Removal of low-concentration tetracycline from water by a two-step process of adsorption enrichment and photocatalytic regeneration.

Developing a high-performance method that can effectively control pollution caused by low concentrations of antibiotics is urgently needed. Herein, a novel three-dimensional PPy/Zn3In2S6 nanoflower composites were prepared for the comprehensive treatment of low-concentration tetracycline (Tc) hydrochloride in wastewater based on the adsorption/photocatalysis of Zn3In2S6 and the conductivity of PPy. In this preparation method, adsorption enrichment and photocatalytic regeneration were conducted in two steps, eliminating the dilution and dispersion effects of aqueous solvents on photocatalytic species and antibiotics. Results showed that Zn3In2S6 could effectively adsorb 87.85% of Tc at pH of 4.5 and photocatalytically degrade Tc at pH of 10.5. Although the adsorption capacity of Zn3In2S6 was slightly reduced after being combined with PPy, its photocatalytic efficiency was substantially enhanced. Specifically, 0.5%PPy/Zn3In2S6 could degrade 99.92% of the surface-enriched Tc in 1 h and induce the regeneration of the adsorption sites. Furthermore, the adsorption capacity remained above 85% even after recycling PPy/Zn3In2S6 ten times. The photocatalytic degradation mechanism analysis revealed that the enrichment of Tc on 0.5%PPy/Zn3In2S6 negatively impacts the photocatalytic efficiency, while •O2- and •OH radicals were the main oxidative species that played an important role in the photoregeneration process.

Cyclic enrichment of chromium based on valence state transformation in metal-free photocatalytic reductive imprinted composite hydrogel.

Cr (VI) exists in anion form and can be reduced to positive charged Cr (III) under certain conditions. Can positive charged Cr (III) be continually used for absorbing Cr (VI) to achieve cyclic accumulation of chromium? In this paper, an ion imprinting material for adsorption of Cr (VI) was prepared by dispersing polypyrrole (PPy) in a gelatin/chitosan (Gel/CS) hydrogel network, named Gel/CS/PPy. Based on the conversion of Cr (VI) to Cr (III), a cyclic enrichment process including adsorption-photoreduction-fixation-readsorption of Cr (VI) was established in Gel/CS/PPy hydrogel. The composition and structure of the Gel/CS/PPy were analyzed by scanning electron microscopy (SEM), Fourier transform-infrared spectroscopy (FT-IR), thermogravimetric (TGA), texture analyzer (Universal TA), zeta potential and ultraviolet-visible-near infrared spectra (UV-vis-NIR). The conversion of Cr (VI) and Cr (III) and its promoting effect on readsorption were verified by XPS. The results showed that Gel/CS/PPy has good adsorption capacity for Cr (VI) and excellent photocatalytic ability to reduce Cr (VI) to Cr (III). Cr (III)-loaded Gel/CS/PPy can be further used to adsorb Cr (VI) and showed good adsorption efficiency even after four cycles. The optimal operating condition for Cr (VI) adsorption is pH = 3; 2 g/L dose of Gel/CS/PPy; and the adsorption capacity of Cr (VI) was about 106.8 mg/g after six adsorption cycles. Since Gel/CS/PPy is composed of organic components, high purity chromium can be recovered by simple calcination method later. Therefore, the synthesized Gel/CS/PPy has great potential in the practical application of low concentration Cr (VI) treatment in water.