宽pH响应下nZVI同步活化过硫酸盐/H2O2对水中双酚类污染物的降解研究

Recently, the water pollution caused by bisphenol chemicals (BPs) has attracted extensive attention all over the world for their great threat to water security and public healty. The endocrine disrupting effect of BPs would induce a series of endocrine diseases, such as infertility, diabetes, coronary heart and renal dysfunction, giving rise to heavy burden to ecoenvironment and society. .Thus, developing high-efficient technologies for BPs removal has become one of the top research aspects in water polllution remediation. The H2O2-based and persulfate-based advanced oxidation technologies can effectively degrade and minerlize these BPs pollutants as reported. However, they face the problems like requirement of acidic reaction pH and difficulty of activator regeneration, respectively. To resolve these problems, this project proposes to construct a dual oxidant system, in which H2O2 and persulfate are simultaneously activated using nanoscaled zerovalent iron (nZVI) as the activator. The BPs will be degraded and mineralized in a wide pH range under the synergistic effect between activated H2O2 and persulfate. The system optimization will be further conducted based on the co-activation of H2O2 and persulfate. In addition, the synchronous transformation of nZVI, generation of reactive radicals, BPs degradation intermediates under multiraicals and their biotoxity will be further investigated to elucidate the BPs degradation and mineralization mechanism by nZVI coactivated H2O2/PS. The obtained results of this project will provide theoretical guidance for the development of remediation technologies for BPs-contaminated water.

近年来，双酚类化合物(BPs)对环境水体污染而产生的水质安全和人体健康问题引起了国内外广泛关注，其所产生的内分泌干扰效应会诱发一系列内分泌相关疾病，如不孕不育、糖尿病、冠心病和肾功能缺陷等，给生态环境和经济社会带来沉重负担。由此聚焦的BPs高效去除是目前水污染修复的前沿研究之一。基于H2O2类芬顿或过硫酸盐(PS)的高级氧化技术可以有效降解BPs，但应用中分别存在反应需要强酸性环境和活化剂再生难等问题。为此，本项目以纳米零价铁nZVI为活化剂，构建同步活化PS和H2O2的双氧化体系，在宽pH响应下协同作用高效降解和矿化BPs。通过研究nZVI同步活化H2O2和PS氧化体系优化、nZVI同步转变过程、活性自由基激发路径以及BPs在多自由基作用下的降解路径和生物毒性变化，阐明nZVI同步活化H2O2/PS降解和矿化BPs的反应机制，为BPs污染水体修复技术的研发提供理论指导。

以双酚类污染物（BPs）为代表的内分泌干扰物是目前国内外广泛关注的一类新污染物，其主要来源是有毒有害化学物质的生产和使用。本项目探究了利用纳米零价铁和铁基催化剂同步活化过氧化氢和过硫酸盐生成活性自由基实现降解BPs的多自由基降解，阐明了过氧化氢和过硫酸盐同步催化活化的协同作用机理以及BPs多自由基的降解路径。项目主要取得以下进展：（1）基于构建nZVI同步活化PS和H2O2降解BPs的高级氧化体系，验证了PS和H2O2同步活化所激发的协同效应。相比于常规芬顿和类芬顿体系需在pH3的酸性条件下进行反应的弊端，nZVI同步活化PS和H2O2在初始pH为7的条件下也可以顺利进行，并充分利用了PS和H2O2两种氧化剂的优点。项目探明了nZVI同步活化PS和H2O2降解BPs的优化条件，并阐明了BPs氧化机理和多自由基作用下的降解路径。（2）研究了nZVI同PS和H2O2三者间的相互作用关系，通过硫改性调控nZVI材料活性位点，制备了硫化的nZVI，揭示了nZVI同步活化PS和H2O2过程中的限制性影响因素以及强化污染物降解的机制。（3）提出了草酸强化亚铁离子同步活化PS和H2O2降解BPs的类Fenton氧化体系，解决了传统Fenton氧化过程中Fe(II)利用效率低，投加量大且反应过程需在pH3-4区间的弊端。（4）提出了生物炭耦合原子铁的新型协同PS催化氧化反应体系，揭示了非自由基降解BPs的反应机制以及BPs的非自由基降解路径。项目总计发表SCI论文17篇，授权发明专利5项，培养硕博士研究生13人，获得湖北省科学技术进步奖二等奖一项（公示期）。