CN115434148B - 一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜及其制备方法和应用 - Google Patents

一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜及其制备方法和应用 Download PDF

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CN115434148B
CN115434148B CN202210936047.3A CN202210936047A CN115434148B CN 115434148 B CN115434148 B CN 115434148B CN 202210936047 A CN202210936047 A CN 202210936047A CN 115434148 B CN115434148 B CN 115434148B
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CN115434148A (zh
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程志林
乐强
相阳
薛帆
朱伟玮
朱华文
刘赞
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Yangzhou University
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Abstract

本发明公开了一种Ag2O/ZIF‑8@PAN核壳结构纳米复合纤维膜及其制备方法和应用，通过分散在纳米纤维中的Zn2+为锚点，通过微波驱动在纤维表面快速的均匀生长了一层Ag2O/ZIF‑8纳米颗粒，形成一层密集的壳层结构，易于从燃料油中分离，具有优异的分离性能和较高的机械强度和耐磨性能，同时制得的Ag2O/ZIF‑8@PAN复合纳米纤维膜具有多孔结构，其纤维表面的Ag2O与料油中的噻吩类硫化物形成π络合作用以及S‑M键合作用，提高吸附能力。本发明制备方法简单，生长时间短，反应条件可控性良好。

Description

一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜及其制备方法 和应用
技术领域
本发明属于功能材料技术领域，具体涉及到一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜及其制备方法和应用。
背景技术
随着对燃料日益增长的需求，这也促使了一系列法律法规对燃料油中硫组分浓度的严格限制，燃料油中硫组分的脱除逐渐引起了人们的研究兴趣，在众多的脱硫技术中，吸附脱硫技术具有操作条件温和、环境友好、可以有效去除传统的加氢脱硫技术难以去除的噻吩类硫化物且不会造成过高的辛烷值损失等优点被认为是一种理想的脱硫方式。吸附脱硫的关键在于吸附剂的制备，目前常用的吸附剂主要有MOFs，金属氧化物，活性炭等，但其都存在着分离效率低和力学强度差的问题，极大了限制了其应用。
基于静电纺丝技术制备的纳米纤维膜具有丰富的孔隙结构且力学强度好，分离效率高的优点，有利于解决常规颗粒状吸附剂分离困难的问题，近些年来在吸附分离领域得到了广泛研究。然而由于常规的共混法制备的静电纺丝纤维膜由于活性位点被包埋而存在吸附容量较低，大量的研究表明将吸附活性位点的表面化是提高其吸附活性的理想方法，目前有研究人员提出了通过水热法在纳米纤维表面一种原位生长一层活性物质的方案，如通过水热法在纤维表面生长了一层MOF壳层。然而通过水热法制备MOF原位生长的纤维膜往往需要较长的时间，这个过程可能会对纤维膜的力学强度造成较大影响，尽可能缩短热处理时间以减小材料力学强度的损耗就成为了亟待解决的问题。目前发现通过微波驱动的方法可以在几分钟内快速的在相界面处生长一层MOF层，这为具有高吸附活性和高力学强度的纳米纤维膜的快速制备提供了可能。然而另一个问题在于ZIF-8晶体虽然具有一定吸附活性但其对噻吩类硫化物的选择性不足，Ag2O作为一种高活性的金属氧化物被证明可以与噻吩化合物的硫元素迅速形成S-M和π-π相互作用，是一种良好的吸附活性组分可以有效提高材料的吸附活性。
发明内容
本部分的目的在于概述本发明的实施例的一些方面以及简要介绍一些较佳实施例。在本部分以及本申请的说明书摘要和发明名称中可能会做些简化或省略以避免使本部分、说明书摘要和发明名称的目的模糊，而这种简化或省略不能用于限制本发明的范围。
鉴于上述和/或现有技术中存在的问题，提出了本发明。
因此，本发明的目的是，克服现有技术中的不足，提供一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜的制备方法。
为解决上述技术问题，本发明提供了如下技术方案：
制备Zn2+/PAN纤维膜：
将PAN溶于DMF溶液中，搅拌均匀得到PAN溶液，加入Zn(NO3)2·6H2O，充分混合得纺丝液，将纺丝液置于注射器中进行纺丝，纺丝得到的纤维膜烘干即得Zn2+/PAN纳米纤维膜；
制备Ag2O/ZIF-8@PAN复合纳米纤维膜：
将二甲基咪唑溶于甲醇形成溶液A，Zn(NO3)2·6H2O以及AgNO3溶于甲醇形成溶液B，将溶液A与溶液B混合，向混合液中加入Zn2+/PAN纳米纤维膜进行微波反应，反应结束后先将膜浸于NaOH溶液，再在乙醇中洗涤三次，烘干后即得Ag2O/ZIF-8@PAN复合纳米纤维膜。
