Releasing Si O tetrahedron and Al O octahedron from montmorillonite to enhance the adsorption performance of carbon@chitosan@montmorillonite nanosheet for cationic dyes: Coupling quantum chemistry simulations with experiments

A novel adsorbent of carbon@chitosan@montmorillonite nanosheet (C@CS@ MTN) was successfully fabricated layer-by-layer assembly method to deal with cationic dye wastewater. Batch adsorption experiments showed that the adsorption capacities of MB and RhB were higher than 325 mg·g-1 and 236 mg·g-1, respectively, indicating that C@CS@MTN exhibited an excellent adsorption performance. Through quantum chemistry simulations, the molecular electrostatic potential, electron density, differential charge density, molecular orbital distribution and adsorption binding energy were analyzed to reveal the adsorption reaction mechanism between C@CS@MTN and cationic dyes. The results indicated that SiO tetrahedron ring and AlO octahedron ring released from montmorillonite with inherent periodic structure was beneficial to electrostatic attraction, while cation-π interaction benefitted from the interaction between Al atoms of AlO octahedron ring and benzene ring. It was noteworthy that the electron transfer direction of electrostatic attraction was from O atoms of SiO tetrahedron ring to the benzene ring of dye molecules, but the electron transfer direction of cation-π interaction was from benzene ring of dye molecules to Al atoms of AlO octahedron ring. These results provide fundamental theoretical support for the functional design of mineral-based adsorbents and the efficient removal of cationic dyes.