N掺杂石墨烯水凝胶负载聚苯胺@ Ag/AgnX纳米阵列的构筑及其吸附、协同可见光催化作用研究

The technology of visible-light photocatalysis to remove the pollutants in an environmentally friendly manner, either in water or air, has been attracted extensive attentions. Aiming at the complex composition in actual wastewater and polluted air, polyaniline@Ag/AgnX nanoarrays on N-doped graphene hydrogels would be fabricated in this project, for efficient absorption and visible-light photocatalytic degradation of many different pollutants. The strategy is mainly based on the structures, properties, and their application characteristics in the adsorption and catalysis of graphene hydrogels and one-dimensional polyaniline nanoarrays, respectively, and also on the advantages of visible light response of Ag/AgnX heterojunction photocatalytic materials. The mineralization ability and reusability are evaluated by degradation of pollutants under the visible-light irradiation. The relationship between the three factors, i.e. the weight ration of graphene hydrogels, polyaniline and Ag/AgnX during the synthesis process, the macro-/micro-scopic structures of prepared complex, and the activities of adsorption-photocatalysis, is also explored. Photoelectriochemical experiments, electron spin resonance techniques, photoluminescence spectra, free radical and hole scavenging experiments and analysis of intermediates are employed to investigate the possible charge processes and the pathway for the photocatalytic activity enhancement mechanism under visible light irradiation. Meanwhile, the possible degradation pathways that as-prepared photocatalysts act on different pollutants are also proposed. The efficient exploration of such a project as this would provide theoretical basis and technical support for the further development of new and highly efficient visible light catalyst.

可见光响应的光催化技术是目前污水和空气净化领域中的研究热点。本项目针对实际污染源种类较多、成分复杂等问题，基于石墨烯水凝胶和一维聚苯胺的结构和性能，以及分别在吸附和光催化领域的应用特点，结合异质结光催化材料Ag/AgnX的可见光响应优点，构筑N掺杂石墨烯水凝胶负载的聚苯胺@ Ag/AgnX纳米阵列，以期实现对多种污染物的高效吸附和协同可见光催化降解，同时考察复合材料对污染物的矿化和循环使用情况，探索石墨烯水凝胶、聚苯胺和Ag/AgnX三者的质量比、复合物的宏/微观结构与吸附-光催化降解性能之间的关系，并通过光电化学实验、电子自旋共振技术、荧光光谱、自由基及空穴捕获实验和中间产物分析实验，获得可见光照射下石墨烯水凝胶和聚苯胺阵列对Ag/AgnX催化降解不同污染物的协同增强机理和光生载流子的传输方向，揭示复合材料对污染物的降解路径，为进一步开发新型高效的可见光催化剂提供理论基础和技术支持。

可见光响应的光催化技术是目前污水和空气净化领域中的研究热点。本项目针对实际污染源种类较多、成分复杂等问题，基于石墨烯水凝胶和一维聚苯胺的结构和性能，以及分别在吸附和光催化领域的应用特点，结合异质结光催化材料Ag/AgnX的可见光响应优点，构筑N掺杂石墨烯水凝胶负载的聚苯胺@ Ag/AgnX纳米阵列，以期实现对多种污染物的高效吸附和协同可见光催化降解的目的。主要研究内容如下：（1）基于三维石墨烯水凝胶（3D-GH）的三维网状多孔结构和优异的导电及离子扩散性能，构筑了可循环用于吸附和光催化降解水中阴/阳离子型芳香染料的3D Ag/Ag@Ag3PO4/GA和3D Ag3PO4/BiPO4/GA复合材料;（2）表面垂直生长有一维PANI的二维碳材料可以为催化剂提供高的比表面积和丰富的电子传递通道，同时基于Ag/AgCl的可见光响应优点和具有的拉曼增强活性，构筑了3D石墨烯水凝胶负载PANI/Ag@AgCl的复合材料（3D GH/PANI/Ag@AgCl）、Fe3O4@C/PANI/Ag@AgCl和碳布（CC）/PANI负载的Ag@AgCl复合材料（CC/PANI/Ag@AgCl）;（3）针对水中含有的重金属离子和苯环类有机微污染物的同时富集、拉曼检测和去除，设计合成了三个贵金属、Ag@AgCl、Ag@Ag3PO4等分别修饰的磁性/石墨烯复合纳米材料体系;（4）制备了用于催化、原位SERS监测污染物的聚苯胺复合纤维。结果表明在二维石墨烯或者三维石墨烯水凝胶的表面以及耐酸、耐碱、高机械强度的导电碳布上生长出均匀的大面积的不同质子酸HnX掺杂的PANI纳米阵列，并使纳米片阵列的生长方向垂直于碳材料的表面，已经通过一系列光电化学实验证明是银基光降解催化剂的良好载体，可以实现对多种污染物的高效吸附、拉曼检测和协同可见光催化降解的目的。. 本项目在国内外核心以上期刊已发表研究论文5篇，在投SCI期刊论文4篇，撰写中2篇；已授权专利三项；参加国际和国内学术会议两次,并以此基金为契机，成功开展了和企业的产学研合作，并申请获得了河南省教育厅科技成果一等奖和河南省科技进步二等奖，同时在项目执行过程中，培养5名相关专业专长的硕士研究生，项目负责人也前往澳大利亚格里菲斯大学进行了为期10个月的访问交流。