Photocatalytic degradation of tetracycline by metal-organic frameworks modified with Bi2WO6 nanosheet under direct sunlight

Abstract

Porous metal-organic frameworks (MOFs) with visible-light response have attracted much attention in the field of environmental purification and solar energy conversion. In this study, MIL-100(Fe) was modified with Bi2WO6 nanosheets by a facile hydrothermal method to fabricate a photocatalyst with direct Z-scheme heterojunction. When treating the tetracycline (TC) solution under natural sunlight, 12 wt%MIL-100(Fe)/Bi2WO6 obtained the highest apparent rate constant of (6.59 ± 0.52)✕10−3 L mg−1 min−1, which was 16.1 and 3.9 times than that of pristine MIL-100(Fe) and Bi2WO6, respectively. In addition to explore the feasibility of sunlight-activated MIL-100(Fe)/Bi2WO6 to remove TC under various conditions, the degradation intermediates and their possible transformation pathway were provided with the aid of three-dimensional excitation−emission matrix spectra and liquid chromatography-mass spectrometry system. The results of Escherichia coli culture demonstrated that the biotoxicity variation of TC solution would first increase and then decrease with the photodegradation time. Ultimately, based on the results of bandgap calculation, radicals trapping and charge flow tracking experiments, the direct Z-scheme heterojunction between MIL-100(Fe) and Bi2WO6 nanosheets was confirmed and the photocatalytic mechanism for TC degradation was rationally proposed. This work enriched MOFs-based heterojunction photocatalysts and provided a promising method to eliminate hazardous TC from aqueous solution.