作为本发明所述的一种优选方案，其中：所述PAN溶液，其中，PAN的质量分数为8～15％。
作为本发明所述的一种优选方案，其中：所述纺丝液中的Zn(NO3)2·6H2O添加量为0～2g。
作为本发明所述的一种优选方案，其中：所述置于注射器中进行纺丝，其中，纺丝电压为15～20V，纺丝速度为0.1～0.8mm/min，针头口径为19～23口，接收滚筒及针头间距为8～20cm。
作为本发明所述的一种优选方案，其中：所述混合溶液B，其中，Zn(NO3)2·6H2O的添加量为0.3～0.5g。
作为本发明所述的一种优选方案，其中：所述向混合液中加入Zn2+/PAN纳米纤维膜进行微波反应，其中，Zn2+/PAN纳米纤维膜的添加量为0.1～0.2g。
作为本发明所述的一种优选方案，其中：所述微波反应，其中，反应时间为1～5min，反应功率为100～400W。
本发明的另一目的是，克服现有技术中的不足，提供一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜，通过分散在纳米纤维中的Zn2+为锚点，通过微波驱动在纤维表面快速的均匀生长了一层Ag2O/ZIF-8纳米颗粒，得到具有多孔结构，力学强度好且易于分离再生的Ag2O/ZIF-8@PAN复合纳米纤维膜。
本发明的再一目的是，克服现有技术中的不足，提供一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜在吸附脱硫中的应用。
本发明有益效果：
(1)本发明中通过分散在纳米纤维中的Zn2+为锚点，通过微波驱动在纤维表面快速的均匀生长了一层Ag2O/ZIF-8纳米颗粒，形成一层密集的壳层结构，易于从燃料油中分离，具有优异的分离性能和较高的机械强度和耐磨性能。
(2)本发明制备的Ag2O/ZIF-8@PAN复合纳米纤维膜具有多孔结构，其纤维表面的Ag2O与料油中的噻吩类硫化物形成π络合作用以及S-M键合作用，具有良好的吸附能力。
(3)本发明制备方法简单，生长时间短，反应条件可控性良好。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其它的附图。其中：
图1为本发明实施例2中添加不同质量Zn(NO3)2·6H2O制备的复合纳米纤维膜的扫描电镜图。
图2为本发明实施例4中采用不同微波处理时间制备的复合纳米纤维膜的扫描电镜图。
具体实施方式
为使本发明的上述目的、特征和优点能够更加明显易懂，下面结合说明书实施例对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明，但是本发明还可以采用其他不同于在此描述的其它方式来实施，本领域技术人员可以在不违背本发明内涵的情况下做类似推广，因此本发明不受下面公开的具体实施例的限制。
其次，此处所称的“一个实施例”或“实施例”是指可包含于本发明至少一个实现方式中的特定特征、结构或特性。在本说明书中不同地方出现的“在一个实施例中”并非均指同一个实施例，也不是单独的或选择性的与其他实施例互相排斥的实施例。
实施例1
将1.2gPAN溶于8.8gDMF溶液中制备12wt％的PAN溶液，在其中加入1.0gZn(NO3)2·6H2O，搅拌12h得到Zn2+/PAN纺丝液；将Zn2+/PAN纺丝液加到10mL的注射器中，将静电纺丝条件设置为电压18kV，推注速率0.1mm/min，使用直径为0.6mm的标准21G针头，收集辊筒与针头之间距离为15cm，辊筒转速50r/min进行纺丝，纺丝结束后将膜置于60℃烘箱中烘干12h以除去多余溶剂得到Zn2+/PAN纤维膜；
将0.2g二甲基咪唑溶于25mL甲醇形成溶液A，称取0.38gZn(NO3)2·6H2O以及0.09gAgNO3溶于25mL甲醇形成溶液B，将溶液A与溶液B混合，向混合溶液中加入0.1gZn2+/PAN纤维膜，微波反应2.5min，浸于NaOH溶液2min后在乙醇中洗涤三次以除去多余的颗粒，在60℃下烘干12h得到Ag2O/ZIF-8@PAN复合纳米纤维膜。
实施例2
本实施例探究纺丝液中不同Zn(NO3)2·6H2O的添加量对制得复合纳米纤维膜性能的影响。
参照实施例1的制备方法，纺丝液中Zn(NO3)2·6H2O的添加量分别为0.4g、0.6g、0.8g、1.0g、1.2g，其余步骤均与实施例1相同。
将制得的复合纳米纤维膜分别取0.1g填装于内径为6mm，长度为75mm的吸附柱中，以0.13mL/min的固定流速注入300ppm噻吩浓度的模拟油，使用GC-9790气相色谱仪检测出液硫浓度，测定其力学强度、摩擦系数、动态突破吸附容量和动态饱和容量，结果如表1。
表1不同Zn(NO3)2·6H2O添加量对复合膜性能的影响
图1为本实施例添加不同质量Zn(NO3)2·6H2O制备的复合纳米纤维膜的扫描电镜图，结合图1和表1可以看出，当Zn(NO3)2·6H2O添加量过低时，纳米纤维膜表面颗粒生长量低或无生长，当Zn(NO3)2·6H2O添加量过高时纳米纤维膜表面生长颗粒粒径过大，只有当Zn(NO3)2·6H2O为1.0g时，复合纳米纤维膜表面才能均匀增长，制得的复合纤维膜具有多孔结构，力学强度好且易于分离再生。
实施例3
本实施例探究不同AgNO3的添加量对制得复合纳米纤维膜性能的影响。
参照实施例1的制备方法，AgNO3的添加量分别为0.01g、0.03g、0.05g、0.07g、0.09g、0.11g，其余步骤均与实施例1相同。
