Tetracycline removal by double-metal-crosslinked alginate/graphene hydrogels through an enhanced Fenton reaction

Polymer hydrogel usually has limited catalytic activity and stability in Fenton catalysis. Here, we presented for the first time the preparation of a novel double-metal-crosslinked alginate hydrogel using graphene oxide to facilitate the Fe(II)/Fe(III) redox cycles. Five multivalent metal cations were used as crosslinkers to prepare different alginate-GO-M (Fe(III), Fe(II), La(III), Ce(III), and Co(II)), and the effects of assisted metal cations (La(III), Ce(III), and Co(II)) on different Fe(II) bimetallic alginate-GO-Fe-M(AG-Fe-M) complexes were investigated. Double-metal-crosslinked alginate-GO hydrogels can degrade tetracycline much faster during the initial 10 min than single-metal-crosslinked hydrogels. In addition, the release of iron from AG-Fe-Ce (10.59 ppm) was less than that from AG-Fe-Co (21.57 ppm) and AG-Fe-La (25.6 ppm) during the Fenton reaction. More importantly, the AG-Fe-Ce did not release TOC and maintained most of the catalytic activity after four reuse cycles, confirmed its excellent stability. For the treatment of raw water containing a high proportion of proteinaceous matter and tetracycline, the AG-Fe-Ce significantly reduced the molecular weight of the dissolved organic matter. We deduced that the humic acid and protein show good complexation ability to tetracycline, thereby reduced its bioavailability. This study provides new insights into the synthesis of polymer catalysts for water treatment.