静电纺特殊形貌纳米纤维的应用研究进展

doi:10.16085/j.issn.1000-6613.2021-2016

摘要/Abstract

摘要：

特殊形貌的纳米纤维可以通过控制静电纺丝过程工艺及参数条件来制备。特殊形貌的纳米纤维具有比普通纳米纤维更大的比表面积和更高的孔隙率，以及掺杂各类有机/无机材料后赋予纤维的多功能性，使其应用研究已经深入能源环境、催化过滤、生物工程、食品安全等诸多领域，成为纳米材料研究的热点领域之一。但特殊形貌纳米纤维存在研究体系不完善、量产化难度高、重现性差等问题。本文通过对多种特殊形貌纳米纤维的成形机理进行阐述，介绍了特殊形貌纳米纤维独特的形貌结构与性能优势，对其在粒子透过、粒子拦截与传输等领域的应用研究进行了概述。此外，本文对特殊形貌的纳米纤维从研究制备到应用过程中面临的局限性进行了讨论，提出建立完善的特殊形貌纳米纤维研究体系，针对应用领域开发功能性特殊形貌纳米纤维膜，从环保性、稳定性角度出发，推进特殊形貌纳米纤维的产业化发展进程。

关键词: 静电纺丝, 特殊形貌纳米纤维, 粒子透过, 粒子拦截, 粒子传输

Abstract:

Special morphology nanofibers were prepared with the in-depth study of the electrospinning technology and process mechanism. It had larger specific surface area and higher porosity than ordinary nanofibers, as well as the versatility given to fibers by doping with various organic/inorganic materials. Its research had penetrated into many fields such as energy and environment, catalytic filtration, bioengineering, food safety, etc., and it was one of the hotspots in the research of nanomaterials fields. However, there were still some problems need to be solved, such as imperfect research system, high difficulty in mass production, poor reproducibility and so on. In this review, the forming mechanism of special morphology nanofiber was highlighted, the unique morphological structure and excellent properties of special morphology nanofiber were summarized, and its application research in the fields of particle penetration, particle interception and transportation were reviewed in detail. In addition, the limitation of special morphology nanofibers was discussed from research and preparation to application. A complete research system for special morphology nanofibers should be established and the functional nanofiber membranes with special morphology should be also developed for various application fields to promote the industrialization of special morphology nanofibers from the perspective of environmental protection and stability.

Key words: electrospinning, special morphology nanofiber, particle penetration, particle interception, particle transportation

中图分类号:

TQ340

王慧, 刘新懿, 王伟, 万同, 厉宗洁, 王劭妤, 程博闻. 静电纺特殊形貌纳米纤维的应用研究进展[J]. 化工进展, 2022, 41(8): 4341-4356.

WANG Hui, LIU Xinyi, WANG Wei, WAN Tong, LI Zongjie, WANG Shaoyu, CHENG Bowen. Research and application of electrospun nanofibers with special morphology: a review[J]. Chemical Industry and Engineering Progress, 2022, 41(8): 4341-4356.

