applications in electrocatalysis, , charge storage, ,− and chemical resistance sensing. − The M 3 (HHTP) 2 nanorod materials based on an electrochemically active metal as the metal center are expected to show high electrocatalytic activity for construction of electrochemical sensors.…”