High-Performance Sensing of Formic Acid Vapor Enabled by a Newly Developed Nanofilm-Based Fluorescent Sensor.

Although it is widely used in industry and food products, formic acid can be dangerous owing to its corrosive properties. Accurate determination of formic acid would not only benefit its qualified uses but also be an effective way to avoid corrosion or injury from inhalation, swallowing, or touching. Herein, we present a nanofilm-based fluorescent sensor for formic acid vapor detection with a wide response range, fast response speed, and high sensitivity and selectivity. The nanofilm was synthesized at a humid air/dimethyl sulfoxide (DMSO) interface through dynamic covalent condensation between two typically designed building blocks, de-tert-butyl calix[4]arene-tetrahydrazide (CATH) and 4,4',4″,4‴-(ethene-1,1,2,2-tetrayl)tetra-benzaldehyde (ETBA). The as-prepared nanofilm is uniform, flexible, fluorescent, and photochemically stable. The thickness and fluorescence intensity of the nanofilm can be facilely adjusted by varying the concentration of the building blocks and the sensing performance of the nanofilm can be optimized accordingly. Based on the nanofilm, a fluorescent sensor with a wide response range (4.4 ppt-4400 ppm) for real-time and online detection of formic acid vapor was built. With the sensor, a trace amount (0.01%) of formic acid in petroleum ether (60-90 °C) can be detected within 3 s. Besides, fluorescence quenching of the nanofilm by formic acid vapor can be visualized. It is believed that the sensor based on the nanofilm would find real-life applications in corrosion and injury prevention from formic acid.