图/表 10

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105	ZHAO H H, KANG W M, MA X M, et al. Fabrication and catalytic behavior of hierarchically-structured nylon 6 nanofiber membrane decorated with silver nanoparticles[J]. Chinese Journal of Catalysis, 2017, 38(1): 73-82.
106	DENG N P, LIU Y, LI Q X, et al. Functional double-layer membrane as separator for lithium-sulfur battery with strong catalytic conversion and excellent polysulfide-blocking[J]. Chemical Engineering Journal, 2020, 382: 122918.
107	WANG Z, PAN Z J. Preparation of hierarchical structured nano-sized/porous poly(lactic acid) composite fibrous membranes for air filtration[J]. Applied Surface Science, 2015, 356: 1168-1179.
108	HU M, YIN L H, ZHOU H X, et al. Manganese dioxide-filled hierarchical porous nanofiber membrane for indoor air cleaning at room temperature[J]. Journal of Membrane Science, 2020, 605: 118094.
109	CHEN S L, DING C, LIN Y, et al. SERS-active substrate assembled by Ag NW-embedded porous polystyrene fibers[J]. RSC Advances, 2020, 10(37): 21845-21851.
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113	CHENG H, ZHOU Z Y, LIU T. Electro-spinning fabrication of nitrogen, phosphorus co-doped porous carbon nanofiber as an electro-chemiluminescent sensor for the determination of cyproheptadine[J]. RSC Advances, 2020, 10(39): 23091-23096.
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特殊形貌纳米纤维	纺丝原料	潜在应用领域	参考文献
蛛网状纳米纤维	聚丙烯酸（PAA），聚丙烯酸/聚乙烯醇（PAA/PVA）	空气过滤材料，湿度传感器	[22,26]
	尼龙6（PA6），尼龙66（PA66），尼龙6/聚丙烯腈（PA6/PAN），聚酰胺6/聚酰胺66（PA6/PA66），聚酰胺-56（PA-56）	存储器集成设备，过滤材料及介质	[24-25, 28, 84-86]
	明胶	组织工程、能量存储、传感器和催化	[18]
	间位芳纶（PMIA）	水/空气过滤芯材、防护服和电绝缘	[20,87]
	聚乙烯亚胺/聚乙烯醇（PEI/PVA）	甲醛传感器	[23]
	聚偏氟乙烯（PVDF）	空气过滤	[27, 88]
	聚氨酯（PU）	超滤器、特种防护服、超灵敏传感器	[89]
	壳聚糖/聚乙烯吡络烷酮（CS/PVP）	PM污染高效过滤	[90]
珠状纳米纤维	乙酸纤维素（CA）	复合过滤材料	[32]
	聚己内酯（PCL）	药物控释，骨组织工程	[33, 91]
