Engineering CuMOF in TiO₂ Nanochannels as Flexible Gas Sensor for High-Performance NO Detection at Room Temperature

As a marker molecule in respiratory gases for the pulmonary disease asthma, nitric oxide (NO) has attracted much attention for real-time gas monitoring. However, low sensitivity, poor selectivity, and high operating temperature limit the practical applications of metal oxide semiconductor (MOS) based chemiresistor gas sensors. Herein, by deliberately introducing metal-organic frameworks (MOFs) in free-standing TiO₂ nanochannels (NCs), a chemiresistor gas sensor with excellent detection ability and outstanding selective traits is developed for sensing NO at room temperature (RT). The precisely engineered Cu(II)-based MOF Cu-TCA (H₃TCA = tricarboxytriphenyl amine) induces more active surface in the NCs, causing the buildup of CuTCA/TiO₂ p-n heterojunctions that improve the sensing response at RT just via a simple UV irradiation (λ = 365 nm). Importantly, the specialized reductive reaction of Cu(II) by NO enables a remarkable selectivity toward NO analysis. Owing to the synergistic large active surface and chemical sensitization effects from Cu-TCA, the resulting Cu-TCA/TiO₂ NCs show outstanding sensing performance; i.e., the response ((R_gas - R_air)/R_air) reaches 124% at 50 ppm of NO with a detection limit of 140 ppb at RT. In addition, the response time decreases to 25.6% if the system is subjected to UV irradiation. The as-formed sensing membrane is also demonstrated to be practically effective for flexible and wearable sensing devices for quantitative NO analysis. This study facilitates the use of MOFs to achieve synergistically enhanced selectivity and sensitivity to develop high-performance gas sensors.