Silk fibroin protein and graphene synergistically boosting the reactive oxygen species generation of PU/AgI photocatalytic membrane for tetracycline sustained removal

Abstract

Solar-light driven organic pollutants degradation by the recyclable photocatalytic membrane materials emerges as a promising technology for sewage purification. However, low generation of reactive oxygen species severely constraints their photocatalytic activity. Herein, we introduce a novel hydrophilic PU/SF/GO/AgI composite photocatalytic membrane fabricated via adding silk fibroin (SF) and graphene oxide (GO) for TC removal. By visible light irradiation, the PU/SF/GO/AgI membrane with 66.7 wt% SF and 0.05 wt% GO degrades TC with 7-fold increase in comparison with the PU/AgI membrane. The enhance photocatalytic activity is primarily attributed to its efficient generation of reactive oxygen species facilitated by the improved hydrophilicity and boosted charge separation. FTIR and electrochemical results demonstrate that the SF and GO with rich surface oxygen-containing groups contribute to the formation of Ag-O bonds for accelerating charge migration and separation. Significantly, the improved hydrophilicity of PU/SF/GO membrane can not only provide rich binging sites for AgI loading, but also be benefitted to attract small molecules for facilitating to reactive oxygen species generation. As a result, •O2−, •OH and H2O2 concentrations produced in PU/SF/GO/AgI membrane system reaches up to 53.20 μmol g−1 h−1, 7.89 μmol g−1 h−1 and 16.52 μmol, respectively, 6.7, 15.4 and 5.1-times higher than PU/AgI membrane system. Meanwhile, under LED irradiation of 12 h, TC degradation efficiency by the dynamic membrane reactor equipped with PU/SF/GO/AgI can reach up to 53 % and achieve 41 % TOC removal, exceeding the pure PU/AgI and those of reported membrane materials. This work proves that tuning hydrophilicity and charge migration of PU membrane can enhance their photocatalytic activity and recyclability, which offers an effective strategy for constructing sustained solar-light driven photocatalytic membrane system.