	PVDF	油水分离	[31]
	聚乳酸（PLA），聚（L-乳酸-ε-己内酯）（PLCL）	空气过滤，药物释放	[34, 92-94]
	聚酰亚胺（PI）	浆料涂层电极	[35]
	聚乳酸-乙醇酸（PLGA）	药物控释，组织工程	[95-97]
	聚氧化乙烯（PEO）	药物载体	[98]
	聚四氟乙烯（PTFE）	光催化降解染料	[99]
	聚丙烯腈（PAN）	过滤介质	[100]
树枝状纳米纤维	聚偏氟乙烯（PVDF），聚偏氟乙烯/氟化丙烯酸酯共聚物（PVDF/FA），聚偏二氟乙烯六氟丙烯（PVDF-HFP），聚偏二氟乙烯-接枝聚丙烯酸（PVDF-g-PAA）	微滤膜，锂离子电池隔膜，pH响应性系统	[36-37, 42, 101-103]
	PA6	水净化，纳米催化剂	[104, 105]
	CA	分离、组织工程、传感器和催化	[38]
	PLA	高效空气过滤	[39]
	聚氨酯（TPU）	防水透气材料	[40]
	PMIA	锂硫电池隔膜	[106]
多孔状纳米纤维	PLA，聚(L-乳酸)（PLLA），聚(L-乳酸)/聚(3-羟丁酸酯-co-3-羟基戊酸酯)（PLLA/PHBV）	空气过滤，油水分离，气体检测，重金属离子吸附，生物医学、储能设备	[34, 47-51, 107]
	聚苯乙烯（PS）	空气净化，可穿戴传感器	[108-109]
	PCL	组织再生	[110]
	聚（甲基丙烯酸甲酯-co-1,8-萘二甲酰亚胺衍生物-co-罗丹明衍生物）	水净化传感过滤器	[111]
	PAN	高效吸附剂	[112]
	PAN/PVP	电致发光传感器	[113]
核-壳纳米纤维	丝素/聚己内酯（SF/PCL），明胶/聚己内酯	血管组织工程支架，骨再生膜	[53, 114]
	胰岛素/聚-D-L-丙交酯-乙交酯	纳米纤维支架	[54]
	聚丙烯腈/聚丁二酸丁二醇酯（PAN/PBS），聚丙烯腈/聚吡咯（PAN/PPy），磷钼酸/聚丙烯腈（PMoA/PAN），TiO₂/PAN	锂离子电池，重金属吸附，空气或水净化、水分解制氢、燃料电池和氢吸附	[55, 57, 68, 115]
	聚（3,3'''-二十二烷基四噻吩）/聚环氧乙烷（PQT-12/PEO）	气体传感器	[56]
	聚（γ-谷氨酸）/聚乳酸（γ-PGA/PLA）	生物组织工程支架	[116]
	聚（甘油癸二酸酯）/聚-L-乳酸/聚异丙基丙烯酰胺（PGS/PLLA/PNIPAM）	药物载体	[117]
中空纳米纤维	锶铁氧体（SrM）	吸波材料	[61]
	乙烯吡咯烷酮/乙酸铜［PVP/Cu(CH₃COO)₂］	透明电极	[63]
	PAN/Co₃O₄，PAN/Mn₃O₄，PAN/Na	储能系统，气体吸附，金属电池	[62, 70, 118]
	Sn/SnO₂@C，SnO₂，SnO₂-CuO	高储能系统，乙醇气体吸附，光学器件，硫化氢气体传感器	[63, 67, 71, 73, 119]
	Pr /BiFeO₃	甲醛气体吸附	[72]
	苯甲酸/菲咯啉/聚苯胺/聚乙烯吡咯烷酮［Tb(BA)₃phen/PANI/Fe₃O₄/PVP］	电磁干扰屏蔽、微波吸收、分子电子学和生物医学	[120]
	ZnO/CoNiO₂	气体检测	[121]
	聚碳硅烷（PCS）	气体分离、高温反应器、催化剂载体等	[122]
	PLA/PVA	油水分离系统	[123]
	聚丙烯腈/聚吡咯烷酮@聚（苯乙烯-共聚丙烯腈）（PAN/PVP@SAN），聚丙烯腈/聚甲基丙烯酸甲酯（PAN/PMMA）	超级电容器	[124-125]
	IrO₂	超级电容器	[126]
带状纳米纤维	PLLA	铜离子吸附	[51]
	玉米醇溶蛋白	食品包装，金属离子检测	[74-75, 78]
	明胶	调节多肽结构	[76]
	PMMA	油水分离系统	[127]
刺状纳米纤维	聚芳醚腈/铁酞菁（PEN/FePc）	传感器、催化剂载体、纳米电子学和组织工程	[79]
刺状纳米纤维	二氧化钛（TiO₂），草酸银/二氧化钛（Ag₂C₂O₄/TiO₂）	超级电容器，水净化，抗菌材料	[80-81]
仙人掌状纳米纤维	PVDF	能量收集，自清洁表面	[82]
羽毛状纳米纤维	聚苯乙烯/N,Nʹ,Nʹʹ-三(1-(甲氧基甲基)丙基)苯-1,3,5-三甲酰胺(PS/BTA)	过滤，催化，能量存储	[83]

