Electroactive PLA/ZnO@PDA nanofibrous membranes for high performance ultrafine particulate matter filtration
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摘要: 静电纺聚乳酸(PLA)纤维滤膜面临PLA在电场下的极化能力弱、电荷储存稳定性低的瓶颈问题。为此，通过静电纺丝-静电喷雾技术将高表面活性的PDA包覆的ZnO (ZnO@PDA)纳米电介质锚定于PLA纳米纤维表面(PLA/ZP)，以增强PLA纳米纤维膜(简称纳纤膜)的驻极性能和摩擦电效应，从而实现静电捕获和长效过滤。对PLA/ZnO@PDA (PLA/ZP)纳纤膜的表面形貌和分子结构进行表征，探讨ZnO@PDA与PLA的界面相互作用与PLA/ZP纳纤膜电活性、过滤性能、电荷再生机制、呼吸监测功能之间的关系。结果表明，PLA/ZP纳纤膜具有高电活性和优异的空气过滤性能，其表面电势和介电性能分别为纯PLA纳纤膜的2.9倍和1.65倍。在85 L/min的高空气流速下，PLA/ZP纳纤膜仍能保持98.82%的PM0.3过滤效率和301.3 Pa的压降。得益于电活性的提升和比表面积的增大，PLA/ZP纳纤膜的输出电压达到11.5 V(10 N，0.5 Hz)，远高于纯PLA纳纤膜(1.56 V)，将其融入呼吸防护面罩能够实现对呼吸的实时监测。所制备的PLA/ZP纳纤膜在颗粒物长效捕获和人体健康监测领域具有广阔应用前景。Abstract: Electrospun poly(lactic acid) (PLA) fibrous filter membranes face the bottleneck problem of the weak polarization ability under electric field and low charge storage stability of PLA. Therefore, high surface-active PDA-coated ZnO (ZnO@PDA) nanodielectrics were anchored to the surface of PLA nanofibers by electrospinning-elctrospray technology (PLA/ZP) to enhance the electret performance and triboelectric effect of PLA nanofibrous membranes, thereby realizing electrostatic capturing and long-lasting filtration. The surface morphology and molecular structure of PLA/ZnO@PDA (PLA/ZP) nanofibrous membranes were characterized to explore the relationship among the interfacial interactions between ZnO@PDA and PLA, and the electroactivity, filtration performance, charge regeneration mechanism, and respiration monitoring capability of PLA/ZP nanofibrous membranes. The results showed that the PLA/ZP nanofibrous membrane had high electroactivity and excellent air filtration performance, and its surface potential and dielectric properties were 2.9 and 1.65 times higher than those of pure PLA nanofibrous membrane, respectively. At a high air flow rate of 85 L/min, the PLA/ZP nanofibrous membrane still maintained 98.82% of PM0.3 filtration efficiency and 301.3 Pa of pressure drop. Benefiting from the improved electroactivity and increased specific surface area, the output voltage of the PLA/ZP nanofibrous membrane achieved 11.5 V (10 N, 0.5 Hz), which was much higher than that of the pure PLA nanofibrous membrane (1.56 V), and integrating it into respiratory masks enabled real-time monitoring of respiration. The proposed PLA/ZP nanofibrous membrane holds a promising application in the fields of long-lasting particle capture and human health monitoring.
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图 1 聚乳酸/ZnO@聚多巴胺(PLA/ZnO@PDA，PLA/ZP)纳纤维膜制备示意图
Figure 1. Schematic diagram of the preparation of Polylactic acid/ZnO@polydopamine (PLA/ZnO@PDA, PLA/ZP) nanofibrous membranes
图 2 自主搭建过滤性能测试设备示意图
Figure 2. Schematic diagram of homemade filtration performance test equipment
图 3 ZnO@PDA 纳米电介质的(a) SEM 图像和(b)包含Zn和 N元素的扫描分布图的STEM 图像
Figure 3. (a) SEM images and (b) STEM image including the scan distribution of Zn and N elements (B) of ZnO@PDA nanodielectrics
图 4 Pure PLA、PLA/ZP-2、PLA/ZP-4、PLA/ZP-8 的(a) SEM 图像和相应的(b)纤维直径分布
Figure 4. SEM images (a) and corresponding fiber diameter distributions (b) of Pure PLA, PLA/ZP-2, PLA/ZP-4 and PLA/ZP-8
图 5 Pure PLA、PLA/ZP-2、PLA/ZP-4、PLA/ZP-8 的(a)全范围FTIR光谱和在(b)
1000 ~1150 cm−1、(c)1600 ~1900 cm−1、(d)3050 ~3800 cm−1处的相应比例放大光谱Figure 5. (a) Full-range FTIR spectra of Pure PLA, PLA/ZP-2, PLA/ZP-4 and PLA/ZP-8 and corresponding scale-expanded spectra located at (b)
1000 ~1150 cm−1, (c)1600 ~1900 cm−1 and (d)3050 ~3800 cm−1
图 6 PLA/ZP纳纤膜的(a)表面电势和(b)介电常数；(c) ZnO@PDA 对驻极效应的影响示意图
Figure 6. (a) Surface potential and (b) dielectric constant of PLA/ZP nanofibrous membranes and (c) schematic representation of the effect of ZnO@PDA on the electret effect
图 7 PLA/ZP 纳纤膜在气流速率为(a) 10 L/min、(b) 32 L/min、(c) 65 L/min、(d) 85 L/min时的过滤效率和压降
Figure 7. Filtration efficiency and pressure drop of PLA/ZP nanofibrous membranes at airflow rates of (a) 10 L/min, (b) 32 L/min,(c) 65 L/min and (d) 85 L/min
图 8 (a) 聚乳酸纳纤膜的摩擦电输出电压；(b) PLA/ZP基 TENG 在呼吸过程中的工作机制示意图；(c) 说话、(d) 咳嗽、(e) 呼吸产生的电流信号
Figure 8. (a) Triboelectric output voltage of PLA nanofibrous membranes, (b) schematic diagram of the working mechanism of PLA/ZP-based TENG during respiration, current signals under (c) speaking, (d) coughing and (e) breathing
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