CN109695096A - 一种一步法制备空气净化用多级孔纳米纤维膜的方法 - Google Patents
一种一步法制备空气净化用多级孔纳米纤维膜的方法 Download PDFInfo
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Abstract
本发明公开了一种空气净化用负载沸石咪唑酯骨架结构材料ZIF‑67的聚苯乙烯多级孔纳米纤维膜的制备方法，属于分离膜制备技术领域。利用硝酸钴和2‑甲基咪唑在水溶液中的自组装合成ZIF‑67纳米颗粒，再将ZIF‑67纳米颗粒掺杂道到聚苯乙烯纺丝液中，采用静电纺丝技术，“一步法”制备具有微孔‑介孔‑大孔的负载沸石咪唑酯骨架结构材料ZIF‑67的聚苯乙烯多级孔纳米纤维膜。本发明工艺简单使用且成本低廉，利用沸石咪唑酯骨架结构材料ZIF‑67丰富的微孔结构，较高的比表面积，以及纳米纤维膜较低的过滤阻力，实现PM2.5和气相污染物一体化高效治理。
Description
技术领域
本发明属于多级孔纳米纤维膜制备技术领域，具体为一种用于空气净化的负载沸石咪唑酯骨架结构材料(ZIF-67)的聚苯乙烯多级孔纳米纤维膜的制备方法。
背景技术
室内装修引起的氨气、甲醛、苯、二甲苯等，以及工业过程产生的烟尘、氮氧化物、酸性气体等都会形成空气污染，给人类的身心健康带来严重威胁。因此研制高效净化材料用于空气污染治理已成为迫切需求。纤维过滤材料因其大比表面积、高孔隙率、柔性、易加工等特性，已在空气过滤材料中占据主导地位，主要包括非织造材料、玻璃纤维、改性聚四氟乙烯薄膜（ePTFE）和纳米纤维膜等。其中，纳米纤维膜，一方面具有较均一的孔径、高孔隙率和比表面积，使纤维与空气中的污染物之间具有更多的有效接触，因此具有过滤效率高的优点；另一方面，纤维直径与空气分子的平均自由程（约66nm）相当，由于“滑脱效应（slipeffect）”，使得过滤阻力降低。因此，纳米纤维膜已成为制备高效低阻空气过滤器的重要发展方向。
金属有机骨架（MOFs）材料具有高孔隙率、结构有序、孔尺寸可控、强的化学稳定性和热稳定性等性能，在吸附、分离和催化等方面均表现出了广阔的应用前景。沸石咪唑酯骨架材料(ZIF-67)是MOFs 材料的一种，它是由过渡金属离子(Co2+)与2-甲基咪唑络合自组装形成的新型具有沸石拓扑结构的超分子微孔网络结构材料。将ZIF-67纳米颗粒掺杂道到聚苯乙烯纺丝液中，采用静电纺丝技术，“一步法”将ZIF-67纳米颗粒嵌入聚苯乙烯纳米纤维的孔道中，制备具有微孔-介孔-大孔的ZIF-67/聚苯乙烯多级孔纳米纤维膜，使纤维膜的比表面积显著提高。ZIF-67纳米颗粒中丰富的微孔结构赋予膜材料优异的吸附性能，使纤维膜再过滤PM2.5等超细粉尘颗粒的同时吸附去除二氧化硫、一氧化氮、甲醛等有害气体，实现PM2.5和气相污染物协同治理。此外，ZIF-67纳米颗粒优异的水热稳定性，使ZIF-67/聚苯乙烯多级孔纳米纤维膜使用寿命长，有效降低成本。
发明内容
本发明的目的是提供一种空气净化用负载沸石咪唑酯骨架结构材料(ZIF-67)的聚苯乙烯多级孔纳米纤维膜的制备方法，该膜材料具有吸附去除气相污染物(如SO2、NO、VOCs等)和过滤超细粉尘(如PM2.5)等多种功能。
本发明所提供的一种空气净化用负载沸石咪唑酯骨架结构材料的聚苯乙烯多级孔纳米纤维膜的制备方法，包括如下步骤：
