Phenyl-Modified Carbon Nitride Quantum Nanoflakes for Ultra-Highly Selective Sensing of Formic Acid: A Combined...

Formic acid (HCOOH) is an important intermediate in chemical synthesis, pharmaceuticals, the food industry, and leather tanning and is considered to be an effective hydrogen storage molecule. Direct contact with its vapor and its inhalation lead to burns, nerve injury, and dermatosis. Thus, it is critical to establish efficient sensing materials and devices for the rapid detection of HCOOH. In the present study, we introduce a chemical sensor based on a quartz crystal microbalance (QCM) sensor capable of detecting trace amounts of HCOOH. This sensor is composed of colloidal phenyl-terminated carbon nitride (Ph-g-C₃N₄) quantum nanoflakes prepared using a facile solid-state method involving the supramolecular preorganization technology. In contrast to other synthetic methods of modified carbon nitride materials, this approach requires no hard templates, hazardous chemicals, or hydrothermal treatments. Comprehensive characterization and density functional theory (DFT) calculations revealed that the QCM sensor designed and prepared here exhibits enhanced detection sensitivity and selectivity for volatile HCOOH, which originates from chemical and hydrogen-bonding interactions between HCOOH and the surface of Ph-g-C₃N₄. According to DFT results, HCOOH is located close to the cavity of the Ph-g-C₃N₄ unit, with bonding to graphitic carbon and pyridinic nitrogen atoms of the nanoflake. The sensitivity of the Ph-g-C₃N₄-nanoflake-based QCM sensor was found to be the highest (128.99 Hz ppm^-1) of the substances studied, with a limit of detection (LOD) of HCOOH down to a sub-ppm level of 80 ppb. This sensing technology based on phenyl-terminated attached-g-C₃N₄ nanoflakes establishes a simple, low-cost solution to improve the performance of QCM sensors for the effective discrimination of HCOOH, HCHO, and CH₃COOH vapors using smart electronic noses.