Insight into Organic Pollutant Adsorption Characteristics on a g-C₃N₄ Surface by Attenuated Total Reflection...

Herein the adsorption characteristics of zwitterionic dye pollutant Rhodamine B (Rh⁺B^-) on a g-C₃N₄ surface were investigated by both an attenuated total reflection spectroscopy (ATRS) experiment and a molecular dynamics simulation (MDS). For experimental investigation, g-C₃N₄ was coated on a silica optical fiber (SOF) surface to fabricate an adsorption film. According to the ATRS response, adsorption thermodynamics and thermodynamics results were in situ obtained and evaluated. The isothermal Langmuir model was used to calculate the adsorption equilibrium constants (K_ads) and adsorption energies (ΔG_ads) for Rh⁺B^- as 27.25 × 10⁴ M^-1 and -31.01 kJ mol^-1, respectively, which indicated the spontaneous adsorption behavior of Rh⁺B^- at the g-C₃N₄ surface. Using dynamic Elovich modeling, the rate constants of Rh⁺B^- were found to be k₁ = 0.0063 min^-1 and k₂ = 0.0004 min^-1, which indicated two-stage adsorption at the g-C₃N₄ surface. For theoretical simulation, adsorption configurations and adsorption energies were systematically calculated by a molecular dynamics simulation (MDS) . Rh⁺B^- molecules were inclined to orient in a parallel position at the g-C₃N₄ surface during low concentration but a perpendicular position at the g-C₃N₄ surface during high concentration. Combined with experimental and calculation results, this work revealed the microscopic adsorption performance and elucidated the intermolecular interaction between localized interfaces of g-C₃N₄ and hazardous dye pollutant. We propose an adsorption model to explain the process of surface interaction, which is based on molecular orientation and a force-driven mechanism. Electrostatic attraction and π-π interaction dominated the adsorption interaction with an adsorption energy of ΔG_low(ads) = -38.96 kJ mol^-1 for low Rh⁺B^- concentration, and electrostatic attraction dominated the adsorption interaction with an adsorption energy of ΔG_high(ads) = -25.76 kJ mol^-1 for high Rh⁺B^- concentration. This work can provide a fundamental basis for a dye-pollutants removal application by g-C₃N₄ in both adsorption and photocatalyzation.