Zn2(Si,Ge)O4:Mn2+/Zn-MOFs异质结构的构筑及其双发射荧光传感机制研究

Construction of new dual-emission luminescence sensing materials with controllable morphology, high sensitivity and stable physical/chemical properties becomes one of the hot research topics in the field of inorganic functional materials. Based on the chemical coordinated bond effect of Zn atoms, this project proposed the design and synthesis of Zn2(Si,Ge)O4:Mn2+/Zn-based metal-organic frameworks (MOFs) heterostructure with dual-emission luminescence characteristic. The Zn2(Si,Ge)O4:Mn2+/Zn-MOFs heterostructure obtained is composed of inorganic micro/nano crystals showing high efficient emission and luminescence metal-organic framework with adjustable luminescent identification function. The heterostructure features controllable morphology and structure, high chemical and thermal stability, and high sensitivity. Screening of heterostructure with high luminescence efficiency, high anti-interference resistance, and specific luminescence responsibility of Zn2(Si,Ge)O4:Mn2+/Zn-MOFs can be developed as a dual-emission luminescent probe. This project will also try to clearly investigate the photochemical sensing and interaction mechanisms of the dual-emission heterostructure, and the principles on how to control the excitation states of different luminescent centers to achieve the ratiometric control of dual-emission sensitively will be also demonstrated. Furthermore, the project will try to investigate its potential applications in the field of ratiometric luminescence sensing of temperature and different heavy metal ions. The implementation of the project will be important and help to provide rational design principles, optimized preparation technologies, and potential theory basis for the study of novel dual-emission luminescence sensing materials.

构筑形貌可控、检测灵敏度高及物化性质稳定的双发射荧光传感体系是无机功能材料领域的一个研究热点。本项目拟基于Zn原子化学键作用，构筑具有双发射荧光特性的Zn2(Si,Ge)O4:Mn2+/Zn-MOFs异质结构，协同实现Zn2(Si,Ge)O4:Mn2+微纳米晶的高效荧光发射和Zn-MOFs的可调控荧光识别功能，获得系列形貌/结构可控、发光效率高、稳定性好且具有特异性荧光响应的异质结构双发射荧光传感体系。考察该异质结构体系的化学组成、组装方式、表界面性质与双荧光发射特性之间的构效关系；探讨异质结构的表界面识别功能及光化学传感机制和作用原理；揭示不同发光中心的激发态调控原则、实现高灵敏度荧光双发射性能比例调控；进一步开发其在比率荧光测温和重金属离子探测领域的应用，为优化和制备新型双发射荧光传感材料提供材料设计思路、关键制备技术与基础理论依据。

开发新型主客体纳米孔无机复合材料化学自组装策略，及其性能开发在功能材料科学领域具有重要研究意义。本项目以无机纳米孔骨架为主体，利用化学键自组装及纳米孔空间限域作用构筑了系列主客体复合材料，拓展了纳米孔复合材料及其衍生物在气敏和光/电化学传感等领域的多功能应用。本项目所完成的代表性工作汇总如下：（1）光功能无机纳米孔主客体复合材料的可控组装及其发光应用研究：基于Zn原子化学键作用和化学后修饰等策略，构筑形貌可控、检测灵敏度高及物化性质稳定的无机复合发光体系，用于比率荧光测温和特异性重金属离子检测；利用化学键作用构筑香豆素-7染料分子功能化Eu-MOF双模式温度传感材料；利用MOF纳米孔空间限域作用构筑MOF限域碳点、CsPbBr3量子点复合发光体系；以纳米孔Beta纯硅分子筛和TS-1钛硅分子筛为主体，采用一步固相扩散法、离子交换-热注入法制备了限域CsPbX3荧光纳米晶复合材料，用于背光显示和防伪及指纹识别，相关研究成果发表在Inorg. Chem.，J. Mater. Chem. C，Mater. Chem. Front.等期刊上。（2）MOFs衍生等级结构多金属氧化物气敏性质研究：以铁基普鲁士蓝为前驱体，通过Sn2+阳离子交换，制备了中空立方笼SnO2/α-Fe2O3；采用Ni2+,Co2+双金属离子交换，制备了尖晶石结构NixCo1-xFe2O4中空立方笼；采用三价态Bi3+,Ga3+离子交换，制备了钙钛矿结构BiFeO3和GaFeO3中空立方笼；采用MO42-阴离子交换，制备α-Fe2O3@α-MoO3中空立方笼，上述中空结构展现出优异的丙酮或三乙胺气敏传感性质，相关研究成果发表在Sensor. Actuat. B-Chem.，J. Mater. Chem. C等期刊。（3）MOFs纳米孔主客体复合材料及其衍生物电化学传感性质研究：采用封装法制备CuO包覆的Ni/Co双金属MOF材料，利用MOF前驱体转换法制备了等级结构α-Fe2O3、Ni/Co-功能化MoS2中空立方笼，用于高灵敏度葡萄糖无酶电化学传感，相关研究成果发表在Appl. Surf. Sci.，Dalton Trans.等期刊上。截至到2021年12月，本项目研究共发表基金资助SCI论文39篇；申请国家发明专利3项；培养研究生19人，其中博士生3人。本项目圆满完成了任务书中预期的研究成果。