DFT study of common anions adsorption at graphene surface due to anion-π interaction

Using density functional theory (DFT) calculations, we researched the different anions adsorption on the graphene and found that anions can be stably adsorbed on the graphene surface due to the anion-π interaction. The adsorption energy decreased as the order of HPO₄^2- > SO₄^2- > F^- > CH₃COO^- > ClO₃^- > NO₃^- > ClO₄^- > SCN^- > Cl^- > Br^-. The adsorption energy markedly increased as the valence of anion increased from negative monovalence (< -20 kcal/mol) to negative bivalence (> -40 kcal/mol). The energy decomposition analysis (EDA) showed that anion-π interaction is mainly induced by orbital effect. This work provides new insights for understanding Hofmeister effect at graphene interface from the molecular level and indicates that the anion-π interaction cannot be ignored at the interface, especially for the substrate with π-electron-rich carbon-based nanomaterials.