Highly exfoliated graphitic carbon nitride for efficient removal of wastewater pollutants: Insights from DFT and statistical modelling

The present work entails the synthesis of thermally modified graphitic carbon nitride (GCN) using a two-step thermal treatment procedure and its subsequent use in the photocatalytic reduction of toxic pollutants such as rhodamine B dye (RhB) and chromium (VI) (Cr(VI)) from aquatic environments. The as-synthesised exfoliated GCN (GCNX) is characterised by X-ray diffraction (XRD) analysis, Fourier transform infrared (FTIR) spectros-copy, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS), Bru-nauer-Emmett-Teller analysis (BET), diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM). These characterisations helped to elucidate the phase formation, chemical structure, composition, surface area, optical properties, and morphology of the sample. With assistance from a visible light source, GCNX can degrade RhB dye within 30 min in the presence of hydrogen peroxide (H2O2) and reduce Cr(VI) to Cr(III) in under 2 h in the presence of formic acid (FA/HCOOH). Variations in different catalytic parameters, including catalyst amount, pH of the solution, initial RhB or Cr(VI) concentration, and variation in H2O2 or FA concentration, are performed to inspect their effects on the photodegradation activity of GCNX. Moreover, the GCNX catalyst exhibits impressive stability and reusability. A thorough statistical evaluation follows the response surface methodology to under-stand the complex interaction between the factors contributing to the catalytic activity. The band alignment of differently functionalised GCN blocks in their pristine form and their H2O2/FA-adsorbed states is investigated using first-principles calculations to provide a further understanding of the RhB and Cr(VI) reduction mecha-nisms. The modified GCN can thus be effectively employed as a low-cost material for removing contamination from aquatic environments.

Automated summary

This study focuses on the synthesis of thermally modified graphitic carbon nitride (GCN) and its application in the photocatalytic reduction of toxic pollutants. The characterisations of the synthesised material helped to understand its structure, composition, and morphology. The GCN catalyst showed impressive stability and reusability, and statistical evaluation and first-principles calculations were conducted to further investigate its catalytic activity and reduction mechanisms.