ABSTRACT Two-dimensional (2D) catalytic ozonation membranes are promising for the treatment of micropollutants in wastewater due to simultaneous ozone-catalyzed degradation and membrane filtration processes. However, it remains challenging for 2D catalytic ozonation membranes to efficiently degrade micropollutants due to low mass-transfer efficiency and poor catalytic activity. Herein, Fe/Mn bimetallic metal–organic framework (MOF) intercalated lamellar MnO 2 membranes with fast and robust ozone-catalyzed mass-transfer channels were developed on the surface of the hollow fiber ceramic membrane (HFCM) to obtain 2D Fe/Mn-MOF@MnO 2 -HFCM for efficiently degrading micropollutants in wastewater. The intercalation of Fe/Mn-MOF expanded the interlayer spacing of the MnO 2 membrane, thereby providing abundant transport channels for rapid passage of water. More notably, the Fe/Mn-MOF provided enriched reactive sites as well as high electron transfer efficiency based on the redox cycling between Mn 3+ /Mn 4+ and Fe 2+ /Fe 3+ , ensuring the effective catalytic oxidative degradation of micropollutants including tetracycline hydrochloride (TCH), methylene blue, and methyl blue. Moreover, the carboxyl groups on the MOF formed covalent bonds (–COO–) with the hydroxyl groups in MnO 2 between layers, which increased the interaction between MnO 2 nanosheets to form stable interlayer channels. Specifically, the optimal composite membrane achieved a high removal rate of TCH micropollutant (93.4%), high water treatment capacity (282 L·m –2 ·h –1 ·MPa –1 ), and excellent long-term stability (1200 min). This study provides a simple and easily scalable strategy to construct fast, efficient, and stable 2D catalytic mass-transfer channels for the efficient treatment of micropollutants in wastewater.
2-Mercaptobenzothiazole (MBT), a widely utilized metal corrosion inhibitor in industrial production processes, has become a typical persistent organic pollutant (POP) in the circulating water of coal chemical pipelines. In this study, Fe/Mn bimetallic MOF materials supported on carbon fiber paper (PC) were employed for the first time as an electro-Fenton cathode (Fe/Mn@MPC) in a heterogeneous electro-Fenton system, achieving efficient degradation of MBT. Specifically, this novel cathode enabled 96.35 % removal of MBT within 2 h. The uniformly rough fiber morphology presented by the Fe/Mn@MPC cathode results in an increased electrochemically active surface area and reduced resistance. Remarkably, it maintains a very stable catalytic activity over a wide pH range (3–11) and after 10 h of continuous operation, which confirms that the bimetallic synergistic effect enhances the stability of the system. EPR and quenching experiments identified hydroxyl radicals as the primary active species. Based on HPLC-MS results, MBT degradation pathways involving sulfur oxidation intermediate cleavage and benzothiazole ring detachment were proposed. This work presents a promising cathode design for the treatment of thiol-containing wastewater and offers new insights into the efficient remediation of coal chemical wastewater.
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