CN113828288B - 一种仿肺泡双层纳微纤维膜光催化剂及其制备方法 - Google Patents

一种仿肺泡双层纳微纤维膜光催化剂及其制备方法 Download PDF

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CN113828288B
CN113828288B CN202010576783.3A CN202010576783A CN113828288B CN 113828288 B CN113828288 B CN 113828288B CN 202010576783 A CN202010576783 A CN 202010576783A CN 113828288 B CN113828288 B CN 113828288B
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韩振邦
李锦芳
邓杨
赵晓明
吕明泽
刘利伟
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Tianjin Polytechnic University
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Abstract

本发明涉及一种仿肺泡双层纳微纤维膜光催化剂及其制备方法，制备步骤如下：(1)首先配制聚苯乙烯的DMF溶液，通过静电纺丝获得疏水层纳微纤维膜；(2)以DMF作为溶剂，配制含有聚丙烯腈、聚乙烯吡咯烷酮、光催化剂和光敏剂的纺丝液，通过逐层静电纺丝获得兼具疏水层和亲水催化层的双层纳微纤维膜；(3)通过中空袋状结构设计，获得仿肺泡双层纳微纤维膜光催化剂。与现有技术相比，本发明能够通过模拟肺泡呼吸过程实现气液固三相高效接触，显著增加反应界面O2浓度，进而大幅提升光敏化催化体系的可见光催化活性，在光降解有机污染物领域具有广阔的应用前景。

