Enhanced air filtration performance and intelligent monitoring by MOF-functionalized ultrafine poly(lactic acid) fibers
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摘要:
在工业和医疗场所，传统不可降解过滤材料的大量使用已造成巨大生态环境压力。为此，研究和发展聚乳酸(PLA)纤维膜已成为前沿热点。在此基础上，提出利用同轴静电纺丝技术将高介电性能金属有机框架材料(MOF)嵌入纤维的表面工程策略，制备了用于呼吸防护装备的驻极效果优异、高电活性、可完全降解的聚乳酸纳米纤维膜，同时实现高效过滤和呼吸状态监测。通过调控纤维形貌和改善电活性，提高纤维的物理拦截和静电吸附能力，提升对颗粒物的过滤效率，多种表征测试结果表明：纤维平均直径降低33%(304 nm)，表面电势提高38% (1.8 kV)，介电常数提高55% (1.7)，输出电压提高74% (87 V)，对PM0.3的过滤效率高达99.65% (32 L/min)，即使在85 L/min的高流量下过滤效率也在99.30%，且无显著衰减。在呼吸防护的基础上集成传感功能，可实现对人呼吸状态的实时监测，为疾病的早期诊断提供了参考，在个体防护领域有广阔的应用前景。
Abstract:The extensive use of traditional non-biodegradable filtration materials in industrial and medical sites has caused tremendous ecological and environmental pressure. For this reason, the research and development of poly(lactic acid) (PLA) fibrous membranes have become a cutting-edge hotspot. Based on this, the surface engineering strategy of using coaxial electrostatic spinning to embed high dielectric performance metal-organic framework (MOF) materials into fibers is proposed to prepare PLA nanofibrous membranes with excellent electronegativity, high electroactivity, and complete degradability for respiratory protection equipment, which can simultaneously achieve high-efficiency filtration and respiratory status monitoring. By regulating the fiber morphology and improving the electroactivity, the physical interception and electrostatic adsorption ability of the fibers were improved to enhance the filtration efficiency of particulate matter. The results of multiple characterization tests showed that the average fiber diameter was reduced by 33% (304 nm), the surface potential was increased by 38% (1.8 kV), the dielectric constant was increased by 55% (1.7), and the output voltage was increased by 74% (87 V). The filtration efficiency for PM0.3 is up to 99.65% (32 L/min), and even at a high flow rate of 85 L/min, the filtration efficiency is still at 99.30% with no significant attenuation. Integrating the sensing function based on respiratory protection can realize the real-time monitoring of human respiratory status, which provides a reference for the early diagnosis of diseases and has a broad application prospect in the field of personal protection.
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图 1 聚乳酸(PLA)/MIL-88A纳米纤维膜制备流程和自主搭建的空气过滤性能测试装置
Figure 1. Preparation process of poly(lactic acid) (PLA)/MIL-88A nanofiber membranes and homemade air filtration test equipment
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图 2 PLA/MIL-88A纳米纤维膜扫描电子显微镜(SEM)图像及纤维直径分布
Figure 2. Scanning electron microscope (SEM) images and diameter distributions of PLA/MIL-88A nanofibrous membranes
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图 3 PLA/MIL-88A纳米纤维膜傅里叶变换红外光谱(FTIR)图
