Humidity-independent NO2 gas sensors based on ZnO-NiOFx nanocomposites and the synergistic humidity-immune effect of fluorine doped NiO

Abstract

Clean, alternative energy sources, especially fuel cells, are gradually attracting global attentions while the produced toxic nitrogen dioxide (NO2) is a greatly hazardous chemical impacting their energy efficiencies. Metal oxide semiconductors (MOS) hold significant promise as NO2 sensors. However, intensive humidity interaction intensifies signal drifts and reliable response inhibitions under variable humidity conditions. In this study, we present a novel approach to address this issue by engineering in-situ F-doped NiO nanocomposites (NiOFx) decorated on ZnO snowflakes achieved through decomposition modulation of ZnOHF precursors. The optimized NO2 sensor demonstrates unparalleled humidity-independence across a wide operating temperature range with prime sensitivity, low detection limit and rapid response/recovery. Matrix algorithm is also implemented in highly precise NO2 identification under complicated atmospheric and humid conditions. Mechanism studies based on temperature programmed desorption (TPD), quasi in-situ X-ray photoelectron spectroscopy (Quasi in-situ XPS) reveal that F− dopants facilitate interfacial electron transferring and inhibit oxygen activity. In-situ diffuse reflectance infrared Fourier transform spectroscopy (In-situ DRIFTS) demonstrates that hygroscopic NiO and electronegative F− synergistically obstruct hydroxyl adsorptions on sensing materials. The innovative approach offers a promising solution for enhancing moisture resistance of MOS sensors for real-time NO2 concentration monitoring in fuel cells and provides valuable insights into anti-humidity mechanisms.