Description

一种仿肺泡双层纳微纤维膜光催化剂及其制备方法
技术领域
本发明属于新材料领域，具体为一种适用于光降解废水中有机污染物领域的仿肺泡双层纳微纤维膜光催化剂及其制备方法。
背景技术
光催化技术作为一种绿色环境净化技术，在环境治理领域应用前景非常广阔。在众多光催化材料中，二氧化钛(TiO2)因具有光化学稳定性好、成本低和无毒无害等优点，成为研究热点。但是TiO2禁带带隙较宽(3.0-3.2eV)，仅能利用太阳光中含量为3-5％的紫外光，限制了其对太阳光的利用效率。如何拓展TiO2的光谱响应范围，使其能够利用可见光(占太阳光50％左右)处理污染物，成为光催化技术的核心问题之一。
光敏化TiO2是构建可见光催化体系的重要策略，其能够通过光敏剂较宽的光谱响应范围，高效利用太阳光处理污染物。在众多光敏剂中，金属酞菁/卟啉作为一类具有含氮芳香性大π环结构的有机配合物，因其优异的结构稳定性和可见光捕捉能力而备受关注。然而目前金属酞菁/卟啉敏化TiO2体系存在光催化效率低下的问题，因此开发高活性光敏化催化材料对于高效利用太阳能具有重要意义。
O2可以捕捉光生电子并产生活性氧物种，因此提高光催化界面O2浓度可以显著提升其光催化活性。Journal of the American Chemistry Society 139(2017)12402-12405报道了将TiO2负载于超疏水多孔碳纤维上，能够借助超疏水材料的拒水性和多孔性能，将空气中O2传递至催化界面构建气(O2)液(H2O)固(TiO2)三相体系，大幅促进光生电荷分离并提升紫外光下TiO2降解污染物活性。由此可见，借助疏水材料构建气液固三相界面，是有效提升光敏化催化体系活性的潜在手段。但是目前疏水材料负载催化剂的常规方法是等离子体、光辐射改性接枝或磁控溅射等，不仅存在能耗高、操作难度大等问题，而且在负载复合光催化剂时，存在均匀负载困难和载体相容性差等不足。再者，目前的三相光催化体系还存在气液固三相接触效率较低的问题。
发明内容
本发明的目的是通过解决上述问题，提供一种仿肺泡双层纳微纤维膜光催化剂，该催化剂具有制备方法简单、成本低、光敏剂/光催化剂负载均匀等特点，而且能够构建高效的气液固三相体系，使其在可见光下具有很高的催化效率。
本发明所采用的技术方案，是使用静电纺丝技术逐层制备用于空气传输的疏水层和负载光敏剂/光催化剂的亲水层，其中疏水层是由PS组成，亲水层由PAN、PVP、光敏剂和光催化剂组成。本发明提供的仿肺泡双层纳微纤维膜光催化剂的制备方法，具体步骤如下：
1)将PS和有机溶剂DMF以质量百分比18-22％的比例配制纺丝液，磁力搅拌4-8h后置于注射器中，采用静电纺丝装置纺丝2-6h，得到疏水层PS纳微纤维膜。
2)以DMF为有机溶剂，配制含有PAN、PVP、光催化剂和光敏剂的纺丝液，其质量百分比分别为6-10％、6-10％、2-8％和0.2-2％，然后在60℃条件下搅拌4-8h制备纺丝液，冷却后置于注射器中，并将1)制备的PS纳微纤维膜作为接收基材，采用静电纺丝装置纺丝4-12h，最后将获得的纤维膜置于60℃水溶液中处理4-12h去除PVP牺牲剂，得到双层纳微纤维膜。
3)将步骤2得到的双层纳微纤维膜裁剪成约4cm×5cm尺寸的长方形，通过卷曲将疏水层置于内层，并分别将其侧面和上下两端进行密封，同时在上端密封时引入内径为5-7mm的针头作为空气入口，最终获得仿肺泡双层纳微纤维膜催化剂。
所述的静电纺丝参数为：电压15-30kV，接收装置与喷丝口距离10-30cm，挤出速率为0.5-2mL/h，温度20-30℃，相对湿度25-50％。
所述的光催化剂为二氧化钛(TiO2)、石墨相氮化碳(g-C3N4)的任意一种；光敏剂为金属酞菁、金属卟啉或其衍生物的任意一种，其中金属离子可以是铁、铜、钴、锌的任意一种。
发明原理：
本发明采用静电纺丝技术逐层制备兼具疏水层和亲水层的双层纳微纤维膜，实现传输气体的疏水层和光催化亲水层之间的有机结合。纤维载体能够提高光敏剂/光催化剂分散性并增加其结构可调控性，尤其是微纳米纤维具有柔性高、比表面积大和孔隙率高等优点，不仅可作为光催化剂的载体材料，而且也是构筑超疏水材料的重要基材。静电纺丝是当前制备微纳米纤维最有效的方法，具有可纺原料种类丰富、纤维结构可调性好、多元技术结合性强等优势。因此本发明首先采用低表面能的聚合物PS进行静电纺丝制备疏水层，再通过逐层纺丝引入PAN/PVP均匀负载光敏剂和光催化剂的亲水层，在后续水处理过程中去除PVP牺牲剂，可以增加亲水层纳米纤维膜的比表面积和孔隙率，使更多的光敏剂/光催化剂活性位能够暴露出来。
此外，本发明还利用纳微纤维膜的高柔性特点，对其进行仿肺泡结构设计。肺泡是完成呼吸的基本单元，其内层覆盖大量约1um厚的疏水性蛋黄素细胞膜，允许空气透过同时可以防止液体渗透，外层则保持高亲水性与血液紧密结合。借助中空半球形状及泡壁内外不对称的亲疏结构，肺泡能使气液固三相接触效率最大化，从而完成高效气体交换。因此，本发明通过模拟肺泡呼吸过程，实现高效气液固三相接触界面构建，进而提升光敏化催化体系的光催化效率。
与现有的光敏化催化剂以及基于三相界面的光催化剂相比，本发明的有益效果在于：
