长效滤除PMs用ZIF-8@CNTs功能化立构复合聚乳酸高电活性纳纤膜研究

Study on ZIF-8@CNTs functionalized stereocomplexed poly(lactic acid) highly electroactive nanofibrous membranes for long-term PMs filtration

  • 摘要: 空气污染中的颗粒物(PMs)已成为全球关注的焦点问题。这些微小的颗粒能够携带众多有害物质,并通过呼吸系统进入人体的血液循环,从而对健康造成严重影响,包括呼吸系统和神经系统的疾病。然而,传统的防护口罩过滤性能存在很大的局限性,且不可生物降解的过滤口罩在丢弃后往往会对环境产生负面影响。因此,迫切需要开发一种可降解的过滤纤维膜,其中聚乳酸(PLA)在可生物降解空气过滤材料领域具有巨大潜力。然而,受制于其低电活性特征,使得其在静电吸附颗粒物方面的能力不足,难以达到高效过滤空气颗粒物的目的。本文采用微波辅助法,在碳纳米管(CNTs)上成功合成了ZIF-8纳米晶体,得到表面规整的纳米杂化结构ZIF-8@CNTs。并将左旋聚乳酸(PLLA)和右旋聚乳酸(PDLA)共混,基于静电纺-电喷技术将ZIF-8@CNTs 纳米杂化体嵌入在纤维上得到立构复合化聚乳酸纳米纤维膜(ZIF-8@CNTs/SC-PLA),在纤维表面上形成凸出状结构,增加了纤维的物理拦截以及静电吸附性能。PLLA和PDLA链之间的氢键相互作用可以触发立体复合晶(SCs)的形成,进而影响PLA的结晶度,提高了ZIF-8@CNTs/SC-PLA纳纤膜的极化性能和电活性。通过调整ZIF-8@CNTs的浓度,调控纤维的表面形貌,评估了在不同呼吸状态下所产生的电信号,并探讨了在不同流速下ZIF-8@CNTs/SC-PLA纳纤膜的过滤性能以及压降。结果表明:随着ZIF-8@CNTs浓度的增加,纤维的表面逐渐粗糙,直径呈先减小后增大的趋势,介电常数(2.5)以及表面电势(7.7 kV)得到明显改善。在不同流速下,ZIF-8@CNTs/SC-PLA纤维膜的压降都明显低于Pure PLLA纤维膜,其中,在85 L/min 流速下,10%ZIF-8@CNTs/SC-PLA纳纤膜的压降仅206.9 Pa,这远低于Pure PLLA纤维膜(465.2 Pa),且在32 L/min流速下,10%ZIF-8@CNTs/SC-PLA纳纤膜对PM0.3和PM2.5的过滤效率分别为86.9%和96.1%,相较于Pure PLLA纤维分别提升13.2%和8.6%。且在不同的呼吸状态下10%ZIF-8@CNTs/SC-PLA纳纤膜可实现不同的信号输出,展现出优异的电活性,为自供电便携式呼吸监测防护装备提供了新的设计参考。

     

    Abstract: Particulate matter (PMs) in air pollution has become a global concern. These tiny particles are capable of carrying numerous harmful substances and entering the human blood circulation through the respiratory system, resulting in serious health effects, including respiratory and neurological diseases. However, conventional protective masks have significant limitations in filtration performance, and non-biodegradable filter masks often have a negative impact on the environment when discarded. Therefore, there is an urgent need to develop a biodegradable filtration fibrous membrane, in which polylactic acid (PLA) has great potential in the field of biodegradable air filtration materials. However, it is limited by its low electroactivity characteristics, which makes its ability in electrostatic adsorption of particulate matter insufficient to achieve efficient filtration of air particulate matter. In this paper, ZIF-8 nanocrystals were successfully synthesized on carbon nanotubes (CNTs) using a microwave-assisted method to obtain ZIF-8@CNTs nanohybrids with regular surfaces. In addition, poly (L-lactic acid) (PLLA) and poly (D-lactic acid) (PDLA) were blended, and the ZIF-8@CNTs NPs were embedded in the fibers based on electrospinning-electrospray technology to obtain the standing composite poly(lactic acid) fibrous membranes (ZIF-8@CNTs/SC-PLA fibrous membranes), the formation of protruding structures on the fiber surface increases the physical interception as well as the electrostatic adsorption properties of the fibers. The hydrogen bonding interaction between PLLA and PDLA chains can trigger the formation of stereocomplexed crystals (SCs), which in turn affects the crystallinity of PLA and improves the polarization properties and electrical activity of ZIF-8@CNTs/SC-PLA fibrous membranes. By adjusting the concentration of ZIF-8@CNTs and modulating the surface morphology of the fibers, the electrical signals generated under different respiration states were evaluated and the filtration performance as well as the pressure drop of the ZIF-8@CNTs/SC-PLA nanofibrous membranes were explored at different flow rates. The results showed that with the increase of ZIF-8@CNTs concentration, the surface of the fibers was rough, and the diameter of the fibers tended to decrease and then increase, the dielectric constant (2.5) and surface potential (7.7 kV) are significantly improved. The pressure drop of ZIF-8@CNTs/SC-PLA nanofibrous membranes was significantly lower than that of pure PLLA fibrous membrane at different flow rates, among which the pressure drop of 10%ZIF-8@CNTs/SC-PLA nanofibrous membranes was only 206.9 Pa at a flow rate of 85 L/min, which was much lower than that of pure PLLA fibrous membranes (465.2 Pa). And at a flow rate of 32 L/min, the filtration efficiencies of the 10%ZIF-8@CNTs/SC-PLA membrane for PM0.3 and PM2.5 were 86.9% and 96.1%, respectively, which were 13.2% and 8.6% higher than that of the pure PLLA fibrous membranes, respectively. Moreover, the 10%ZIF-8@CNTs/SC-PLA fibrous membranes can achieve different signal outputs under different respiratory states, showing excellent electrical activity, which provides a new design reference for self-powered portable respiratory monitoring and protective equipment.

     

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