锆基金属有机骨架材料/活性碳纤维复合材料的制备及其降解性能  

Preparation of zirconium-based organic framework material/activated carbon fiber composites and their degradation properties

作　　者：刘其霞[1,2] 张天昊 季涛[1,2] 葛建龙 单浩如 LIU Qixia;ZHANG Tianhao;JI Tao;GE Jianlong;SHAN Haoru(School of Textile and Clothing,Nantong University,Nantong,Jiangsu226019,China;National&Local Joint Engineering Research Center of Technical Fiber Composites for Safety and Protection,Nantong University,Nantong,Jiangsu226019,China)

机构地区：[1]南通大学纺织服装学院,江苏南通226019 [2]南通大学安全防护用特种纤维复合材料研发国家地方联合工程研究中心,江苏南通226019

出　　处：《纺织学报》2023年第9期134-143,共10页Journal of Textile Research

基　　金：国家自然科学基金青年项目(52003126,52003125);江苏省研究生科研与实践创新计划项目(KYCX22_3351);南通市面上项目(MS22022029);江苏省科技厅基础研究计划(自然科学基金)青年基金项目(BK20200967;BK20200968)。

摘　　要：为改善活性碳材料在芥子气防护过程中存在的吸附易饱和、处置不当易造成二次污染等问题,制备了一种以活性碳纤维(ACF)为基材的新型降解材料。首先利用抽滤法将纳米锆溶胶沉积到ACF表面,随后采用层层自组装法,以ZrCl 4为金属簇、对苯二甲酸为有机配体,在纤维表面原位生长锆基金属有机骨架材料(Zr-MOF),最终制备出一种对芥子气模拟剂2-氯乙基乙基硫醚(CEES)有较高降解性能的Zr-MOF/ACF复合材料,综合采用扫描电子显微镜、X射线衍射、比表面积及孔结构分析等手段进行表征,并测试了其对CEES的降解性能和力学性能。结果表明:锆溶胶的引入有效提高了Zr-MOF在ACF表面的负载量,从而提升了所得材料对CEES的降解性能,并且力学性能也获得显著提高;综合考虑样品的降解性能、拉伸强度与制备效率,将经锆溶胶处理后进行15次循环处理的样品定为最佳工艺样品,经过24 h反应后,对CEES的降解率为83.08%,断裂强度为0.40 MPa,相比于酸化处理的活性碳纤维毡,复合材料的拉伸强度提升了80.99%。Objective Mustard gas,as a typical and widely-used chemical warfare agent,poses serious damage to human beings and ecosystem ascribing to their high toxicity and fast-diffusion.How to effectively protect against these hazards is the focus and challenge of the current research.Carbon-based materials,especially activated carbon fibers,have been applied for producing breathable chemical protective clothes,benefitting from their high adsorption capacity,fast adsorption rate,and extensive sources.However,the removal of toxic chemical agents by activated carbon fibers is mainly based on the physical-adsorption process,which is easy to reach adsorption saturation and cause secondary pollutions.Endowing the existing activated carbon fibers with high-efficient catalytic performance against chemical agents seems an effective route to tackle this problem.Method The commercial activated carbon fibers were first cleaned and then deposited with zirconia sol through suction filtration at ambient temperature.Subsequently,the preprocessed activated carbon fibers(ACF)were sequentially immersed into ZrCl 4 and terephthalic acid solutions at 130℃for 15 min to enable the layer-by-layer growth of zirconia-based metal-organic frameworks(Zr-MOF)on the fiber surface.Different consecutive cycles(3,6,9,12,15,18 and 21)were performed to prepare various Zr-MOF/ACF composites using the similar procedure.The surface morphologies and micro-structures of the resultant fibrous composites were characterized using scanning electron microscopy(SEM),X-ray diffraction(XRD),and chemisorption-physisorption analysis.Moreover,the degradation and mechanical properties of the composites were tested.Result It was found that a layer of microscopic zirconium nanoparticles was uniformly loaded on the surface of activated carbon fibers after pre-treated using zirconia sol.After the subsequent layer-by-layer assembly process,the synthesized Zr-MOF particles were loaded onto the fiber surface,and amount of loading was proportional with cyclic number(Fig.3).By co

关 键 词：锆基金属有机骨架材料 层层自组装法 2-氯乙基乙基硫醚 活性碳纤维 化学战剂 

分 类 号：TJ92[兵器科学与技术—武器系统与运用工程] TS156[轻工技术与工程—纺织材料与纺织品设计]