角蛋白自组装交联策略制备羽毛炭基吸附-光催化材料并应用于高浓度制药废水深度治理

This project focuses on the deeply treating of the pharmaceutical industry wastewater with high concentration, high toxicity, and the various types. The strategy to prepare the novel adsorbent/photocatalyst is investigated. In this project, based on renewable idea, a high specific surface graphene-like activated carbon is prepared from the waste poultry feather, and tantalates with high edge potential are selected as photocatalyst. According to the abundant keratins and disulfide bonds in the feather litter, tantalate is uniformly embedded in biochar grid by the strategies of self-assembly cross linking, biochar hydrothermal preparation, and high temperature activation. Meanwhile, nitrogen is also doped into carbon grid. Thus photocatalyst/feather biochar possess the highly redox ability, excellent absorption performance, well stability, and visible light responsive. We will build a green technological route for the preparation of the crosslinked semiconductor. Also we will investigate the methods about the controlled morphology and the surface modification. We will explore the mechanical model to improve synergistically the light adsorption ability, photocatalytic activity, and reusable stability. The competitive adsorption and degradation mechanism of pharmaceutical residues will be proposed. The prepared materials will be applied to the pretreatment of high concentration pharmaceutical sewage outlet through the simple transformation facilities. The concentration of antibiotics will be larger decreased to match with the level of the reliability and safety of drainage water treatment engineering. The results from this project provide valuable data accumulation and application demonstration for the administration of the industry wastewater in the field of the fine chemicals in Inner Mongolia Region.

本项目聚焦于高浓度、多种类残留物制药外排废水，研究自组装交联方法制备高效吸附-光催化材料。基于可再生思想，采用废弃家禽羽毛制备高比表面类石墨烯活性炭为广谱、强效吸附剂，光催化剂选用具有较高带边势的钽酸盐。依据家禽羽毛的结构和组成特点，利用羽毛中大量角蛋白和丰富二硫键，通过自组装交联、生物炭水热制备、高温活化等技术相互融合，将钽酸盐均匀镶嵌于羽毛活性炭网架并同时实现氮掺杂，制备出光催化剂/羽毛活性炭复合材料，在成本、可见光响应、氧化还原能力、再循环利用等综合性能提升方面有所突破。获得交联的最佳工艺、控制形貌和表面修饰方法；提出药物分子竞争吸附和降解机理；探讨吸附、光催化和稳定性协同促进的理论模型；并在试点制药企业已有设施上进行简单改造，应用于制药厂高浓度外排废水的预处理，有效降低污水出口抗生素的浓度；本研究成果为内蒙古面临形势严峻的精细化工水环境污染治理提供有价值的数据积累和应用示范。

本项目聚焦制药外排废水的残留，研制高效吸附-光催化脱污材料。在这个项目中，1）应用废弃羽毛、秸秆等制备了系列可应用于吸附抗生素残留的生物质炭吸附材料，进一步将光催化剂拟合在制备的生物炭材料上，并应用于工业废水中高浓度抗生素降解及光再生；2）制备了系列新型异质结光催化材料，对单一抗生素、混合抗生素以及模拟废水等研究了其光催化降解抗生素反应活性和稳定性；3）采用密度泛函理论结合原位光谱方法（LCMS\IR-DRIFT等）对催化分解抗生素的降解路径以及光吸收、光催化和稳定性的协同促进机理进行了研究；4）制备净化大气中VOCs 的光催化剂，探索了光催化分解气体有机物（甲醛、苯等）的活性及作用机理。本项目已经获得前改性生物炭、超声前改性生物炭和微波辅助前改性生物炭制备工艺，并已制备出高活性生物炭材料3种（羽毛、秸秆、蒲棒），制备出高活性生物炭吸附-光再生材料3种（TiO2/羽毛生物炭、SnS2/羽毛生物炭、CdS/碳材料），制备出高效光催化材料16种，包括H3PW12O40/K4Nb6O17、Ag3PO4/Bi2MoO6、Bi2O3-Bi3TaO7、BiVO4/Bi3TaO7、Ag3VO4/mpg-C3N4、BiOCl-CdS、Sn2Ta2O7/SnO2、CdS/NH4V4O10、Cu2O/Cu/SrTiO3、Ag/MxH2-xTa2O6(M=H，Li，Na，K，Sr) 、Cu2O@CeO2、Ag/Ag3PO4/CeO2、Ag2Ta4O11/Ag8(Nb0.5Ta0.5)26O69、 Bi2MoO6/Bi/g-C3N4、Bi2MoO6/Bi/g-C3N4、CsPbBr3/CsPb2Br5，通过对药物分子污染物的降解实验证明这些材料在应用于降解四环素、阿莫西林以及硝基芳烃等药物中间体残留过程中具有高氧化还原活性、高量子效率、可见光响应以及高稳定性。而且获得了药物分子竞争吸附和降解机理，提出吸附、光催化和稳定性协同促进的机理和理论模型；项目研究成果已发表SCI 收录论文27篇，其中1区论文12篇，获授权专利3项。本课题组成员（含学生）参加学术会议共15人次，其中会议报告和会议论文10人次(邀请报告3次)，参与组织学术会议2次。本项目培养博士研究生4人，硕士研究生15人。本研究对内蒙古面临形势严峻的精细化工水环境污染治理具有重要意义，提供有价值的数据积累和应用示范。