Detection of NO2 Down to One ppb Using Ion-in-Conjugation-Inspired Polymer

Abstract

Nitrogen dioxide (NO₂ ) emission has severe impact on human health and the ecological environment and effective monitoring of NO₂ requires the detection limit (limit of detection) of several parts-per-billion (ppb). All organic semiconductor-based NO₂ sensors fail to reach such a level. In this work, using an ion-in-conjugation inspired-polymer (poly(3,3'-diaminobenzidine-squarine, noted as PDBS) as the sensory material, NO₂ can be detected as low as 1 ppb, which is the lowest among all reported organic NO₂ sensors. In addition, the sensor has high sensitivity, good reversibility, and long-time stability with a period longer than 120 d. Theoretical calculations reveal that PDBS offers unreacted amine and zwitterionic groups, which can offer both the H-bonding and ion-dipole interaction to NO₂ . The moderate binding energies (≈0.6 eV) offer high sensitivity, selectivity as well as good reversibility. The results demonstrate that the ion-in-conjugation can be employed to greatly improve sensitivity and selectivity in organic gas sensors by inducing both H-bonding and ion-dipole attraction.

Keywords: ion-dipole attraction; ion-in-conjugation; nitric dioxide sensors; ppb; zwitterionic.