Covalent Triazine Framework C₆N₆ as an Electrochemical Sensor for Hydrogen-Containing Industrial Pollutants. A DFT Study

Industrial pollutants pose a serious threat to ecosystems. Hence, there is a need to search for new efficient sensor materials for the detection of pollutants. In the current study, we explored the electrochemical sensing potential of a C₆N₆ sheet for H-containing industrial pollutants (HCN, H₂S, NH₃ and PH₃) through DFT simulations. The adsorption of industrial pollutants over C₆N₆ occurs through physisorption, with adsorption energies ranging from -9.36 kcal/mol to -16.46 kcal/mol. The non-covalent interactions of analyte@C₆N₆ complexes are quantified by symmetry adapted perturbation theory (SAPT0), quantum theory of atoms in molecules (QTAIM) and non-covalent interaction (NCI) analyses. SAPT0 analyses show that electrostatic and dispersion forces play a dominant role in the stabilization of analytes over C₆N₆ sheets. Similarly, NCI and QTAIM analyses also verified the results of SAPT0 and interaction energy analyses. The electronic properties of analyte@C₆N₆ complexes are investigated by electron density difference (EDD), natural bond orbital analyses (NBO) and frontier molecular orbital analyses (FMO). Charge is transferred from the C₆N₆ sheet to HCN, H₂S, NH₃ and PH₃. The highest exchange of charge is noted for H₂S (-0.026 e^-). The results of FMO analyses show that the interaction of all analytes results in changes in the E_H-L gap of the C₆N₆ sheet. However, the highest decrease in the E_H-L gap (2.58 eV) is observed for the NH₃@C₆N₆ complex among all studied analyte@C₆N₆ complexes. The orbital density pattern shows that the HOMO density is completely concentrated on NH₃, while the LUMO density is centred on the C₆N₆ surface. Such a type of electronic transition results in a significant change in the E_H-L gap. Thus, it is concluded that C₆N₆ is highly selective towards NH₃ compared to the other studied analytes.