新型POM/铁系MOFs/g-C3N4复合材料的制备及其光催化降解水体中有机污染物的效能研究

This project is aimed at the problems existing in currently photocatalytic treatment of persistent organic pollutants in water: low catalytic efficiency, poor stability and visible light absorption. By using Fe/Co/Ni-based MOFs as carriers of POMs, a new kind of photocatalyst materials based on POMs, Fe/Co/Ni-based MOFs and g-C3N4 will be synthesized and researched. The photocatalyst make full use of the advantages of physicochemical properties of each, namely, good absorption, conductivity and large specific surface area of layered g-C3N4; carriers of POMs, adsorption and enrichment of organic pollutants, synergistic catalysis from metal centre (Fe/Co/Ni) for Fe/Co/Ni-based MOFs; oxidative catalysis, photoactivity and POMs as electron "storage", which will greatly improve the separation and utilization of photogenerated electron and cavity, to reach perfect matching of structure and charge between “POMs-Fe/Co/Ni-based MOFs-g-C3N4”. The photocatalyst materials maybe exhibit high efficiency and good stability, and then are applied to the photocatalytic treatment of persistent organic pollutants. The forming mechanism, properties and the relationship between their structures and performance are deeply explored. The migration and transformation, the degradation mechanism of organic pollutants and adsorption-catalytic synergy effect in the photocatayltic process are also systemically studied. Significantly, this research will also provide new theoretical basis and technical support for the design and preparation of novel photocatalysts, and the application in actual wastewater treatment.

针对当前光催化处理水体中难降解有机污染物催化效率低、稳定性差及可见光利用率低等关键问题，本项目拟以铁系MOFs作为多酸载体，充分利用多酸、铁系MOFs与g-C3N4物化特性的优点，即层状g-C3N4良好光吸收、导电性和大的比表面积，铁系MOFs固载多酸、吸附富集有机污染物和金属中心(Fe/Co/Ni)的协同催化，多酸的氧化催化及电子“储存器”的特性，大大提高光生电子和空穴分离和利用率等，研制高效稳定的POM/铁系MOFs/g-C3N4复合材料，实现“多酸-铁系MOFs-g-C3N4”之间结构和电荷的有效匹配，并将其应用于难降解有机污染物的光催化处理。探索各种POMs/铁系MOFs/g-C3N4复合材料的形成机理，材料性能及构效关系；系统研究有机污染物在光催化降解过程中的迁移转化规律，降解机理和吸附-催化协同效应，为新型光催化剂的设计和制备以及在实际废水处理中的应用提供理论依据和技术支持。

针对当前光催化处理水体中难降解有机污染物催化效率低、稳定性差及可见光利用率低等关键问题，本项目以铁系MOFs作为多酸载体，充分利用多酸及铁系MOFs物化特性的优点，即：铁系MOFs固载多酸、吸附富集有机污染物和金属中心(Fe/Co/Ni)的协同催化，多酸的氧化催化及电子“储存器”的特性，从多例不同POMOFs出发（多酸分别位于MOF的孔道及节点），构建了PMo12@MIL-101-NH2活化PDS高效降解对氯苯酚(4-CP)体系，其在无外加能量的条件下，120 min内活化PDS通过非自由基的电子诱导过程降解4-CP的效率为98.95%；构建了Co4(2-mim)6MoO4·x(solvent) (HZIF-CoMo)及其衍生物Co/Mo2C@C活化PMS降解抗生素卡马西平（CBZ）体系，Co/Mo2C@C能在15min内去除99.27%的CBZ，从构效关系深入阐述其活化PMS过程中的活性物质由单一自由基途径转变为有非自由基参与的双途径的增效机制；为克服由于严重的离子浸出导致材料的不稳定性而改变项目计划策略，构建了以Anderson型多金属氧酸盐(NH4)3[Fe(III)Mo6O24H6]·6H2O作为前驱体的相关衍生物FeS/MoS2纳米花活化PMS高效降解4-氯苯酚体系及碳包裹铁掺杂碳化钼催化剂Fe-Mo2C@C活化PMS氧化降解苯酚体系，并探讨了材料组分间的协同活化途径及机理、催化剂稳定性等关键科学问题。此外，我们还展开了FeNi-MOFs用于过硫酸盐高级氧化PS-AOPs降解四环素TC及β-FeC2O4·2H2O活化分子氧产生的羟基自由基高效降解微囊藻毒素MC-LR等的研究；以及相关材料用于光催化水分解产氢和产双氧水等性能研究及电催化二氧化碳还原等的研究，为多功能材料的开发提供借鉴。.在期刊Applied Catalysis B: Environmental（3篇），Science Bulletin（1篇），Journal of Materials Chemistry A（1篇）, ACS EST Water（1 篇）等发表高影响因子SCI论文共6篇（IF ˃ 10），其他研究结果已整理成2-3篇文章待发表；受理中国发明专利6件，其中授权4件；共培养硕士研究生毕业5名，目前在读硕士研究生7名；项目执行期间荣获2021年江西省“青年井岗”人才称号；荣获202