金属硫化物/金属有机框架异质结的微乳可控合成及其对废水中抗生素可见光催化降解的特性和机理研究

The novel visible light-responsive photocatalytic materials are of great scientific significance in solving the pollution problem of antibiotics in wastewater. The use of sulfide as a photocatalyst in the degradation of waste water has been studied, but no report has been shown in the use of heterojunction materials based on metal sulfide and metal organic framework for degradation of antibiotic wastewater. In this project, the microemulsion technology is planning to be used to synthesize the metal sulfide / metal organic framework heterojunction materials and regulate interface to improve the ability of antibiotics degradation in wastewater. The microstructure, chemical composition and properties of the photocatalytic materials were characterized, and the internal mechanism of microemulsion regulation was discussed. Further, metal sulfides/MOF composites photocatalyst properties, including adsorption behavior, photocatalytic activity and anti-photocorrosion, will be comprehensively studied for elucidating the intrinsic mechanism of photocatalytic degradation of antibiotics. The photocatalytic mechanism will be elucidated by combining the free radicals, the intermediate products, the dynamically degrade process in solid-solution interface, the degradation dynamics and the transient change of photocatalyst. Finally, a photocatalytic reactor based on metal sulfide/MOF photocatalyst will be designed and applied to treat the real wastewater. In this study, it is expected to solve the uncontrolled synthesis-structure-performance of photocatalyst and the reaction mechanism of antibiotic in water-solid-microinterface under visible light irradiation. In a word, this study will provide the theory basis and practicable methods for pollutants control.

新型可见光响应型光催化材料对解决废水中抗生素的污染问题具有重要的科学意义。利用硫化物作为光催化剂降解废水中的污染物已有研究，但未见使用金属硫化物与金属有机框架制成异质结材料降解废水中的抗生素。本项目采用微乳技术进行金属硫化物/金属有机框架异质结材料的合成及界面的调控，提高降解废水中抗生素的能力；表征该类光催化材料的微观结构、化学组成及性质的变化，探讨微乳调控内在机制；研究光催化剂对抗生素的吸附分配、可见光催化降解特性及光催化剂抗光腐蚀性能，结合抗生素降解动力学、光催化剂变化的瞬态过程及抗生素在固-液微界面转化的动态过程，阐明光催化降解抗生素的内在机理；设计基于该类复合光催化材料的光催化反应器并实现实际废水中抗生素的控制。本项目将解决复合光催化剂的可控合成-结构-性能和可见光条件下抗生素在水-固-微界面反应过程规律的问题，为高效可见光催化技术应用于实际水污染控制提供理论依据与实践方法。

本项目采用微乳法等可控合成了Sn0.215In0.38S/还原氧化石墨烯(SIS/RGO)复合材料和MoS2/Sb2S3复合材料、分层的微球状Zn2In2S5/Ti3C2(O,OH)x异质结、SnS2/MIL-(Fe)复合材料、In2S3/UiO-66复合材料、In2S3/ InVO4复合材料、AgI改性的UiO-66(NH2)、Sn-BiOBr/BiOIO3异质结等多种异质结复合材料，探索了表界/面调控机制。考察了Zn2In2S5/Ti3C2(O,OH)x异质结、In2S3/UiO-66复合材料和AgI改性的UiO-66(NH2)复合材料对水体中四环素的吸附/降解行为，研究了催化体系外部条件对光催化效率的影响，并探究了盐酸四环素在光催化剂表面和内部的降解行为，结合光生载流子转移与捕获及自由基的作用方式，降解中间产物及影响因素的动态追踪与分析，阐明了水中抗生素分子光催化降解与演变的内在机制。同时，探讨了硫修饰的Fe-MOF对废水中四环素的光催化降解行为机理和动力学过程，分析了微观结构的影响；考察了钛金属有机框架煅烧获得的不同晶型Ti3+和Ov掺杂的TiO2改性材料，对废水中四环素和金霉素的光催化行为、机理和动力学过程；并探讨了Sn-BiOBr/BiOIO3异质结对其废水中多种有机污染物的光催化降解效果，调查和量化Sn-BiOBr/BiOIO3的理化性质和光电性能，得到了光催化反应过程活性中心的动态形成过程，及其光催化反应微观机制。此外，本项目设计合成的多种异质结催化剂对自然水体中的抗生素进行了光催化去除，并探讨了实际水体的水质对光催化降解过程的影响。因此，本项目为高效复合光催化剂的可控合成及可见光条件下抗生素在水-固-微界面反应过程及规律揭示等提供了理论和实践指导。