Figure 3. Fourier transform infrared spectroscopy (FTIR) images of PLA/MIL-88A nanofiber membranes
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图 4 PLA/MIL-88A纳米纤维膜表面电势和介电常数
Figure 4. Surface potential and dielectric constant of PLA/MIL-88A nanofiber membranes
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图 5 PLA/MIL-88A纳米纤维膜组装的摩擦纳米发电机示意及其输出电压
Figure 5. Schematic of triboelectric nanogenerator assembled with PLA/MIL-88A nanofiber membranes and their voltage output
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图 6 PLA/MIL-88A纳米纤维膜的PM0.3过滤性能评价。(a-d)过滤效率和压降、(e)品质因子、(f)与已报道的纤维滤料的PM0.3过滤性能对比
Figure 6. Filtration efficiency evaluation for PM0.3 of PLA/MIL-88A nanofiber membranes. (a-d) Filtration efficiency, (e) Quality factor, (f) Comparison of PM0.3 filtration efficiency with other existing fibrous filter
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目的
在工业和医疗场所，人们使用大量的呼吸防护装备以避免粉尘和病毒气溶胶被吸入，而商用呼吸防护装备中的不可降解过滤材给生态环境带来了极大的压力。聚乳酸(PLA)得益于良好的热稳定性、可加工性、生物相容性、抗溶剂性、力学性能有望成为下一代空气过滤材料。为此，本文提出利用同轴静电纺丝技术将高介电性能金属有机框架材料(MOF)嵌入纤维的表面工程策略，研究其对于纤维形貌、电活性、过滤性能的影响，探索纤维膜在呼吸监测方面的应用。
方法采用水热法制备出MIL-88A纳米晶，利用同轴静电纺丝技术，将MIL-88A纳米晶嵌入PLA纤维制备了超细直径的可降解生物相容性驻极体纤维膜(PLA/MIL-88A)。采用扫描电镜(SEM)观察样品的外观形貌。采用傅里叶变换红外光谱仪表征样品的化学性质。采用介电测试仪检测样品的介电常数。采用静电测试仪测试样品的表面电势。采用微型滑台电缸测试样品的摩擦电输出性能。采用自主搭建的过滤性能测试装置测试样品的PM过滤效率。采用自主搭建的呼吸监测装置研究样品在呼吸状态监测方面的应用。
结果随着MIL-88A含量的增加，PLA/MIL-88A纤维膜的直径不断降低，其中PLA/30MIL-88A的直径最低，为304 nm。超细的纤维直径提高了纤维膜的物理拦截能力，提高对于较大直径颗粒物的过滤效率。同时，MIL-88A的引入提高了纤维膜的电活性，表面电势提高38%(1.8 kV)，相对介电常数提高55%(1.7)，电活性的提高意味着纤维表面能够贮存更多电荷，提高了纤维膜依靠静电吸附的过滤效果。此外摩擦电输出电压提高了74%(87V)，纤维膜依靠摩擦起电可以补偿其在使用和存放过程中的电荷损耗，延长使用寿命。在PM过滤测试中，PLA/30MIL-88A效果最好，在较低的流速(32 L/min)下，过滤效率高达99.65%，并且展现除了对流速变化的良好抵抗性，即使在流速升高至85 L/min也能保持99.30%的过滤效率。最后，利用自主搭建的呼吸监测装置，以摩擦电信号作为变量对人呼吸的频率进行监测，信号波峰和波谷对应呼气和吸气，极小的峰宽度能够保证频率测量的准确度，为呼吸健康状况评估提供依据。
结论(1)水热法制备了生物相容性MOF材料MIL-88A；MIL-88A直接分散在聚乳酸溶液中进行静电纺丝制备了纤维膜；制备方法简单迅速，产物可完全降解且对人体无毒害作用。(2)MIL-88A的引入，对于纤维膜的微观形貌、电活性、电荷再生性能均有改善，共同提高了纤维膜的过滤效率。随着MIL-88A含量的不断增加，纤维平均直径从455 nm降低至304 nm，得到细化；表面电位和介电常数分别提高至1.8 kV和1.7，纤维膜储存电荷的能力增强；输出电压从50 V升高到87 V，再生电荷可以弥补储存和使用过程中耗散的电荷；对于PM的过滤效率在85 L/min的流量下也能实现高达99.30%。(3)在呼吸防护基础上集成了呼吸传感功能，能够提供准确的呼吸状态监测，为疾病的早期诊断提供参考依据。
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聚乳酸(PLA)得益于良好的热稳定性、可加工性、生物相容性、抗溶剂性、力学性能有望取代目前商用的聚丙烯成为下一代空气过滤材料，但较差的驻极效果限制了其在空气过滤领域的应用。金属有机框架材料MIL-88A具有比表面积大、吸附性能好、表面活性高、介电性能优异的特点，与PLA复合可以进一步提高纤维的驻极效果和表面活性，提高纤维膜对于PM0.3的过滤效率。
本文将高介电、纳米尺寸MIL-88A分散在聚乳酸溶液中进行同轴静电纺丝，制备出了超细直径、高过滤效率(PM0.3)的可降解生物相容性驻极体纤维膜。MIL-88A的引入，对于纤维膜的微观形貌、电活性、电荷再生性能均有改善，共同提高了纤维膜的过滤效率。随着MIL-88A含量的不断增加，纤维平均直径从455 nm降低至304 nm，得到细化；表面电位和介电常数分别提高至1.8 kV和1.7，纤维膜储存电荷的能力增强；摩擦电输出电压从50 V升高到87 V，再生电荷可以弥补储存和使用过程中耗散的电荷；对于PM0.3的过滤效率在85 L/min的流量下也能实现高达99.30%。以摩擦电信号作为变量对人呼吸的频率进行监测，信号波峰和波谷对应呼气和吸气，极小的峰宽度能够保证频率测量的准确度，为呼吸健康状况评估提供依据。
PLA/MIL-88A纳米纤维膜在85 L/min时的过滤效率(PM0.3)和呼吸监测应用
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