特殊形貌纳米纤维	纺丝原料	潜在应用领域	参考文献
蛛网状纳米纤维	聚丙烯酸（PAA），聚丙烯酸/聚乙烯醇（PAA/PVA）	空气过滤材料，湿度传感器	[22,26]
	尼龙6（PA6），尼龙66（PA66），尼龙6/聚丙烯腈（PA6/PAN），聚酰胺6/聚酰胺66（PA6/PA66），聚酰胺-56（PA-56）	存储器集成设备，过滤材料及介质	[24-25, 28, 84-86]
	明胶	组织工程、能量存储、传感器和催化	[18]
	间位芳纶（PMIA）	水/空气过滤芯材、防护服和电绝缘	[20,87]
	聚乙烯亚胺/聚乙烯醇（PEI/PVA）	甲醛传感器	[23]
	聚偏氟乙烯（PVDF）	空气过滤	[27, 88]
	聚氨酯（PU）	超滤器、特种防护服、超灵敏传感器	[89]
	壳聚糖/聚乙烯吡络烷酮（CS/PVP）	PM污染高效过滤	[90]
珠状纳米纤维	乙酸纤维素（CA）	复合过滤材料	[32]
	聚己内酯（PCL）	药物控释，骨组织工程	[33, 91]
	PVDF	油水分离	[31]
	聚乳酸（PLA），聚（L-乳酸-ε-己内酯）（PLCL）	空气过滤，药物释放	[34, 92-94]
	聚酰亚胺（PI）	浆料涂层电极	[35]
	聚乳酸-乙醇酸（PLGA）	药物控释，组织工程	[95-97]
	聚氧化乙烯（PEO）	药物载体	[98]
	聚四氟乙烯（PTFE）	光催化降解染料	[99]
	聚丙烯腈（PAN）	过滤介质	[100]
树枝状纳米纤维	聚偏氟乙烯（PVDF），聚偏氟乙烯/氟化丙烯酸酯共聚物（PVDF/FA），聚偏二氟乙烯六氟丙烯（PVDF-HFP），聚偏二氟乙烯-接枝聚丙烯酸（PVDF-g-PAA）	微滤膜，锂离子电池隔膜，pH响应性系统	[36-37, 42, 101-103]
	PA6	水净化，纳米催化剂	[104, 105]
	CA	分离、组织工程、传感器和催化	[38]
	PLA	高效空气过滤	[39]
	聚氨酯（TPU）	防水透气材料	[40]
	PMIA	锂硫电池隔膜	[106]
多孔状纳米纤维	PLA，聚(L-乳酸)（PLLA），聚(L-乳酸)/聚(3-羟丁酸酯-co-3-羟基戊酸酯)（PLLA/PHBV）	空气过滤，油水分离，气体检测，重金属离子吸附，生物医学、储能设备	[34, 47-51, 107]
	聚苯乙烯（PS）	空气净化，可穿戴传感器	[108-109]
	PCL	组织再生	[110]
	聚（甲基丙烯酸甲酯-co-1,8-萘二甲酰亚胺衍生物-co-罗丹明衍生物）	水净化传感过滤器	[111]
	PAN	高效吸附剂	[112]
	PAN/PVP	电致发光传感器	[113]
核-壳纳米纤维	丝素/聚己内酯（SF/PCL），明胶/聚己内酯	血管组织工程支架，骨再生膜	[53, 114]
	胰岛素/聚-D-L-丙交酯-乙交酯	纳米纤维支架	[54]
	聚丙烯腈/聚丁二酸丁二醇酯（PAN/PBS），聚丙烯腈/聚吡咯（PAN/PPy），磷钼酸/聚丙烯腈（PMoA/PAN），TiO₂/PAN	锂离子电池，重金属吸附，空气或水净化、水分解制氢、燃料电池和氢吸附	[55, 57, 68, 115]
	聚（3,3'''-二十二烷基四噻吩）/聚环氧乙烷（PQT-12/PEO）	气体传感器	[56]
	聚（γ-谷氨酸）/聚乳酸（γ-PGA/PLA）	生物组织工程支架	[116]
	聚（甘油癸二酸酯）/聚-L-乳酸/聚异丙基丙烯酰胺（PGS/PLLA/PNIPAM）	药物载体	[117]
中空纳米纤维	锶铁氧体（SrM）	吸波材料	[61]
	乙烯吡咯烷酮/乙酸铜［PVP/Cu(CH₃COO)₂］	透明电极	[63]
	PAN/Co₃O₄，PAN/Mn₃O₄，PAN/Na	储能系统，气体吸附，金属电池	[62, 70, 118]
	Sn/SnO₂@C，SnO₂，SnO₂-CuO	高储能系统，乙醇气体吸附，光学器件，硫化氢气体传感器	[63, 67, 71, 73, 119]
	Pr /BiFeO₃	甲醛气体吸附	[72]
	苯甲酸/菲咯啉/聚苯胺/聚乙烯吡咯烷酮［Tb(BA)₃phen/PANI/Fe₃O₄/PVP］	电磁干扰屏蔽、微波吸收、分子电子学和生物医学	[120]
	ZnO/CoNiO₂	气体检测	[121]
	聚碳硅烷（PCS）	气体分离、高温反应器、催化剂载体等	[122]
	PLA/PVA	油水分离系统	[123]
	聚丙烯腈/聚吡咯烷酮@聚（苯乙烯-共聚丙烯腈）（PAN/PVP@SAN），聚丙烯腈/聚甲基丙烯酸甲酯（PAN/PMMA）	超级电容器	[124-125]
	IrO₂	超级电容器	[126]
带状纳米纤维	PLLA	铜离子吸附	[51]
	玉米醇溶蛋白	食品包装，金属离子检测	[74-75, 78]
	明胶	调节多肽结构	[76]
	PMMA	油水分离系统	[127]
刺状纳米纤维	聚芳醚腈/铁酞菁（PEN/FePc）	传感器、催化剂载体、纳米电子学和组织工程	[79]
刺状纳米纤维	二氧化钛（TiO₂），草酸银/二氧化钛（Ag₂C₂O₄/TiO₂）	超级电容器，水净化，抗菌材料	[80-81]
仙人掌状纳米纤维	PVDF	能量收集，自清洁表面	[82]
羽毛状纳米纤维	聚苯乙烯/N,Nʹ,Nʹʹ-三(1-(甲氧基甲基)丙基)苯-1,3,5-三甲酰胺(PS/BTA)	过滤，催化，能量存储	[83]

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