(1)ZIF-67纳米颗粒的合成：将一定质量的六水合硝酸钴和2-甲基咪唑分别溶于50 mL去离子水中，配制成硝酸钴溶液和2-甲基咪唑溶液，再向硝酸钴溶液中加入少量阳离子型表面活性剂(十六烷基三甲基溴化铵)，随后将硝酸钴溶液快速加入2-甲基咪唑溶液中，室温下剧烈搅拌10分钟后，静置合成一段时间，然后离心分离，用去离子水反复洗涤离心3次后，置于烘箱中干燥；
(2)纺丝液的配制：取一定质量的ZIF-67纳米颗粒置于N,N-二甲基甲酰胺中，放置于超声波仪中进行超声分散一定时间，再向其中加入适量四氢呋喃和聚苯乙烯颗粒，室温下搅拌至聚苯乙烯完全溶解；
(3)静电纺丝：将上述配制的纺丝液置于注射器中，通过平口金属针头，进行静电纺丝，采用附有铝箔的辊筒收集器接受，得到ZIF-67/聚苯乙烯多级孔纳米纤维膜，然后放置于烘箱中干燥。
上述方案步骤(1)中所述的六水合硝酸钴、2-甲基咪唑、十六烷基三甲基溴化铵和去离子水的摩尔比为1:55:0.02-0.04:4360。
上述方案步骤(1)中所述的ZIF-67静置合成时间为3-24 h，干燥温度为60-100℃，干燥时间为12-24 h。
上述方案步骤(2)中所述的纺丝液中ZIF-67和聚苯乙烯加入量的质量比为0.05-0.4:1。
上述方案步骤(2)中所述的纺丝液中聚苯乙烯的质量分数为10%-20%，四氢呋喃和N,N-二甲基甲酰胺的质量比为1:4-3:2。
上述方案步骤(2)中所述的超声分散时间为10-30 min。
上述方案步骤(3)中所述的纺丝电压为10-18 kV，接收距离为15-25 cm，纺丝速率为0.5-1.5 mL/h，纺丝针头横向平移距离为80-100 mm，接收辊转速为50-80 r/min，温度为20-30 ℃，相对湿度为35%-55%。
上述方案步骤(3)中所述的干燥温度为40-60 ℃，干燥时间为30-90 min。
本发明的有益效果：
本发明提供了一种空气净化用负载沸石咪唑酯骨架结构材料的聚苯乙烯多级孔纳米纤维膜的制备方法，该方法简单有效，易于调控且成本低廉，兼具多级孔材料的高比表面积，利于吸附和纳米纤维膜的高孔隙率，强传质性能，实现气相污染物(如SO2、NO、VOCs等)和超细粉尘(如PM2.5)的协同去除。并且，ZIF-67纳米颗粒被嵌入到聚苯乙烯纳米纤维上的介孔中，不易被PM2.5污染失活，所以该膜材料使用寿命长，在多功能空气净化领域具有良好的应用前景。
附图说明
图1为本发明的制备流程图。
图2为实施例1中制备的ZIF-67纳米颗粒的扫描电镜图
图3(a)为实施例3制备的负载ZIF-67的聚苯乙烯多级孔纳米纤维膜表面的扫描电镜图。
图3(b)为实施例3制备的负载ZIF-67的聚苯乙烯多级孔纳米纤维膜截面的扫描电镜图。
图4为实施例4制备的负载ZIF-67的聚苯乙烯多级孔纳米纤维膜的SO2动态吸附曲线图。
具体实施方式
下面结合实施例对本发明做更进一步地解释。下列实施例仅用于说明本发明，但并不用来限定本发明的实施范围。
实施例1
称取2-甲基咪唑5.4 g溶解于50 mL去离子水中，配置成2-甲基咪唑溶液待用；称取0.35 g六水合硝酸钴溶解于50 mL去离子水中，再加入0.009 g十六烷基三甲基溴化铵，继续搅拌至溶解，配制成硝酸钴溶液待用；将硝酸钴溶液快速倒入2-甲基咪唑溶液中，室温下剧烈搅拌10 min后，静置3 h；然后在8000 r/min转速下离心5 min，分离得到紫色固体，再用去离子水反复洗涤离心分离3次，最后置于80 ℃烘箱中干燥24 h，制得ZIF-67纳米颗粒。
