柔性光催化防护材料的构筑及光催化降解化学毒剂机理研究

The development of functional fabrics has become a key research subject in today's textile technology. Aramid fabric has been widely used in petroleum chemical industry, fire protection, military and other fields based on its special characters, such as high temperature resistant, flame retardant, fire protection, etc. In order to widen the use of aramid fabric, the flexible protective composite material bismuth visible light catalyst/ polypyrrole/aramid fabric was constructed in this subject. The conductive polypyrrole was in situ polymerized onto the surface of aramid fabric, then the semiconductor bismuth visible light catalysts were self-assembled on polypyrrole by layer-by-layer method to prepare the flexible protective composite material. The conductivity of polypyrrole will improve the photocatalytic property of bismuth visible light catalysts, so the relationship of the conductivity and photocatlytic property will be studied in detail. The study of the photocatalytic degradation property of chemical agents of this composite material, and the realization of degradation the chemical agents under visible light will provide the possible use of the composite material for preparing chemical protective clothing. Because of the special toxicity of the chemical agents, the mimetic agents of the chemical agents will be used to study the photocatalytic degradation property of the composite material. The flame-retardant properties of the flexible material will also be studied. This flexible protective material with unique electrical and optical catalytic properties, clarify its conductive and photocatalytic relationships will provide theoretical basis for development of high-performance photocatalytic protective material, which has important academic value and theoretical significance.

研究开发功能纺织品，已成为当今纺织科技界的重点攻关课题。芳纶织物具有耐高温、阻燃、防火等特征，主要用于石油化工、消防、军队等领域。为了更好地发挥芳纶的优异性能，本课题以芳纶织物为载体，采用原位聚合法将导电聚吡咯整理到芳纶表面，再用层层自组装的方法将铋系可见光催化剂修饰到聚吡咯/芳纶导电织物上，构建铋系可见光催化剂/聚吡咯/芳纶柔性防护材料。聚吡咯良好的导电性能有助于提高光生电子和空穴的分离效率，从而提高光催化剂的催化活性；进一步研究外加电场是否有助于提高光催化活性。在研究过程中，采用与化学毒剂结构相似的化合物作为模拟剂，来研究其光催化性能及机理，实现在可见光下催化降解化学毒剂；并研究该柔性材料的阻燃性能。该材料具有独特的导电、阻燃和光催化性能，阐明其导电与光催化性能的关系，为研制光催化防化服提供基础，具有重要的学术价值和理论意义。

本项目首先利用层层离子吸附法（SILAR）在芳纶表面完成了不同自组装次数下BiOI纳米片的负载，组装20次（C-20）的复合材料在3 h内对于20 mg/L活性蓝KN-R的光催化降解可达90.7 %，在循环使用5次后，催化降解效率仍保持在80 %以上。为进一步提高光催化降解效率，利用原位聚合法将聚吡咯（PPy）整理在芳纶表面赋予织物导电性，当吡咯单体（Py），六水合三氯化铁和二水合磺基水杨酸钠的浓度均为0.36 mol/L时，在0 ℃反应36 h，可以获得方阻为5 Ω/sq的PPy/芳纶复合材料，具有良好的导电性能，能够快速分离光生电子和空穴，提高光催化剂的效率。以PPy/芳纶作为BiOI的载体，构建BiOI/PPy/芳纶体系，组装15次（P-15）可以获得最佳光催化性能的复合材料，在3 h内对20 mg/L活性蓝KN-R降解率达99 %以上，相比不含Ppy的C-20复合织物的光催化性能具有明显提升。. 在SILAR法基础上，基于染整常用的浸轧设备对传统SILAR法进行改进，开发了浸轧离子层吸附反应法，有效精简了SILAR法的步骤，适用于规模化推广应用。浸轧离子层吸附反应法具有较好的适用性，可在不同柔性织物（棉织物、涤纶、芳纶和聚吡咯@芳纶）表面负载碘氧化铋光催化剂，也可在柔性基材表面实现不同光催化剂的负载，赋予织物光催化降解有机污染物、抗菌、红外隐身和催化双氧水分解等多种性能。浸轧离子层吸附反应法所制备的BiOI-CF-P织物具有较好可见光催化活性，经过300 min光照射后，对溶液中罗丹明B的降解率达到90%以上。浸轧离子层吸附反应法可实现不同比例碘氧化铋与溴氧化铋光催化剂在棉织物表面的复合负载，制备了BiOBrxI1-x固溶体负载的BiOBrxI1-x-CF-P（0≤x≤1）多功能织物。该织物展现了良好的光催化降解织物表面有机污渍和有毒物质的能力，对毒剂模拟物农药异丙隆的降解率达到90%以上。因此，BiOBrxI1-x-CF-P有望作为多功能纺织品应用于自清洁和防护领域。. 本项目开发的浸轧离子层吸附反应法制备柔性光催化防护材料，为研制光催化防化服提供基础，具有重要的学术价值和理论意义。