将制得的复合纳米纤维膜分别取0.1g填装于内径为6mm，长度为75mm的吸附柱中，以0.13mL/min的固定流速注入300ppm噻吩浓度的模拟油，使用GC-9790气相色谱仪检测出液硫浓度，测定其力学强度、摩擦系数、动态突破吸附容量和动态饱和容量，结果如表2。
表2不同AgNO3添加量对复合膜性能的影响
由表2可以看出，AgNO3的添加量对复合纳米纤维膜的力学强度和摩擦性能未造成显著性影响，对复合纳米纤维膜的吸附性能影响较大，当AgNO3的添加量过低时，突破吸附容量及饱和吸附容量由于活性位点不足均较低，当AgNO3的添加量过高时，突破吸附容量及饱和吸附容量由于孔道被堵塞因此均较低，只有添加量在0.09g时，复合纳米纤维膜的吸附性能最佳。
实施例4
本实施例探究不同微波驱动时间对制得复合纳米纤维膜性能的影响。
参照实施例1的制备方法，微波驱动的时间分别为1.0min、1.5min、2.0min、2.5min、3.0min，其余步骤均与实施例1相同。
将制得的复合纳米纤维膜分别取0.1g填装于内径为6mm，长度为75mm的吸附柱中，以0.13mL/min的固定流速注入300ppm噻吩浓度的模拟油，使用GC-9790气相色谱仪检测出液硫浓度，测定其力学强度、摩擦系数、动态突破吸附容量和动态饱和容量，结果如表3。
表3不同微波处理时间对复合膜性能的影响
图2为本实施例采用不同微波处理时间制备的复合纳米纤维膜的扫描电镜图，结合图2和表3可以看出，当微波处理时间过短时，纤维膜表面生长的颗粒过小，当微波处理时间过长时，纤维膜表面生长的颗粒容易团聚，只有当处理时间为2.5min时复合纳米纤维膜表面生长均匀，制得的复合纤维膜具有多孔结构，力学强度好，吸附性能最佳且易于分离再生。
由上述实验可以看出，在本发明中，纺织液中Zn(NO3)2·6H2O的最佳添加量为1.0g，AgNO3的最佳添加量为0.09g，最佳微波处理时间为2.5min。
对比例1
本实施例探究水热法对制得复合纳米纤维膜性能的影响。
参照实施例1的制备方法，区别在于，Ag2O/ZIF-8的生长过程通过水热合成法在80℃下分别处理6、8、10、12、14h，其余步骤均与实施例1相同。
将制得的复合纳米纤维膜分别取0.1g填装于内径为6mm，长度为75mm的吸附柱中，以0.13mL/min的固定流速注入300ppm噻吩浓度的模拟油，使用GC-9790气相色谱仪检测出液硫浓度，测定其力学强度、摩擦系数、动态突破吸附容量和动态饱和容量，结果如表4。
表4不同水热处理时间对复合膜性能的影响
表4可以看出，水热处理的过程整体耗时较长，使得复合纤维膜的力学性能和减磨性能均产生了较大的负面影响，这是因为长时间的水热处理使纤维的结构造成了破坏。且经过长时间水热处理的复合纤维膜吸附性能也较低。
对比例2
本实施例探究水热共混改性法对制得复合纳米纤维膜性能的影响。
将0.2g二甲基咪唑溶于25mL甲醇形成溶液A，称取0.38gZn(NO3)2·6H2O以及0.09gAgNO3溶于25mL甲醇形成溶液B，将溶液A与溶液B混合，室温下搅拌24h，过滤后浸于NaOH水溶液中，过滤后60℃烘干24h得到Ag2O/ZIF-8纳米颗粒。
将1.2gPAN溶于8.8gDMF溶液中制备12wt％的PAN溶液，分别在其中加入1.0g的Ag2O/ZIF-8得到纺丝液，将纺丝液加到10mL的注射器中，将静电纺丝条件设置为电压18kV，推注速率0.1mm/min，使用直径为0.6mm的标准21G针头，收集辊筒与针头之间距离为15cm，辊筒转速50r/min进行纺丝，纺丝结束后将膜置于60℃烘箱中烘干12h以除去多余溶剂得到共混法改性的纤维膜。
将制得的复合纳米纤维膜分别取0.1g填装于内径为6mm，长度为75mm的吸附柱中，以0.13mL/min的固定流速注入300ppm噻吩浓度的模拟油，使用GC-9790气相色谱仪检测出液硫浓度，测定其动态突破吸附容量和动态饱和容量，测得结果为其突破吸附容量为21.64mg/g，饱和吸附容量为21.65mg/g。
由该对比例可以看出，采用共混法改性整体耗时较长，并且尽管由于硬质Ag2O/ZIF-8颗粒的加入能够使材料的力学性能和减磨性能得到提升，然而由于共混法制备的复合纳米纤维膜存在活性位点被包埋的问题整体吸附性能相比采用微波法有所不足。
本发明发现通过微波驱动的方法可以在几分钟内快速的在相界面处生长一层MOF层，这为具有高吸附活性和高力学强度的纳米纤维膜的快速制备提供了可能。本发明还采用过UIO-66，CuBDC和ZnBDC作为原料，但在制备过程中发现这些原料合成温度需求较高，微波驱动反应时间过短无法满足需求，反应时间过高长无法合成完整的纤维膜。同时ZIF-8晶体虽然具有一定吸附活性但其对噻吩类硫化物的选择性不足，而Ag2O作为一种高活性的金属氧化物被证明可以与噻吩化合物的硫元素迅速形成S-M和π-π相互作用，是一种良好的吸附活性组分可以有效提高材料的吸附活性。
综上，本发明以分散在纳米纤维中的Zn2+为锚点，通过微波驱动在纤维表面快速的均匀生长了一层Ag2O/ZIF-8纳米颗粒，形成一层密集的壳层结构，易于从燃料油中分离，具有优异的分离性能和较高的机械强度和耐磨性能，制备工艺简单，耗时短，具有广阔的应用前景。
应说明的是，以上实施例仅用以说明本发明的技术方案而非限制，尽管参照较佳实施例对本发明进行了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的精神和范围，其均应涵盖在本发明的权利要求范围当中。

