高级氧化体系对水环境中内分泌干扰物动态降解的研究

本研究是基于国家自然科学基金的研究课题，为我国新兴污染物的防治而进行的基础研究。选取具有生物毒性的双酚A（BPA）、阿特拉津（ATZ）等内分泌干扰物（EDCs）作为研究对象，将过一硫酸盐（PMS）催化氧化与光催化技术耦合联用，构建了太阳光/催化剂/PMS反应体系以快速降解EDCs。

通过不同的合成方法得到三种吸附性能好、催化性能依次增强的多元金属氢氧化物（Layered double hydroxides, LDHs）基催化剂，通过XRD、XPS、UV-Vis DRS等标准表征技术测试了它们的结构和性质，通过降解实验研究了太阳光/催化剂/PMS反应体系对模拟废水中EDCs的降解效率，研究了影响该体系降解效率的因素，通过ESR和掩蔽实验探究了反应体系的降解机理，结合污水处理厂二沉池出水配制的模拟废水，测试了反应体系在污水三级处理过程中的适用性。

对于CuMnFe LDHs催化剂，当Cu:Mn:Fe摩尔比为0.355:0.355:0.290时，催化剂具有最佳的吸附和催化性能，此时太阳光/催化剂/PMS反应体系可在15 min时去除93.5%的BPA。研究发现Cl^-和碱性条件可增强反应体系降解BPA的能力，而H₂PO₄^-、NO₃^-、HCO₃^-和酸性条件会降低反应体系降解BPA的能力。在该反应体系中作用最强的活性基团是光生空穴（h⁺）和超氧自由基（O₂^·-）：PMS掠夺电子促进了h⁺的产生；而LDHs的过渡金属元素与PMS形成的稳定中间体，会掠夺其他PMS分子的电子进而激发产生O₂^·-。

将CuMnFe LDHs与BiFeO₃以1:1的质量比复合，得到了0D/2D负载结构的复合催化剂。此时太阳光/催化剂/PMS反应体系可在15 min内降解99.3%的BPA，Cl^-、NO₃^-、HCO₃^-和碱性条件促进BPA降解，而酸性条件或H₂PO₄^-抑制BPA降解。反应中活性基团的作用强弱依次为：h⁺ > O₂^·- > ¹O₂ > SO₄^·- > ·OH，其中SO₄^·-和¹O₂仅在有光照的条件大量产生。

最后，通过共煅烧法合成了具有2D/2D结构的具有极强的催化性能的1:2LDOs-C₃N₄催化剂，应用此催化剂的太阳光/催化剂/PMS反应体系可在15 min内降解99.6%的难降解有机物ATZ，并对BPA、盐酸四环素、苯酚等多种污染物均具有良好的去除效果。Cl^-、NO₃^-和碱性条件会促进污染物的降解，而H₂PO₄^-、HCO₃^-和酸性条件抑制降解反应。反应体系中作用最强的·OH可由太阳光催化、PMS激发、太阳光/催化剂/PMS协同等多途径产生。

This fundamental study is supported by the national natural science foundation of China, which aims for the prevention and control of emerging pollutants in the aqueous environment of China. Chosen pollutants, including bisphenol A (BPA) and atrazine (ATZ) are both environmental endocrine disrupting chemicals (EDCs), which are potentially harmful for organisms. In this study, peroxymonosulfate (PMS) based advanced oxidation and photocatalysis are coupled to be the sunlight/catalyst/PMS reaction system, which could realize the rapid degradation of EDCs.

In this study, three kinds of layered double hydroxides (LDHs) catalysts with sequentially enhanced catalytic performance are synthesized through various synthetic methods. XRD, XPS, UV-Vis DRS and other characterizations are carried out to analyze the structure and property. The degradation efficiency of sunlight/catalyst/PMS system on EDCs are studied and the influencing factors are explored. The mechanism is also investigated through ESR and radical quenching experiment. Finally, the applicability of the reaction system in advanced wastewater treatment is tested using the EDCs solution prepared with secondary effluent.

When the molar ratio of Cu:Mn:Fe is 0.355:0.355:0.290, CuMnFe LDHs performs best as a catalyst, and the sunlight/catalyst/PMS system could remove 93.5% BPA within 15 min. The efficiency decreases with increasing acidity, H₂PO₄^-, NO₃^- and HCO₃^-, while Cl^- and alkalinity promote the degradation of BPA. O₂^·- and h⁺ contribute the most to the degradation of BPA. h⁺ is caused by photoelectrochemical separation and accelerated by HSO₅^-. The intermediate, which is formed by the transition metal and PMS, will capture the electrons of HSO₅^- and then produce O₂^·-.

When the mass ratio is 1:1, CuMnFe LDHs and BiFeO₃ are combined to form the 0D/2D loaded composition. The degradation rate of BPA could reach 99.3% within 15 min by the sunlight/catalyst/PMS system. The degradation reaction is accelerated by Cl^-, NO₃^-, HCO₃^- and alkalinity, but the reaction is inhibited by H₂PO₄^- or in acidic conditions. The radicals’ performance in this system is following the order: h⁺>O₂^·->¹O₂>SO₄^·->·OH, and SO₄^·- and ¹O₂ can only be produced under solar light.

The 2D/2D lamellar supported 1:2LDOs-C₃N₄ is formed by co-calcination, which perform strong in catalytic ability. The degradation rate of ATZ (refractory organic pollutant) could reach 99.3% within 15 min by the sunlight/catalyst/PMS system. BPA, tetracycline hydrochloride and phenol can also be decomposed by this system. Cl^-, NO₃^- and alkalinity could accelerate the degradation, while the reaction will be inhibited by H₂PO₄^- and HCO₃^-, and under acidic conditions. ·OH performs most powerfully, which has a variety of pathways to generate, including photocatalysis, PMS excitation, and solar light/catalyst/PMS coordination.

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