Enhanced adsorption of bisphenol A, tylosin, and tetracycline from aqueous solution to nitrogen-doped multiwall carbon nanotubes via cation-π and π-π electron-donor-acceptor (EDA) interactions

Doping heteroatoms in carbon nanotubes can substantially enhance the electronic polarizability of the carbon surface and thus may facilitate adsorptive interactions of organic contaminants. Here, the adsorption isotherms of three polar/ionizable emerging organic contaminants, bisphenol A, tylosin, and tetracycline from aqueous solutions to synthesized heteroatom nitrogen-doped multiwall carbon nanotubes (N-MCNT) were compared with those to commercial non-doped multiwall carbon nanotubes (MCNT) at pH ~ 6. N-MCNT exhibited much stronger adsorption (3–4 folds higher sorption distribution coefficients, Kd) towards the three adsorbates than MCNT. The hydroxyl group-substituted bisphenol A molecule is rich in π-electrons and thus interacts with the polarized π-electron-depleted N-heterocyclic aromatic ring on N-MCNT via π-π electron-donor-acceptor (EDA) interaction, whereas the protonated amino group and enone groups in the tylosin molecule are deficient in electrons and interact with the neighboring π-electron-rich aromatic ring on N-MCNT via cation-π and π-π EDA interactions, respectively. The tetracycline molecule contains both electron-rich moiety (phenol ring) and electron-depleted moieties (protonated amino group and enone groups), which interact with the corresponding π-electron-acceptor/donor sites on N-MCNT. The proposed adsorption mechanisms were tested by the effects of ionic strength (NaCl or CaCl2), co-present Cu2+ ion, and changing pH on adsorption, and further by the adsorption behavior of a model organic cation (tetraethylamine). These results indicate that enhanced adsorption of emerging organic contaminants to carbon nanotubes can be achieved by doping with heterocyclic nitrogen atoms to facilitate specific EDA interactions. Capsule: Nitrogen-doped multiwall carbon nanotubes exhibit enhanced adsorptive removal of bisphenol A, tylosin, and tetracycline from aqueous solutions. [Display omitted] •N-MCNT exhibits strong adsorption of bisphenol A, tylosin, and tetracycline.•N-MCNT is a superior adsorbent to non-doped MCNT.•N-doping creates more π-electron-depleted and rich sites on N-MCNT.•EDA interaction is the dominant driving force for adsorption to N-MCNT.•EDA properties of bisphenol A, tylosin, and tetracycline change with pH.