席夫碱功能化MIL-101(Fe)的制备及其对水中磷酸根的荧光检测  

Preparation of MIL-101(Fe)-Schiff and its performance on fluorescence detection of phosphate in aqueous solution

作　　者：韩静[1] 李耀威[1,2] 刘荃 陈玉祥 HAN Jing;LI Yaowei;LIU Quan;CHEN Yuxiang(School of Environment,South China Normal University,Guangzhou 510006,China;Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety,MOE Key Laboratory of Theoretical Chemistry of Environment,South China Normal University,Guangzhou 510006,China)

机构地区：[1]华南师范大学环境学院,广州510006 [2]华南师范大学广东省化学品污染与环境安全重点实验室,环境理论化学教育部重点实验室,广州510006

出　　处：《环境工程学报》2024年第11期3271-3279,共9页Chinese Journal of Environmental Engineering

基　　金：国家自然科学基金资助项目(21006037);广东省自然科学基金资助项目(2022A1515011102)

摘　　要：为预防水体富营养化,开发一种简单且快速的方法检测水中的磷酸根(PO_(4)^(3−))势在必行。金属-有机骨架材料优异的热稳定性、高比表面积、灵活的结构与孔隙可调性等特点使其在荧光传感领域备受关注。采用后合成修饰法制备了席夫碱功能化金属-有机骨架材料MIL-101(Fe)-Schiff,利用XRD、FT-IR、SEM-EDS、TEM、XPS等表征其结构和形态,并通过紫外-可见吸收光谱和荧光光谱进一步研究其荧光性质及对磷酸根的荧光检测性能。结果表明,MIL-101(Fe)-Schiff在水溶液中显示出良好的荧光稳定性,能够快速地实现对磷酸根的荧光增强检测。在最佳条件下,MIL-101(Fe)-Schiff的发光强度和磷酸根浓度之间具有良好的线性关系(相关系数R^(2)=0.9979),其线性范围为0.01~1 mmol·L^(−1),检测限低至4.82μmol·L^(−1)(S;N=3),在实际水样中也表现出良好的磷酸根检测性能。磷酸根引起的荧光增强效应主要归因于MIL-101(Fe)-Schiff上Fe-oxo和亚胺基团分别与磷酸根形成的配位和氢键作用。本研究结果可为便捷的原位检测磷酸根荧光方法的进一步开发和应用提供参考。Developing a simple and rapid method for phosphate(PO_(4)^(3−))detection is imperative to address eutrophication problems of water bodies.Metal-organic frameworks(MOFs)have drawn increasingly attentions as fluorescence sensors due to their good thermal stability,high specific surface area,flexible modifiable structures and tunable porosity.The Schiff base-functionalized metal-organic framework material MIL-101(Fe)-Schiff was prepared by post-synthetic modification method,and its structure and morphology were characterized by XRD,FT-IR,SEM-EDS,TEM and XPS.The fluorescence properties of MIL-101(Fe)-Schiff and its performance on fluorescence detection of phosphate were further investigated by UV-vis absorption spectroscopy and fluorescence spectroscopy.The results showed that MIL-101(Fe)-Schiff had a good fluorescence stability and could achieve the fluorescence enhanced detection of phosphate in aqueous solution with the preferable sensitivity and specificity.Under the optimal conditions,MIL-101(Fe)-Schiff showed a good linear correlation between the luminescence intensity and phosphate concentration(correlation coefficient R^(2)=0.9979),within a linear range of 0.01-1 mmol·L^(−1) and a low detection limit(LOD)of 4.82μmol·L^(−1)(S;N=3).It also showed a good phosphate detection performance in practical applications.The fluorescence enhancement effect induced by phosphate was mainly attributed to the coordination and hydrogen bonding interactions between Fe-oxo,imine groups on MIL-101(Fe)-Schiff and phosphate,respectively.This study can provide a reference for the further development and application of convenient fluorescence methods for in-situ detection of phosphate.

关 键 词：MIL-101(Fe)-Schiff 亚胺基 荧光探针 磷酸根 传感机理 

分 类 号：X703[环境科学与工程—环境工程]