Metalloporphyrin-Based Metal–Organic Frameworks for the Ultrasensitive Chemiresistive Detection of NO2: Effect of the Central Metal on Tuning the Sensing Performance

The highly sensitive and selective detection of trace hazardous gases at room temperature is very promising for health protection and environmental safety. Herein, chemiresistive sensors for NO2 were fabricated based on self-assembled films of the four metalloporphyrin (MPor)-based metal–organic frameworks PCN-222-M (M = Cu, Ni, Co, Fe) by the quasi-Langmuir–Shäfer method. It is found that the relative responses of the four PCN-222-M films are linearly related to the NO2 concentration, and the PCN-222-Cu possessed an unprecedented high response to NO2 with a sensitivity of 2209% ppm–1 in the 4–20 ppb range and a low limit of detection (LOD) of 0.93 ppb, achieving the best performance reported so far for NO2 detection at room temperature. Meanwhile, PCN-222-Ni showed the fastest recovery among the four PCN-222-M films, which can be used for the rapid detection of NO2. Excellent reproducibility, stability, selectivity, and moisture resistance are shown for both PCN-222-Cu and PCN-222-Ni. Combining the experimental study and density functional theory (DFT) calculation, the essential roles of MPor units and the MPor/Zr6 cluster hybrid material in tuning the Fermi level and the electron transfer between PCN-222-M and NO2 were further proved. These were less considered topics in previous studies on MOFs. This work explores the application of MPor-based MOFs in gas sensing by selecting appropriate MPor units, thus providing guidance for the development of MOF-based chemiresistive sensors.