本实施例中制得的ZIF-67纳米颗粒采用扫描电镜分析，如图2所示，ZIF-67具有较规整的三维立方体结构，尺寸分布均匀。
实施例2
称取2-甲基咪唑5.4 g溶解于50 mL去离子水中，配置成2-甲基咪唑溶液待用；称取0.35 g六水合硝酸钴溶解于50 mL去离子水中，再加入0.015 g十六烷基三甲基溴化铵，继续搅拌至溶解，配制成硝酸钴溶液待用；将硝酸钴溶液快速倒入2-甲基咪唑溶液中，室温下剧烈搅拌10 min后，静置20 h；然后在8000 r/min转速下离心5 min，分离得到紫色固体，再用去离子水反复洗涤离心分离3次，最后置于60 ℃烘箱中干燥24 h，制得ZIF-67纳米颗粒。
取上述制得的ZIF-67纳米颗粒0.4 g加入到7.2 g N,N-二甲基甲酰胺中，置于超声波仪中超声10 min，使ZIF-67纳米颗粒完全分散于N,N-二甲基甲酰胺中，再加入1.8 g四氢呋喃和1 g聚苯乙烯颗粒，室温下搅拌至聚苯乙烯完全溶解，配置成聚苯乙烯质量分数为10%的纺丝液，待用。将上述纺丝液分别放置在四个5 mL注射器中，每个注射器中注入1.5mL溶液，采用四个平口针头同时进行静电纺丝，纺丝电压为10 kV，接收距离为15 cm，纺丝速率为0.5 mL/h，针头横向平移距离为100 mm，接收辊转速为50 r/min，温度为20 ℃，相对湿度为35%。进行静电纺丝1.5 h后，从接收辊上取下纳米纤维膜，置于60 ℃烘箱中干燥90min，制得负载ZIF-67的聚苯乙烯多级孔纳米纤维膜。
实施例3
称取2-甲基咪唑5.4 g溶解于50 mL去离子水中，配置成2-甲基咪唑溶液待用；称取0.35 g六水合硝酸钴溶解于50 mL去离子水中，再加入0.018 g十六烷基三甲基溴化铵，继续搅拌至溶解，配制成硝酸钴溶液待用；将硝酸钴溶液快速倒入2-甲基咪唑溶液中，室温下剧烈搅拌10 min后，静置24 h；然后在8000 r/min转速下离心5 min，分离得到紫色固体，再用去离子水反复洗涤离心分离3次，最后置于100 ℃烘箱中干燥12 h，制得ZIF-67纳米颗粒。
取上述制得的ZIF-67纳米颗粒0.05 g加入到1.6 g N,N-二甲基甲酰胺中，置于超声波仪中超声30 min，使ZIF-67纳米颗粒完全分散于N,N-二甲基甲酰胺中，再加入2.4 g四氢呋喃和1 g聚苯乙烯颗粒，室温下搅拌至聚苯乙烯完全溶解，配置成聚苯乙烯质量分数为20%的纺丝液，待用。将上述纺丝液分别放置在四个5 mL注射器中，每个注射器中注入1.5mL溶液，采用四个平口针头同时进行静电纺丝，纺丝电压为18 kV，接收距离为25 cm，纺丝速率为1.5 mL/h，针头横向平移距离为80 mm，接收辊转速为80 r/min，温度为30 ℃，相对湿度为55%。进行静电纺丝1.5 h后，从接收辊上取下纳米纤维膜，置于40 ℃烘箱中干燥30min，制得负载ZIF-67的聚苯乙烯多级孔纳米纤维膜。
采用扫描电镜对本实施例中负载ZIF-67的聚苯乙烯多级孔纳米纤维膜的表面和横截面形貌进行观察，如图3(a)和(b)所示，ZIF-67纳米颗粒在纤维表面和纤维交织形成的大孔中几乎没有分布，主要分布在聚苯乙烯纳米纤维内部的介孔中，形成具有微孔-介孔-大孔的多级孔结构纳米纤维膜。
实施例4
