BiOX催化剂的计算设计、可控合成及其对饮用水中内分泌干扰物的光催化降解研究

Natural water environments today are threatened by a variety of hazardous chemical substances derived from man-made products. Various contaminants such as azo dyes and organochlorine and aromatic hydrocarbons have been.detected, and a number of these chemical components are suspected endocrine disrupting chemicals (EDCs). It has been argued that EDCs are related to a number of reproductive and sexual abnormalities seen in wildlife and sperm counts decline in males. .To have their danger reduce to minimum, we will synthesize facet-controlled BiOX (X=Cl,Br,I) microspheres with nanosheets-assembly, as a promising and efficient method for the further improvement of the catalytic performance. In this work, we will investigate the structural and electronic properties of BiOX facets by the periodic density functional theory (DFT) method employing a slab model, and then synthesized BiOX via controlled synthesis, and using experimental approaches, we demonstrated that the catalytic activity of BiOX (X=Cl,Br,I) is facet-dependent,. To the best of our knowledge, this is the first report on directed morphological and facet-controlled synthesis of BiOX (X=Cl,Br,I) microspheres, with nanoparticles- assembly, nanorods-assembly or nanosheets-assembly. The experimental results of the present study show that single crystal BiOX (X=Cl,Br,I) with exposed highly reactive facets can be endocrine disrupting chemicals, For example, Bisphenol A and 17 -β estradiol, photocatalytic degradation and TOC will be investigated, their intermediates will be formed during photocatalytic degradation, and their evolution will be discussed. On the basis of the evidence of oxidative intermediate formation, a detailed degradation pathway of BPA degradation by BiOX (X=Cl,Br,I) microspheres photocatalysts will be proposed.

环境内分泌干扰物是全球被公认的第三大环境污染问题，这些有机污染物的矿化去除一直是困扰环境科学家的难题。本课题申请借助第一性原理计算和分子动力学模拟的方法研究3D BiOX(X=Cl,Br,I)光降解催化剂的催化晶面，在此指导下，采用溶剂热方法控制合成沿择优催化晶面生长的纳米粒子﹑纳米棒（线）﹑纳米片等低维纳米材料组装的3D BiOX微米球光降解催化剂材料，研究它们的合成工艺﹑探索其合成机理，评估它们在可见光光照下，催化降解内分泌干扰物质雌二醇和双酚A的效果和雌激素活性变化。该技术将推动非均相BiOX在可见光下催化的应用和发展，为同类环境内分泌干扰物的去除提供理论方法和实验基础，为降低和评价我国饮用水源水中环境内分泌干扰物质对人和生物体健康威胁提供一项有效的处理技术，具有一定的理论研究价值和实际应用前景。

本课题是在材料计算模拟与实验相结合的基础上研究无机纳米材料在光催化讲解中的应用。在材料计算中将密度泛函理论和含时密度泛函理论计算与分子动力学模拟相结合，用于材料的几何优化和物理化学性能研究，将材料设计的理念和方法应用到光降解催化材料的可控合成中，有助于深入有机物的吸附、催化降解过程等理论问题，并紧密结合实验，将建立起材料微观原子和电子结构与光降解催化效率之间的联系，知道未来高性能光降解催化材料的研究和开发。因此，借助第一性原理计算和分子动力学模拟的方法，本课题研究计算BiOX（X=Cl, Br, I）光降解催化剂的催化晶面，并采用溶剂热方法控制合成沿优化催化晶面生长的纳米粒子、纳米棒（线）、纳米片等低维度等纳米材料组装的3D BiOX 微米球新型光降解催化剂材料，研究它们的合成工艺、探索合成机理，评估3D BiOX在可见光光照下，催化降解双酚A的效果，同时在现有高效液相等分析仪器的检测限下，分析提出光降解机理，进而实现光降解催化剂与饮用水本体快速、有效分离。该技术将推动高效能非均相介孔光降解催化剂在可见光下催化的应用和发展，由理论计算知道可控合成高性能催化材料提供有效的实验基础，为同类环境内分泌干扰物的去除提供理论方法和实验基础，为降低和评价我国饮用水水源中环境内分泌干扰物对人和生物体健康威胁提供一项有效的处理技术，具有理论研究价值和实际应用前景。