缺陷调控设计高PMS活化性能MOFs基类芬顿光催化剂去除抗生素的研究

For the restrictions in activation performance of peroxymonosulfate because of the limited metal active sites in Fe-based MOFs Fenton-like photocatalysts and the potential risk of antibiotics pollution, this study establishes the degradation of wastewater containing multi-component beta lactam antibiotics as an application object, and proposes the in-situ growth of Fe base MOFs with high stability on the stainless steel wire, and will induce the formation of ligand vacancy defects through the combination of the heterogeneous mixed ligands, and then the preparation methods and technologies of novel Fe-based MOFs catalysts with high density of unsaturated metal active sites, high photocatalytic activity, high PMS activation efficiency and stable structure will be developed. Explore the influence of the defect structures of Fe-based MOFs on the stability, properties and catalytic properties of the as-prepared catalysts and the roles in the generation of sulfate radicals in Fenton-like reactions; investigate the key factors affecting the degradation and removal of multi-component antibiotic pollutants by new Fe-based MOFs Fenton-like photocatalysts and propose the optimal control strategy; illuminate the principle of degradation and removal technology of multi-component antibiotic system; reveal the internal synergetic mechanism between photocatalysis and Fenton-like interactions. The study could provide the theoretical basis and technical support for the construction and practical application of coupling advanced oxidation technology based on Fe-based MOFs for the degradation and removal of multi-component antibiotic pollutants in water.

针对Fe基MOFs类芬顿光催化剂中有限的金属活性位点限制过一硫酸盐(PMS)活化性能的技术障碍以及当前水体中抗生素污染的潜在风险，本研究以含β-内酰胺类多组分抗生素复杂体系废水的降解处理为应用对象，拟以不锈钢铁丝网为基底从制备原位生长的高稳定Fe基MOFs材料出发，通过异构混合配体策略诱导形成配体空缺缺陷，发展高密度金属活性位点、光催化活性高、PMS活化效率高且结构稳定的新型Fe基MOFs催化剂的制备方法和技术。探索Fe基MOFs的缺陷结构对其稳定性、性质及催化性能的影响规律，尤其对类芬顿催化效率的影响；研究影响新型Fe基MOFs催化剂降解去除水体中多组分抗生素的关键因素，提出体系优化调控策略；阐明多组分抗生素复杂体系废水的降解处理技术原理，揭示光催化-类芬顿相协同的内在联动机制，为构建高效的MOFs基耦合型高级氧化体系有效处理水体抗生素污染提供理论依据和技术支撑。

针对Fe基MOFs类芬顿光催化剂中有限的金属活性位点限制过硫酸盐活化性能的技术障碍以及当前水体中抗生素污染的潜在风险，项目构建了以缺陷型铁基MOF催化剂为核心的类芬顿-光催化降解体系，主要研究结果如下：（1）通过异构混合配体策略诱导形成配体空缺缺陷，发展出了高密度金属活性位点、光催化活性高、PMS活化效率高且结构稳定的新型Fe基MOFs催化剂的制备方法和技术；不饱和金属活性位点的增加提高了PS活化效率，在TCH降解性能提升过程中起重要作用，而缺陷结构的引入在一定程度上提高了光生载流子的分离效率，光催化和类芬顿的协同效应增强了体系对TCH的降解性能。（2）项目发展了Fe基MOFs复合粒料的绿色合成新方法，通过预混合机制促进成核位点形成，实现了致密有序MOF纳米晶在氧化铝颗粒表面的自组装生长，Fe基MOF负载率最低(约3wt%)的颗粒复合材料在60 min内对TCH的吸附效率(95%)高于活性氧化铝(51%)和Fe基MOF粉末(72%)，Fe基MOF晶体层与活性氧化铝载体之间的协同作用导致了颗粒状MOF复合材料优异的吸附性能。（3）项目针对抗生素饱和吸附的失效Fe基MOF吸附剂进行再生转化，开发了简便的一步热解法并制备出石墨烯基氮掺杂碳的高效杂化催化剂，通过PS活化及界面电子转移作用，对水体中抗生素污染物显示出了优异的降解去除性能，研究表明FexNC的铁物相和石墨烯结构有利于提高FexNC界面电子转移能力，非自由基1O2和O2•−以及表面电子转移的协同效应是TCH快速降解的主要原因。项目的研究结果为构建高效的MOFs基耦合型高级氧化体系有效处理水体抗生素污染提供了理论依据和技术支撑。