1)本发明的一种仿肺泡双层纳微纤维膜光催化剂的制备方法，借助静电纺丝技术将光敏剂和光催化剂同时均匀负载于亲水纳米纤维膜，获得连续性好、光电传输率高的光敏化催化剂；同时借助逐层静电纺丝实现疏水纤维膜与亲水纤维膜的有机结合，为构建高效三相光催化体系提供了一种简单有效的新方法。
2)本发明的一种仿肺泡双层纳微纤维膜光催化剂的制备方法，通过对高柔性的双层纳微纤维膜进行结构设计，获得仿肺泡结构的光催化剂，使其能够模拟肺泡呼吸过程，使气液固三相接触效率最大化，从而构建更为高效的三相光催化体系。
3)本发明的一种仿肺泡双层纳微纤维膜光催化剂，借助高效三相接触界面，实现光敏化催化界面O2的持续稳定供应，进而高效捕捉光生电子并产生活性氧物种，从而在可见光下显示出更高的光敏化催化效率。
附图说明
图1为本发明中所述的一种仿肺泡双层纳微纤维膜光催化剂(实施例一)光催化反应时的实物图片；
图2为本发明中所述的一种仿肺泡双层纳微纤维膜光催化剂(实施例一)疏水层的SEM图片和表面水接触角图片。
图3为本发明中所述的一种仿肺泡双层纳微纤维膜光催化剂(实施例一)亲水层的SEM图片和表面水接触角图片。
图4为本发明中所述的实施例一和对比例一对四环素光催化降解的活性比较(测试条件：四环素浓度：50mg/L，TiO2浓度：～0.4g/L，pH＝5.0，温度：25℃，可见光λ＞420nm；降解反应中，对比例一浸入反应溶液中，进行常规液固两相光催化反应；实施例一浸入反应溶液后，通过中空结构内部引入空气，形成高效的气液固三相接触界面进行光催化反应)。
具体实施方式
下面将结合实施例及附图进一步阐明本发明的内容，但这些实施例并不限制本发明的保护范围。
实施例一：
1)将PS和有机溶剂DMF以质量百分比19.5％的比例配制纺丝液，磁力搅拌4h后置于注射器中，采用静电纺丝装置纺丝4h，得到疏水层PS纳微纤维膜。静电纺丝参数：电压21kV，接收装置与喷丝口距离13cm，挤出速率为0.5mL/h，温度25℃，相对湿度25％。
2)以DMF为有机溶剂，分别添加质量百分比均为8％的PAN和PVP，搅拌均匀后加入P25 TiO2和酞菁铁(FePc)，其质量百分比分别为4.0％和1.44％，然后在60℃条件下搅拌6h制备纺丝液，冷却后置于注射器中，将1)制备的PS纳微纤维膜作为接收基材，采用静电纺丝装置纺丝8h，最后将获得的纤维膜置于60℃水溶液中处理6h去除PVP牺牲剂，得到双层纳微纤维膜。静电纺丝参数：电压21kV，接收装置与喷丝口距离13cm，挤出速率为0.5mL/h，温度25℃，相对湿度25％。
3)将步骤2得到的双层纳微纤维膜裁剪成约4cm×5cm尺寸的长方形，卷曲后使用2mm宽脉冲封口机分别将其侧面和上下两端进行密封，同时在上端密封时引入内径为5-7mm的针头作为空气入口，然后使用Kapton胶带对密封处进行保护，获得第一种仿肺泡双层纳微纤维膜催化剂，其光敏剂FePc与TiO2的比例为36％。
实施例二、三：
将实施例一步骤2中FePc质量百分比分别调整为0.36％和2.16％，其余同实施例一，得到第二种和第三种仿肺泡双层纳微纤维膜催化剂，其光敏剂FePc与TiO2的比例分别为9％和54％。
实施例四、五、六：
将实施例一步骤2中光敏剂分别调整为酞菁铜、酞菁钴、酞菁锌，其余同实施例一，得到第四种、第五种和第六种仿肺泡双层纳微纤维膜光催化剂，其亲水层中光敏剂金属活性中心分别为铜离子、钴离子和锌离子。
实施例七：
将实施例一步骤2中光敏剂调整为氯化血红素(hemin)，其余同实施例一，得到第七种仿肺泡双层纳微纤维膜光催化剂，其亲水层中光敏剂为铁卟啉配合物hemin。
实施例八：
将实施例一步骤2中光催化剂调整为g-C3N4，其余同实施例一，得到第八种仿肺泡双层纳微纤维膜光催化剂，其亲水层中含有光敏化的g-C3N4催化材料。
实施例九、十、十一、十二：
将实施例一步骤2中光催化剂调整为g-C3N4，光敏剂分别调整为酞菁铜、酞菁钴、酞菁锌、hemin，其余同实施例一，得到第九种第十种、第十一种和第十二种仿肺泡双层纳微纤维膜光催化剂，其亲水层中光催化剂为g-C3N4，光敏剂分别为酞菁铜、酞菁钴、酞菁锌和hemin。
对比例一：
将实施例一中前2步获得的双层纳微纤维膜光催化剂作为对比例一，与实施例一相比其主要区别是未经过仿肺泡结构设计。
图1显示，本发明中所述的实施例一外观为绿色，FePc和TiO2分布均较为均匀，而且通过引入空气能够在光催化过程中形成中空的仿肺泡结构。图2显示，本发明中所述的实施例一的疏水层由纤维直径较大的纳微纤维组成，其表面接触角高达140±2°，具有明显的疏水特性。图3显示，本发明中所述的实施例一的亲水层由纤维直径较小的纳米纤维组成，其表面接触角为28±2°，具有明显的亲水特性。这些结果证实本发明所述的仿肺泡双层纳微纤维膜具有内外亲疏不对称的结构，为其构建气液固三相体系提供了条件。
图4显示，对比例一建立的常规两相光催化反应中，90min后仅有不足30％的四环素发生降解反应；本发明所述的实施例一构建的高效三相光催化体系中，90min后四环素几乎全部被氧化降解。这说明本发明所述的仿肺泡双层纳微纤维膜光催化剂，能够通过构建高效气液固三相接触界面，在可见光下赋予光敏化催化材料优异的催化效率，有望解决目前光敏化催化技术存在的瓶颈问题，具有良好的应用前景。

