Tailored Ionic Electronic Hybrid Porous Conductors for Ultrasensitive Flexible Chemical Sensor

Abstract The rapid rise of artificial intelligence and the Industrial Internet of Things has brought new opportunities for developing flexible intelligent gas sensors. Ammonium hydroxide, as an important industrial and food processing raw material, can pose a great threat to human health and the ecological environment. In addition, the NH ₃ detection together with high humidity is of great significance for the clinical diagnosis of patients' exhaled gas ( e.g ., asthma and nephropathy). Herein, novel mixed ionic‐electronic conductors (MIECs) with porous structure have been in situ synthesized based on ionic conductive metal‐organic framework (Zn ₃ (HITP) ₂ ) (HITP = 2,3,6,7,10,11‐hexaiminotriphenylene) and electronic conductive π‐conjugated polymer (N‐alkyl‐diketopyrrolo‐pyrroledithienylthieno[3,2‐b]thiophene, DPP‐DTT) through a facile liquid–liquid interface self‐assembly strategy. The tailored Zn ₃ (HITP) ₂ /DPP‐DTT sensor exhibits excellent sensing performance toward ammonium hydroxide without heating, including unique selectivity, high sensitivity, rapid response speed, low detectable limit ( ca . 200 ppb), low theoretical limit of detection (LOD) (2.3 ppb), and more interestingly, ultra‐low operation voltage (down to 30 mV) owing to its unique electron‐ion coupling and synergistic effects. Interestingly, the sensor can even detect NH ₃ gas under ultrahigh humidity (95%), and it also exhibits dual‐functional sensing potential to recognize ammonium hydroxide and NH ₃ molecules. As a demonstration, miniaturized and flexible sensors are integrated into a portable device wirelessly linked with a smartphone for real‐time monitoring. Density functional theory (DFT) calculations confirm that the junction films have high adsorption energy toward NH ₃ molecules in the existence of H ₂ O molecules, implying the strong adsorption interaction between host and guest molecules. This MIECs‐sensing material provides a new candidate for ultrasensitive intelligent flexible gas sensors.