Ecofriendly and antibacterial poly(lactic acid) nanofibrous membranes forhigh-efficiency and low-resistance filtration of airborne particulate matters
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摘要: 工业生产过程中所产生的细微颗粒物(PMs)对人体健康构成了严重威胁，是引起工作职业病的主要危害之一。当下传统面罩过滤效果不佳、呼吸阻力高、容尘量低、不易降解及抗菌效果不明显，为此，开发了一种环境友好型高效低阻的聚乳酸(PLA)抗菌可降解纳米过滤膜。通过微波辅助合成方法在碳纳米管(CNT)上诱导沸石咪唑酯框架-8 (ZIF-8)生长，成功合成了结构规整、比表面积大的纳米杂化结构CNT@ZIF-8。基于静电纺-电喷技术将CNT@ZIF-8成功嵌入到PLA纤维上，通过调控CNT@ZIF-8的质量分数，制备了不同纤维直径的聚乳酸复合纳纤膜(CNT@ZIF/PLA)，探讨了在不同流速下CNT@ZIF/PLA纳纤膜的过滤性能以及空气阻力，系统研究了不同CNT@ZIF-8质量分数对纳纤膜力学性能以及抗菌性能的影响。结果表明：CNT@ZIF/PLA纳纤膜相较于Pure PLA纳纤膜拉伸强度最高增幅达47% (18.5 MPa)，断裂韧性提升100% (2.9 MJ/m3)。随着CNT@ZIF-8质量分数的增加，空气阻力逐渐降低，当测试流速在32 L/min时，12wt%CNT@ZIF/PLA纳纤膜的空气阻力仅为78.7 Pa，较Pure PLA纳纤膜减小了40.8%，且经过180 min长时间过滤测试，对PMs的过滤效率无明显变化。在测试流速在85 L/min时，CNT@ZIF/PLA纳纤膜对PM0.3的过滤效率均高达89%以上。并且经过太阳光模拟器照射5 min后，对大肠杆菌与金黄色葡萄球菌抗菌效率均达到100%。Abstract: Fine particulate matters (PMs) generated during industrial production pose a serious threat to human health and are one of the main hazards causing occupational diseases at work. The contemporary traditional masks have poor filtration effect, high breathing resistance, low dust holding capacity, not easy to degrade as well as insignificant antibacterial effect, for this reason, a high-efficiency and low-resistance poly(lactic acid) (PLA) antibacterial biodegradable nanofibrous filtration membrane has been developed. Structurally ordered nanohybrid structure CNT@ZIF-8 with large specific surface area were successfully synthesized by inducing the growth of zeolitic imidazolium ester framework-8 (ZIF-8) on carbon nanotubes (CNT) by microwave-assisted synthesis method. Based on the electrospinning-electrospray technology, CNT@ZIF-8 was successfully embedded onto PLA fiber, and PLA composite fibrous membranes (CNT@ZIF/PLA) with different fiber diameters were prepared by regulating the mass fraction of CNT@ZIF-8. The filtration performance and air resistance of CNT@ZIF/PLA nanofibrous membranes at different flow rates were investigated, and the effects of different mass fractions of CNT@ZIF-8 on the mechanical properties and antibacterial properties were investigated. The results show that the tensile strength of CNT@ZIF/PLA nanofibrous membrane increases up to 47% (18.5 MPa) and the fracture toughness increases 100% (2.9 MJ/m3) compared with that of pure PLA membrane. As the mass fraction of CNT@ZIF-8 increases, the air resistance gradually decreases, and at the test flow rate of 32 L/min, the air resistance of 12wt%CNT@ZIF/PLA nanofibrous membrane is only 78.7 Pa, which is 40.8% less than that of Pure PLA fiber membrane, and after the 180 min long filtration test, there is no significant change observed in the filtration efficiency of PMs. At the test flow rate of 85 L/min, the filtration efficiency of CNT@ZIF/PLA nanofibrous membrane for PM0.3 is more than 89%, and after 5 min of irradiation by the sunlight simulator, the antibacterial efficiency against both E. coli and S. aureus reach 100%.
