Mechanisms for strong adsorption of tetracycline to carbon nanotubes: A comparative study using activated carbon and graphite as adsorbents

Significant concerns have been raised over the presence of antibiotics including tetracyclines in aquatic environments. We herein studied single-walled carbon nanotubes (SWNT) and multi-walled carbon nanotubes (MWNT) as potential effective adsorbents for removal of tetracycline from aqueous solution. In comparison, a nonpolar adsorbate, naphthalene, and two other carbonaceous adsorbents, pulverized activated carbon (AC) and nonporous graphite, were used. The observed adsorbent-to-solution distribution coefficient (Kd, L/kg) of tetracycline was in the order of 104−106 L/kg for SWNT, 103−104 L/kg for MWNT, 103−104 L/kg for AC, and 103−105 L/kg for graphite. Upon normalization for adsorbent surface area, the adsorption affinity of tetracycline decreased in the order of graphite/SWNT > MWNT ≫ AC. The weaker adsorption of tetracycline to AC indicates that for bulky adsorbates adsorption affinity is greatly affected by the accessibility of available adsorption sites. The remarkably strong adsorption of tetracycline to the carbon nanotubes and to graphite can be attributed to the strong adsorptive interactions (van der Waals forces, π−π electron-donor−acceptor interactions, cation-π bonding) with the graphene surface. Complexation between tetracycline and model graphene compounds (naphthalene, phenanthrene, pyrene) in solution phase was verified by ring current-induced 1H NMR upfield chemical shifts of tetracycline moieties.