碳基量子点/类石墨烯结构FeOX（X=Cl，Br）材料的构筑及其光催化降解环境内分泌干扰物研究

This project focuses on the light Fenton oxidation technology in the treatment for environmental persistent endocrine disruptors. The iron-type metal-based functional ionic liquids are constructed by iron salts and halogen-containing ionic liquids. Employing the iron-type metal-based functional ionic liquids acted as direct reactant and template to control the synthesis of ultrathin iron oxyhalides nanosheets materials. Carbon-based quantum dots materials were controllable prepared by using graphite, melamine and glucose as precursors. The project designs a class of non-metallic functional ionic liquids which has good dispersion, intercalative exfoliation function and hydrogen-bonding combining function with carbon-based quantum dots. In order to obtain the carbon-based quantum dots/iron oxyhalides composites, this non-metallic functional ionic liquids as solvent for carbon-based quantum dots and ultrathin iron oxyhalides nanosheets will be employed, using sonic or electrochemically assisted exfoliating method which in situ controlled exfoliation of iron oxyhalides ultrathin nanosheets and coupling with carbon-based quantum dot at the same time. Such materials have a wide spectrum of absorption, high separation efficiency of the photo-generated charge carriers, the up-converted fluorescence and photo-Fenton catalytic functions, which could achieve efficient photocatalytic degradation of endocrine disruptors. The intrinsic relationship between the composition, structure, surface characteristic of the material and degradation activity of pollutant as well as the degradation kinetics model will be explored. The internal mechanism of degradation of endocrine disruptors by the composites will be revealed.

本项目是针对光芬顿催化氧化技术在环境持久性内分泌干扰物治理方面的研究。拟使用含铁无机盐与卤素离子液体构建铁型金属基功能化离子液体，并以该类离子液体为直接反应源和模板合成超薄卤氧化铁片状材料。同时以石墨，氰胺和葡萄糖等为前驱体制备碳基量子点材料，并设计一类具有良好的分散、插层剥离及与碳基量子点氢键结合功能的非金属功能化离子液体。以该类非金属功能化离子液体为超薄卤氧化铁纳米片材料与碳基量子点的反应介质，通过声波或电化学原位可控辅助剥离法实现卤氧化铁纳米片材料剥离，并同时使之与碳基量子点复合，得到碳基量子点/类石墨烯结构卤氧化铁复合光催化材料。该类材料具有宽光谱吸收、高载流子分离效率、上转换荧光及光芬顿催化等功能，能实现内分泌干扰物的高效光催化降解。深入研究材料组成、结构和表面性质与内分泌干扰物降解活性之间的内在关系，建立污染物降解的动力学模型。揭示复合材料降解内分泌干扰物的内在机理。

本课题研究主要围绕功能化离子液体体系中卤氧化物（MOX）材料的设计、可控制备及其光催化降解环境有机污染物的研究。主要运用表面缺陷、Z机制构筑、超薄层状结构调控、表面量子点修饰和异质结构建等策略来设计光催化材料。已成功制备出表面碳缺陷超薄g-C3N4纳米片、g-C3N4/FeOCl、g-C3N4/Bi4O5Br2、Bi4O5I2超薄纳米片、CPDs/PbBiO2Br和Bi/BiOCl复合材料。通过X射线衍射（XRD）、扫描电镜（SEM）、透射电镜（TEM）和比表面积测试（BET）等表征手段对所制备材料的结构与形貌进行了表征，并对其进行光催化性能探究。实验结果表明，所制备的材料均展现出较好的光催化活性，其中表面碳缺陷限域超薄g-C3N4纳米片、Bi4O5I2超薄纳米片、g-C3N4/FeOCl和g-C3N4/Bi4O5Br2复合材料在可见光照射的条件下对水体中有色染料如罗丹明B（RhB）有很好的光催化降解活性。同时g-C3N4/FeOCl复合材料对无色的水体污染物四环素（TC）具有很好的可见光光催化性能。Bi4O5I2超薄纳米片和g-C3N4/Bi4O5Br2复合材料对水体无色污染物环丙沙星（CIP）有很好的可见光光催化降解活性。此外，对比单体PbBiO2Br材料，CPDs/PbBiO2Br复合材料在光照条件下表现出显著增强的光催化二氧化碳还原活性。原位Bi自掺杂BiOCl复合材料在光电检测环丙沙星时有着较好的稳定性和宽线性范围。本课题通过采用多种调控策略，成功实现了高光催化性能的卤氧化物及其复合光催化剂的设计与可控制备。研究了不同策略制备的光催化剂的活性机理，并结合材料的结构与光催化活性结果，阐述了材料的构效关系。