In situ quantitative determination of the intermolecular attraction between amines and a graphene surface using atomic force microscopy

Abstract

The adsorption of pollutants on carbonaceous environmental media has been widely studied via batch sorption experiments and spectroscopic characterization. However, the molecular interactions between pollutants and interfacial sites on carbonaceous materials have only been indirectly investigated. To comprehend the adsorption mechanisms in situ, we applied atomic force microscopy force spectroscopy (AFM-FS) to quantitatively determine the molecular interactions between typical amines (methylamines and N-methylaniline) and the surface of highly oriented pyrolytic graphite (HOPG), which was supported by the single molecule interaction derived from density functional theory and batch adsorption experiments. This method achieved direct and in situ characterization of the molecular interactions in the adsorption process. The molecular interactions between the amines and the adsorption sites on the graphite surface were affected by pH and peaked at pH 7 due to strong cation-π interactions. When the pH was 11, the attractions were weak due to a lack of cation-π interaction, whereas, when the pH was 3, the competitive occupation of hydronium ions on the surface reduced the attraction between the amines and HOPG. Based on AFM-FS, the single molecule force of methylamine and N-methylaniline on the graphite surface was estimated to be 0.224 nN and 0.153 nN, respectively, which was consistent with density functional theory (DFT) calculations. This study broadens our comprehension of cation-π interactions between amines and electron-rich aromatic compounds at the micro/nanoscale.