Exploring of laccase-lake nanozyme and membrane filters for efficient removal of tetracycline hydrochloride

Laccase is utilized as green catalyst in the environmental catalysis. Nevertheless, the drawbacks such as poor stability and difficulty in recycling have seriously restricted its application. Here, we simulated the binding pocket and catalytic active site of nature laccase, and designed a laccase-mimicking nanozyme (named as GA-Cu and the average diameter was 600 nm) with high activity and stability by using Cu²⁺ as the active center, 2-aminoimidazole as well as glutathione (GSH) as the ligand. Compared with natural laccase, the GA-Cu nanozymes showed excellent stability and reusability under extreme conditions. Furthermore, to overcome the problems of difficult recycling and easy secondary contamination, we innovatively proposed to load GA-Cu nanozymes onto nylon membranes (GA-Cu@CS/GA-Cu/nylon membranes) by vacuum-assisted filtration using chitosan (CS) as a binder to degrade tetracycline hydrochloride (TC) by filtration. Encouragingly, 50 mg/L of TC was almost completely removed by filtration once at 0.15 MPa pressure. The results have showed that the GA-Cu@CS/GA-Cu/nylon membrane removed TC mainly through degradation, and more than 80 % of TC was degraded through desorption experiments. Finally, some degradation products were identified by LC-MS and three possible degradation pathways were proposed. These findings demonstrate the potential of GA-Cu@CS/GA-Cu/nylon membrane for environmental remediation, and will be a general and important strategy for the design of membrane filters based on the excellent performance of nanozyme.