多酸/石墨烯Fenton降解环境激素类有机污染物机理研究

Polyoxometalates (POMs) are a kind of solid metal-oxygen clusters with definite components and structure, which are widely applied in acidic and oxidative catalysis. It is a challenge and development that enhancement of their catalytic properties and enlargement of their catalytic field using super-molecular designing theory. This project aims at the scientific problems and research difficulties in degradation of phenol pollutants, using oxidative graphene(GO) supports to design and synthesize a series of POMs/GO complexes with different components, structure, high redox property, which could act as Fenton-like agents.Through some chemical characterization, the rule of the interaction beteen POMs and GO, catalysts and intermidiates, reaction mechanism could be given. This kind of POMs/GO hybrids could exhibit properties such as higher stability, higher efficiency, good selectivity, reusability, and environmental benign, which could catalyze the oxidative degradation of endocrine disrupting chemicals (EDCs) by H2O2. The project focus on the study of catalytic activity, reaction mechanism and dynamic model in catalytic degradation reactions.The unique property of these POMs/GOs is that the easy regeneration and reued process without significant loss of catalytic activity. It is meaningful for development a new POM oxdative catalysis in Fenton-like reaction, providing methods to degradation of EDCs waste water in industrial fields.

针对日益严重的天然水体污染（特别是环境激素污染）问题，本项目提出采用自主设计合成多酸/石墨烯复合物（POMs/GO），Fenton法实现饮用水源中典型环境激素类有机污染物的有效降解。优化制备技术，得到高氧化还原催化能力、高有机底物的富集能力的POMs/GO材料；通过两种典型环境激素邻苯二甲酸甲酯和双酚A的降解反应来考察复合催化剂的Fenton活性，研究各因素对多酸/石墨烯Fenton活性影响及其催化降解环境激素类有机污染物的作用机理，建立其动力学模型。该复合催化剂的显著优点是针对低浓度环境激素、催化活性高、降解完全，不需分离回收步骤，具有实际应用价值。本研究可为POMs/GO较大规模下的实际应用提供基础数据。

随着化学工业的高速发展，大量的有机化学品被应用到农药、合成树脂、化肥、农药、油漆、纺织品及橡胶等多种化工产品的生产中，产生很多毒性大、生物稳定的有机污染物，其中“环境激素” （endocrine disrupting chemicals，EDCs）对人类的繁衍和健康产生巨大威胁，已被列为与臭氧层破坏、温室效应共存的又一全球性的重大问题。典型的环境激素邻苯二甲酸酯（PAEs）分子中带有稳定的苯环，化学结构稳定难降解、且毒性强、潜伏期长、环境滞留性高，是一类持久性有机污染物(POPs)。本项目按计划完成了多种多酸复合材料包括多酸（POMs，H5PMo10V2O40）/石墨烯复合物催化剂H5PMo10V2O40@lipid(n)/GO-f、双亲型多酸催化剂[C16H33N(CH3)3]nH5-nPMo10V2O40 ((CTA)nH5-nPMoV，n = 1 ~ 5)、Lewis/Redox型多酸催化剂AgnH5-nPMoV （n = 1 ~ 5)和C16PW(O2)2/PNIPAM的设计合成，利用H2O2为氧化剂，考察了四种具有不同活性位点的POMs基材料对实验室配水和实际污水中PAEs类污染物的降解性能，研究四种多酸复合材料催化H2O2作用机理及催化反应路径，揭示了水中PAEs降解的可能降解路径以及POMs基材料对不同环境污水中PAEs去除的普遍性，开发基于多酸的类Fenton替代剂。.项目以H5PMo10V2O40为催化活性中心，并对其进行功能化，设计合成了四种不同性质的非均相型多酸基PAEs降解材料，实现了实验室配水以及生活污水中PAEs较高效率的去除，不同PAEs的去除效率可以达到90% 以上、TOC和COD的去除在70%以上，有效地降低了二级出水中PAEs的浓度以及水中PAEs类污染物造成的生态风险。同时催化剂均可回收使用，解决了均相材料回收困难、难以循环利用、处理成本高等问题。得到基于多酸的复合材料，完成富集、水解、氧化、有效地用于不同水环境中PAEs类污染物的高效去除，提高出水水质，降低生态风险。