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氧化铜/多壁碳纳米管过滤器去除水中病毒的效率和稳定性评价。

Efficiency and stability evaluation of CuO/MWCNTs filters for virus removal from water.

机构信息

Laboratory for High Performance Ceramics, Empa, Swiss Federal Laboratories for Materials Science and Technology, Dübendorf, Switzerland; Faculty of Materials Science and Ceramics, AGH, University of Science and Technology, Krakow, Poland.

Department of Process Engineering, Eawag, Swiss Federal Institute of Aquatic Science and Technology, Dübendorf, Switzerland.

出版信息

Water Res. 2020 Jul 15;179:115879. doi: 10.1016/j.watres.2020.115879. Epub 2020 Apr 28.

Abstract

Both multi-walled carbon nanotubes (MWCNTs) and metal or metal oxides have demonstrated virus removal efficacy in drinking water applications. In this study, MWCNTs were coated with copper(I) oxide (CuO) using three distinct synthesis procedures (copper ion attachment, copper hydroxide precipitation, and [Cu(NH)] complex attachment) and virus removal efficacy (using MS2 bacteriophages) was evaluated. All synthesis procedures resulted in the presence of adsorbed, nanosized CuO particles on the MWCNTs, shown using X-ray diffraction. Further, transmission electron microscopy confirmed uniform copper(I) oxide distribution along the MWCNTs for all three materials. Virus removal efficacy was assessed for all three synthesised composites both before and after material conditioning (filtering for at least 24 h/280 mL/h), and accounting for additional MS2 inactivation in the permeate due to continued copper inactivation from dissolved/desorbed copper in permeate (time-control). Material conditioning influenced virus removal, with the first litres of water containing higher concentrations of copper than the sixth litres of water, suggesting excess or non-bonded copper species dissolve from filters. Higher copper dissolution was observed for water at pH 5 than at pH 7, which decreased with time. Copper dissolution most likely caused an associated decrease in copper adsorbed to MWCNTs in the filters, which may explain the observed lower MS2 removal efficacy after conditioning. Additionally, the time-control study (immediately after filtration as compared to 2 h after filtration) highlighted continued MS2 inactivation in the permeate over time. The obtained results indicate that the synthesis procedure influences virus removal efficacy for MWCNTs coated with copper oxides and that virus removal is likely due to not only virus electrostatic adsorption to the coated MWCNTs, but also through antiviral properties of copper which continues to act in the permeate. In conclusion, it is highly important to revise the methods of testing filter materials for virus removal, as well as procedure for virus concentration evaluation.

摘要

多壁碳纳米管(MWCNTs)和金属或金属氧化物已在饮用水应用中表现出去除病毒的功效。在这项研究中,使用三种不同的合成程序(铜离子附着、铜氢氧化物沉淀和[Cu(NH)]络合物附着)在 MWCNTs 上涂覆了氧化铜(CuO),并评估了病毒去除效果(使用 MS2 噬菌体)。所有合成程序都导致吸附在 MWCNTs 上的纳米尺寸的 CuO 颗粒的存在,这一点通过 X 射线衍射证明。此外,透射电子显微镜证实了所有三种材料中 CuO 沿 MWCNTs 的均匀分布。对所有三种合成复合材料进行了评估,包括在材料调理前后(至少过滤 24 小时/280 毫升/小时),并考虑到由于溶解/解吸的铜在渗透物中持续失活而导致的渗透物中 MS2 额外失活(时间控制)。材料调理会影响病毒去除,前几升水中的铜浓度高于第六升水中的铜浓度,这表明过滤后会从过滤器中溶解出多余的或非键合的铜物种。在 pH 值为 5 的水中观察到的铜溶解量高于 pH 值为 7 的水,并且随着时间的推移而降低。铜溶解最可能导致过滤器中吸附在 MWCNTs 上的铜的相关减少,这可以解释调理后观察到的 MS2 去除效率降低。此外,时间控制研究(与过滤后立即相比,过滤后 2 小时)强调了随着时间的推移,渗透物中 MS2 的持续失活。结果表明,合成程序会影响涂覆氧化铜的 MWCNTs 的病毒去除效率,并且病毒去除不仅可能是由于涂覆的 MWCNTs 对病毒的静电吸附,还可能是由于铜的抗病毒特性在渗透物中继续发挥作用。总之,非常有必要修改测试过滤材料去除病毒的方法,以及评估病毒浓度的程序。

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