治理水中环境内分泌干扰物的仿生分子印迹光催化剂的制备及其性质研究

The bad effects of Endocrine Disrupting Chemicals (EDCs) to human health and environment are concerned by the whole society. How to remove EDCs, which is in low concentration and with high toxicity, from environment especially from water has become a hotpot and difficulty in environmental management. Recently, molecular imprinted photocatalysts, which can degrade EDCs with high selectivity, have received extensive attention. To obtain the molecular imprinted photocatalysts, the surface of TiO2 was usually coated with organic molecular imprinted polymers (MIP). Under a long period of UV-light illumination, these organic polymers can be oxidized easily by photo-generated reactive OH? radicals and may cause the instability of the materials. In this project, a bionic inorganic molecular imprinted TiO2 phoyocatalyst, which is of high stability and selectivity for photocatalytic degradation of trace EDCs, will be developed. The porous TiO2 phoyocatalyst will be prepared with biological template and inorganic molecular imprinting technique. Meanwhile, transition metals which have strong interaction with EDCs molecules will be doped into the TiO2 photocatalyst. The transition metals will help to broaden the absorbance spectrum range of the photocalyst as well as to develop synergistic selectivity effect on EDCs molecules. Therefore, doping transition metals will be benefit for increasing both photocatalytic efficiency and selectivity. The application of the catalyst will also be investigated in this project. The prepared photocatalyst will be applied to degrade the EDCs in the model pollution system. The relationship between chemical composition, microstructure and the property of selective degradation will be studied carefully. Emphasis will be put on investigating and concluding the general law of design and synthesis of the inorganic molecular imprinted photocatalyst for degrading EDCs and proving up the selective photocatalysis mechanism. Research in this project would has significant theoretical value and good application prospect.

环境中高毒性低浓度的环境内分泌干扰物（EDCs）对人类健康和生态环境带来极大危害，已成为环境治理的热点和难点。分子印迹光催化剂是近期发展的一种高选择性催化降解EDCs的材料,其普遍采用TiO2与表面有机印迹聚合物层结合而得到，但有机印迹聚合物层易于被光催化产生的羟基自由基氧化而使材料的稳定性不高，使用寿命不长。本研究将仿生制备全无机型分子印迹TiO2光催化材料，使其对EDCs的光催化降解具有高选择性，且材料具有高稳定性。拟采用生物模板法，结合分子印迹技术及金属掺杂，制备出性能优越的全无机型多孔印迹二氧化钛选择性光催化剂，并将其应用于治理环境内分泌干扰物的模拟污染体系中，考察其化学组成及微观结构与选择性光催化降解性能之间的关系，重点研究和总结具有普适性的全无机型分子印迹光催化剂的设计和制备规律，探明其对EDCs选择性光催化降解的机理，具有重要的理论价值和应用前景。

环境内分泌干扰物污染问题是当前环境领域研究的热点之一，探索去除水体中内分泌干扰物的新技术具有重要意义。二氧化钛光催化降解污染物是绿色、环保、最有前途的深度处理技术之一。但由于二氧化钛比表面积小，由于表面羟基大量存在，对低浓度、强疏水性、高毒性的内分泌干扰物基本没有吸附能力。研究表明吸附对光催化过程非常重要，这是因为材料吸附污染物的速率要比光生电子-空穴复合率低一至几个数量级。如果污染物不能快速地迁移至催化剂表面，则不能充分利用光生电子和空穴，降解效率极低，且常有降解中间体生成，有可能产生二次污染的问题。针对这些问题，我们提出构筑具有吸附/光催化复合光催化剂。采用吸附/光催化协同作用去除的思路，制备了对环境内分泌干扰物有高效富集功能的仿生吸附剂，并进一步通过结合分子印迹技术、吸附剂与催化剂复合等方式，制备了一系列分子印迹TiO2光催化剂以及具有吸附/光催化活性的TiO2复合光催化剂，并应用于双酚A（BPA）、17-β-雌二醇（E2）和17α-乙炔基雌二醇（EE2）这3种环境内分泌干扰物的去除研究，可为其它内分泌干扰物和新型有机污染物的安全彻底去除提供有益的启发。另外，针对TiO2光催化剂对可见光利用效率低的问题，制备了系列铋系异质结光催化剂，实现了环境内分泌干扰物的可见光催化降解。