非晶态中空CoSx增强丁基黄原酸钠的去除和抗菌活性及其可能的实际应用

Enhanced sodium butyl xanthate removal and antibacterial activity by amorphous hollow CoSx and its possible practical application

  • 摘要: 钴基金属有机框架材料因其卓越的催化和抗菌性能,在废水处理领域受到广泛关注。本研究通过溶剂热法硫化ZIF-67成功合成CoSₓ,其中CoS-0.25和CoS-1.00分别在去除丁基黄原酸钠(SBX)和抑制大肠杆菌(E.coli)方面表现出优异性能。CoS-0.25通过活化过一硫酸盐(PMS)在1分钟内去除89%的SBX,并在较宽pH范围(3-11)内保持高效去除性能。此外,CoS-0.25/PMS体系可以连续10小时保持80%以上的SBX去除率,在实际水体中去除率可达90%。同时,CoS-1.00表现出优于ZIF-67的抗菌性能,在120分钟内对E.coli的抗菌率达98%,最小抗菌浓度为31.30 μg/mL。这是因为CoS-0.25和CoS-1.00增强的亲水性促进了与SBX和细菌细胞的界面接触,也更有利于活性氧物种的产生。机制研究表明,超氧自由基(·O2−)是SBX去除过程中的主要活性氧物种,S物种通过加速Co3+/Co2+氧化还原循环促进PMS活化。此外,活性氧物种通过破坏细菌细胞壁实现细菌灭活,从而获得强效抗菌性能。

     

    Abstract: Co-based metal-organic frameworks (MOFs) have gained significant attention in wastewater treatment owing to their exceptional catalytic and antibacterial properties. In this work, CoSₓ were successfullysynthesized via the sulfurization of ZIF-67 using a solvothermal method. Among the synthesized materials, CoS-0.25 and CoS-1.00 exhibited outstanding performance in the removal of sodium butyl xanthate (SBX) and the inhibition of Escherichia coli (E.coli), respectively. CoS-0.25 activated peroxymonosulfate (PMS) to remove 89% of SBX within 1 minute and maintained high removal efficiency over a broad pH range (3-11). Furthermore, the CoS-0.25/PMS system sustained an SBX removal rate of over 80% for 10 consecutive hours, achieving up to 90% removal in actual water bodies. Meanwhile, CoS-1.00 demonstrated antibacterial performance superior to that of ZIF-67, achieving a 98% antibacterial rate against E.coli within 120 minutes, with a minimum inhibitory concentration of 31.30 μg/mL. The enhanced hydrophilicity of CoS-0.25 and CoS-1.00 promoted interfacial contact with SBX and bacterial cells, respectively, and also facilitated the generation of reactive oxygen species (ROS). Mechanistic investigations revealed that the superoxide radical(·O2−) was the primary ROS responsible for SBX removal, and S species accelerated the Co3+/Co2+redox cycle, thereby promoting PMS activation. In addition, ROS contributed to bacterial inactivation by disrupting the cell wall, resulting in potent antibacterial performance.

     

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