Claims (5)

1.一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜的制备方法，其特征在于：包括，
制备Zn2+/PAN纤维膜：
将PAN溶于DMF溶液中，搅拌均匀得到质量分数为8~15%的PAN溶液，加入质量为0.4~2g的Zn(NO3)2·6H2O，充分混合得纺丝液，将纺丝液置于注射器中进行纺丝，纺丝得到的纤维膜烘干即得Zn2+/PAN纳米纤维膜；
制备Ag2O/ZIF-8@PAN复合纳米纤维膜：
将二甲基咪唑溶于甲醇形成溶液A，添加0.3~0.5g的Zn(NO3)2·6H2O以及0.01~0.2g的AgNO3溶于甲醇形成溶液B，将溶液A与溶液B混合，向混合液中加入 Zn2+/PAN纳米纤维膜进行微波反应，反应时间为1~5min，反应功率为100~400W，反应结束后先将膜浸于NaOH溶液，再在乙醇中洗涤三次，烘干后即得Ag2O/ZIF-8@PAN复合纳米纤维膜。
2.如权利要求1所述的Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜的制备方法，其特征在于：所述置于注射器中进行纺丝，其中，纺丝电压为15~20V，纺丝速度为0.1~0.8mm/min，针头口径为19~23口，接收滚筒及针头间距为8~20cm。
3.如权利要求1所述的Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜的制备方法，其特征在于：所述向混合液中加入 Zn2+/PAN纳米纤维膜进行微波反应，其中，Zn2+/PAN纳米纤维膜的添加量为0.1~0.2g。
4.如权利要求1~3任一项所述方法制备得到的Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜，其特征在于：通过分散在纳米纤维中的Zn2+为锚点，通过微波驱动在纤维表面快速的均匀生长了一层Ag2O/ZIF-8纳米颗粒，得到具有多孔结构，力学强度好且易于分离再生的Ag2O/ZIF-8@PAN复合纳米纤维膜。
5.如权利要求4所述的一种Ag2O/ZIF-8@PAN核壳结构纳米复合纤维膜在吸附脱硫中的应用。
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