取实施例2中制得的ZIF-67纳米颗粒0.1 g配置成聚苯乙烯质量分数为15%的纺丝液进行静电纺丝，纺丝电压为15 kV，接收距离为15 cm，纺丝速率为1.0 mL/h，针头平移距离为100 mm，接收辊转速为50 r/min，温度为25 ℃，相对湿度为50%，得到的纳米纤维膜置于60℃烘箱中干燥30 min得到负载ZIF-67的聚苯乙烯多级孔纳米纤维膜。
取上述制得的纳米纤维膜0.05 g进行动态二氧化硫气体吸附，二氧化硫气体浓度为500ppm，气流速度为50 mL/min，吸附温度为20 ℃，相对湿度为50%。图4所示为负载ZIF-67的聚苯乙烯多级孔纳米纤维膜对二氧化硫气体的动态吸附曲线图，经过10 h后达到吸附平衡，平衡吸附量为866 mg/g。
Claims (7)
1.一种一步法制备空气净化用多级孔纳米纤维膜的方法，其特征在于，包括以下步骤：
(1)ZIF-67纳米颗粒的合成：将一定质量的六水合硝酸钴和2-甲基咪唑分别溶于一定体积的去离子水中，配制成硝酸钴溶液和2-甲基咪唑溶液，再向硝酸钴溶液中加入少量十六烷基三甲基溴化铵阳离子型表面活性剂，随后将硝酸钴溶液快速加入2-甲基咪唑溶液中，室温下剧烈搅拌10分钟后，静置一段时间，然后离心分离，用去离子水反复洗涤离心3次后，置于烘箱中干燥；
(2)纺丝液的配制：取一定质量的ZIF-67纳米颗粒置于N,N-二甲基甲酰胺中，超声分散一定时间，再向其中加入适量四氢呋喃和聚苯乙烯颗粒，室温下搅拌至聚苯乙烯完全溶解；
(3)静电纺丝：将上述配制的纺丝液置于注射器中，通过平口金属针头，进行静电纺丝，采用附有铝箔的辊筒收集器接收，得到ZIF-67/聚苯乙烯多级孔纳米纤维膜，然后放置于烘箱中干燥。
2.根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(1)中所述的六水合硝酸钴、2-甲基咪唑、十六烷基三甲基溴化铵和去离子水的摩尔比为1:55:0.02-0.04:4360。
3.根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(2)中所述的纺丝液中ZIF-67和聚苯乙烯加入量的质量比为0.05-0.4:1。
4.根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(2)中所述的纺丝液中聚苯乙烯的质量分数为10%-20%，四氢呋喃和N,N-二甲基甲酰胺的质量比为1:4-3:2。
5. 根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(2)中所述的超声分散时间为10-30 min。
6. 根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(3)中所述的纺丝电压为10-18 kV，接收距离为15-25 cm，纺丝速率为0.5-1.5 mL/h，纺丝针头横向平移距离为80-100 mm，接收辊转速为50-80 r/min，温度为20-30 ℃，相对湿度为35%-55%。
7. 根据权利要求1所述的用于空气净化的多级孔纳米纤维膜的制备方法，其特征在于，步骤(3)中所述的干燥温度为40-60 ℃，干燥时间为30-90 min。
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