Claims (4)

1.一种仿肺泡双层纳微纤维膜光催化剂的制备方法，其特征在于，所述方法具有如下步骤：
1)配制质量百分比为18-22％的聚苯乙烯/DMF纺丝液，常温搅拌4-8h后置于注射器中，进行静电纺丝4-8h得到疏水层聚苯乙烯纳微纤维膜；
2)以DMF为有机溶剂，配制含有聚丙烯腈、聚乙烯吡咯烷酮、光催化剂和光敏剂的纺丝液，其质量百分比分别为6-10％、6-10％、2-8％和0.2-2％，在60℃条件下搅拌4-8h，冷却后置于注射器中，并将步骤1)制备的聚苯乙烯纳微纤维膜作为接收基材，静电纺丝4-12h后，将获得纤维膜置于60℃水溶液中处理4-12h，得到双层纳微纤维膜；
3)将步骤2)得到的双层纳微纤维膜裁剪成约4cm×5cm尺寸的长方形，通过卷曲将疏水层置于内层，然后分别将其侧面和上下两端进行密封，同时在上端密封时引入内径为5-7mm的针头作为空气入口，获得仿肺泡双层纳微纤维膜光催化剂；
所述仿肺泡双层纳微纤维膜光催化剂由亲疏不对称的双层纳微纤维膜组成，并且呈现出类似肺泡结构的中空袋状结构；所述光催化剂为二氧化钛、石墨相氮化碳中的任意一种；所述光敏剂为金属酞菁、金属卟啉中的任意一种。
2.根据权利要求1所述的仿肺泡双层纳微纤维膜光催化剂的制备方法，其特征在于，所述的静电纺丝参数为：电压15-30kV，接收装置与喷丝口距离10-30cm，挤出速率为0.5-2mL/h，温度20-30℃，相对湿度25-50％。
3.根据权利要求1所述的仿肺泡双层纳微纤维膜光催化剂的制备方法，其特征在于，所述金属酞菁或金属卟啉中的金属元素是铁、铜、钴、锌中的任意一种。
4.一种根据权利要求1所述的方法制备得到的仿肺泡双层纳微纤维膜光催化剂，其特征在于，所述疏水层聚苯乙烯纳微纤维膜的厚度为300-600μm，纤维直径为0.8-1.5μm。
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