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图 1 碳纳米管(CNT)@沸石咪唑酯框架-8 (ZIF-8)/聚乳酸(PLA)纳纤膜示意图
Figure 1. Schematic diagram of carbon nanotubes (CNT)@zeolitic imidazolium ester framework-8 (ZIF-8)/poly(lactic acid) (PLA) nanofibrous membranes
PMs—Particulate matters
图 2 PMs滤除效果评价的空气过滤性能测试装置示意图
Figure 2. Schematic diagram of air filtration performance test device for PMs filtration effect evaluation
图 3 (a) CNT@ZIF-8粉末；(b) CNT@ZIF-8纳米杂化结构SEM图像；(c) CNT@ZIF-8与ZIF-8的XRD图谱；(d) CNT@ZIF-8与ZIF-8的FTIR图谱
Figure 3. (a) CNT@ZIF-8 powder; (b) SEM images of CNT@ZIF-8 nanohybrid structure; (c) XRD patterns of CNT@ZIF-8 and ZIF-8; (d) FTIR spectra of CNT@ZIF-8 and ZIF-8
图 4 不同CNT@ZIF-8质量分数的CNT@ZIF/PLA纳纤膜的SEM图像：(a) 0wt%；(b) 8wt%；(c) 10wt%；(d) 12wt%
Figure 4. SEM images of CNT@ZIF/PLA nanofibrous membranes with different CNT@ZIF-8 mass fractions: (a) 0wt%; (b) 8wt%; (c) 10wt%; (d) 12wt%
图 5 不同CNT@ZIF-8质量分数的CNT@ZIF/PLA纤维直径分布：(a) 0wt%；(b) 8wt%；(c) 10wt%；(d) 12wt%
Figure 5. CNT@ZIF/PLA fibrous diameter distribution with different CNT@ZIF-8 mass fractions: (a) 0wt%; (b) 8wt%; (c) 10wt%; (d) 12wt%
$\overline D $—
图 6 (a) CNT@ZIF/PLA纳纤膜的XRD图谱；(b) CNT@ZIF/PLA纳纤膜的FTIR图谱
Figure 6. (a) XRD patterns of CNT@ZIF/PLA nanofibrous membranes; (b) FTIR spectra of CNT@ZIF/PLA nanofibrous membranes
图 7 CNT@ZIF/PLA纳纤膜的力学性能：(a) 应力-应变曲线；(b) 拉伸强度与断裂伸长率；(c) 杨氏模量与断裂韧性
Figure 7. Mechanical properties of CNT@ZIF/PLA nanofibrous membranes: (a) Stress-strain curves; (b) Tensile strength and elongation at break; (c) Young's modulus and fracture toughness
图 8 CNT@ZIF/PLA纳纤膜的介电常数(a)与表面电势(b)
Figure 8. Dielectric constant (a) and surface potential (b) of CNT@ZIF/PLA nanofibrous membranes
图 9 不同CNT@ZIF-8质量分数的CNT@ZIF/PLA纳纤膜的过滤性能随流速变化曲线：(a) PM0.3过滤效率；(b) PM2.5过滤效率；(c) 压降；(d) PM0.3品质因子；(e) 气溶胶发生器使用时间与PM2.5的过滤效率；(f) 长时间过滤PM0.3以及PM2.5的效率
Figure 9. Filtration performance in relation to flow rate of CNT@ZIF/PLA nanofibrous membranes with different CNT@ZIF-8 mass fractions: (a) PM0.3 filtration efficiency; (b) PM2.5 filtration efficiency; (c) Pressure drop; (d) PM0.3 quality factor; (e) Aerosol generator operating time and PM2.5 filtration efficiency; (f) Filtration efficiency of PM0.3 and PM2.5 in a long-service time
图 10 CNT@ZIF/PLA纳纤膜的抗菌性能： (a) 纳纤膜抗菌实物图；(b) 1, 3-二苯基异苯并呋喃(DPBF)的紫外可见光谱
Figure 10. Antibacterial properties of CNT@ZIF/PLA nanofibrous membranes: (a) Antibacterial physical drawing of fibrous membrane; (b) UV-visible spectra of 1, 3-diphenylisobenzofuran (DPBF)
图 11 纳纤膜长效抗菌性能评价：(a) CNT@ZIF/PLA纳纤膜抗菌性能循环测试；(b) 日光下CNT@ZIF/PLA纳纤膜抗菌性能测试；(c) CNT@ZIF/PLA纳纤膜抗菌性能与其他体系复合聚乳酸纳纤膜作比较(PLLA/地塞米松(Dex)/Ag[40]、PLLA/Ag-2MI[41]、PLA/ZnO-Ag[42]、Cur-ICG@ZIF-8/PLA[43])
Figure 11. Evaluation of the long-term antibacterial performance of nanofibrous membranes: (a) Cyclic testing of antimicrobial properties of CNT@ZIF/PLA nanofiber membranes; (b) Antibacterial performance test of CNT@ZIF/PLA nanofibrous membranes under sunlight; (c) Comparing the antibacterial performance of CNT@ZIF/PLA nanofibrous membranes with the other systems of PLA nanofibrous composite membranes (Poly(L-lactide) (PLLA)/dexamethasone (Dex)/Ag[40], PLLA/Ag-2MI[41], PLA/ZnO-Ag[42], Cur-ICG@ZIF-8/PLA[43])
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