Surface Complexation of the Zwitterionic Fluoroquinolone Antibiotic Ofloxacin to Nano-Anatase TiO_2 Photocatalyst Surfaces

摘要

The surface complexation behavior of ofloxacin (OFX), a zwitterionic fluoroquinolone antibiotic, to nano-anatase titanium dioxide (TiO_2) was characterized. OFX adsorption in aqueous TiO_2 suspensions was measured as a function of pH, OFX concentration, and electrolyte type and concentration, and structural information was derived from in situ spectroscopic observations. An ultraviolet-visible spectral red shift upon OFX adsorption indicated formation of inner-sphere coordination complexes. Fourier transform infrared spectra of TiO_2-adsorbed OFX were invariable over a wide concentration and pH range and were similar to measured spectra of dissolved species wherein die carboxylate group is deprotonated. A charge distribution surface complexation model constrained by spectroscopic observations was developed to describe macroscopic adsorption trends. A tridentate mode of adsorption involving bridging bidentate inner-sphere coordination of the deprotonated carboxylate group and hydrogen bonding through the adjacent carbonyl group on the quinoline ring resulted in successful predictions of observed adsorption trends. In NaClO_4 electrolyte, spectroscopic data and model fitting suggested that OFX ion pairing with ClO_4~ -enhanced adsorption under acidic conditions. Moreover, comparison of OFX adsorption data with the pH trend in the kinetics of OFX degradation by visible light (λ > 400 nm) photocatalysis suggested that adsorbed OFX-ClO_4~- ion pairs inhibit photodegradation.