Effect of copper ion on adsorption of chlorinated phenols and 1-naphthylamine to surface-modified carbon nanotubes

Understanding the adsorptive interactions between organic contaminants and carbon nanotubes (CNTs) is critical to both environmental applications and risk management of CNTs. The objective of the present study was to understand how transitional metal ions with strong complexing capabilities might affect the adsorption of hydroxyl- and amino-substituted aromatics to surface O-functionality-rich single-walled CNTs (O-SWNT) and N-functionality-rich single-walled CNTs (N-SWNT). Adsorption of 2,4-dichlorophenol, pentachlorophenol, and 1-naphthylamine to O-SWNT and N-SWNT can be significantly enhanced in the presence of Cu(II) (50 mg/L), whereas adsorption of 1,2-dichlorobenzene is essentially unaffected. The most likely mechanism for the Cu-enhanced adsorption is that Cu(II) serves as a bridging agent between organic solutes and the functional groups on CNT surfaces. For the adsorption of 1-naphthylamine to N-SWNT, an additional mechanism might be possible; that is, the complexation of Cu(II) with the N-functional groups of N-SWNT can change these groups from strong Lewis bases to Lewis acids and thereby significantly enhance adsorption via the mechanism of Lewis acid-base interactions. In addition, adsorption of Cu(II) can be significantly enhanced by the adsorption of organic cosolutes.