基于锆基荧光金属-有机骨架材料的水体全氟辛烷磺酸的快速筛查
Rapid fluorescent sensing of perfluorooctane sulfonate in water using a zirconium-based luminescent metal-organic framework
王恩语 1朱飞越 1杨正爽 1瞿晓磊 2付翯云2
作者信息
- 1. 南京大学环境学院,污染控制与资源化研究国家重点实验室,南京,210093
- 2. 南京大学环境学院,污染控制与资源化研究国家重点实验室,南京,210093;南京大学(苏州)高新技术研究院,苏州,215127
- 折叠
摘要
本文以锆基荧光金属-有机骨架材料UiO-66-NH2为传感器,建立了水体全氟辛烷磺酸(PFOS)的快速荧光筛查方法.利用扫描电子显微镜、X射线衍射、傅里叶变换红外光谱和荧光光谱等手段对UiO-66-NH2的结构和光学性质进行了分析,并且考察了 UiO-66-NH2传感器对PFOS的传感灵敏度、速度和稳定性,及其在实际水体中的可应用性.研究结果显示,UiO-66-NH2与其配体(2-氨基对苯二甲酸/BDC-NH2)具有相似的荧光性质,均可在光激发下产生稳定的蓝色荧光,但发光强度明显弱于BDC-NH2.这是因为UiO-66-NH2中锆与BDC-NH2间的配体-金属电荷转移(LMCT)抑制了 BDC-NH2的荧光发光.而PFOS可与UiO-66-NH2锆金属节点发生作用,影响锆与BDC-NH2间的LMCT过程,进而恢复BDC-NH2的荧光,产生荧光"开启"响应.在0.1-4.0 mg·L-1浓度范围内,PFOS浓度与UiO-66-NH2的荧光增强程度呈现良好线性正相关(R2=0.993).UiO-66-NH2对PFOS的检出限为3.46 μg·L-1(即0.0069 μmol·L-1),低于文献中报道的多数PFOS荧光传感器.UiO-66-NH2还具有较快的PFOS响应速度,在与PFOS作用400s之内即可达到荧光响应平衡.此外,UiO-66-NH2对PFOS的传感过程基本不受水体常见阴、阳离子的影响,具有良好的可重复利用性,在实际水体筛查中也显示了高加标回收率(95.0％-106.5％),表明基于UiO-66-NH2的荧光法在水体PFOS的快速筛查中具有良好的应用潜能.
Abstract
In this study,a fluorescent method was established for the rapid sensing of perfluorooctane sulfonate(PFOS)in water using a zirconium-based luminescent metal-organic framework,UiO-66-NH2.The structural and optical spectral properties of the UiO-66-NH2 were characterized by combined techniques including scanning electron microscopy,X-ray diffraction,Fourier transform infrared spectroscopy,and fluorescence spectroscopy.The sensing sensitivity,speed and stability of the UiO-66-NH2 sensor for PFOS,and its applicability in real water samples were investigated.The results showed that UiO-66-NH2 exhibited stable blue emission in water under light excitation,mainly originating from the 2-aminoterephthalic acid(BDC-NH2)ligand.The fluorescence emission of BDC-NH2 was weakened upon its integration into the framework of UiO-66-NH2 due to the ligand-to-metal charge transfer(LMCT).The competitive coordination of PFOS with the zirconium node would interrupt the LMCT process and thus recover the emission of BDC-NH2,resulting in a fluorescent"turn-on"response.In the concentration range of 0.1-4.0 mg·L-1,the enhancement of UiO-66-NH2 fluorescence intensity(at excitation wavelength of 330 nm and emission wavelength of 438 nm)showed a good linear positive correlation with the concentration of PFOS(R2=0.993).The detection limit of PFOS by the fluorescence method based on UiO-66-NH2 was 3.46 μg·L-1(i.e.,0.0069 μmol·L-1),lower than that of most reported PFOS fluorescence sensors.Moreover,UiO-66-NH2 afforded a rapid response speed towards PFOS,with a response equilibrium time within 400 s.The sensing performances of UiO-66-NH2 was scarcely affected by common interfering ions in water.The UiO-66-NH2-based sensing method also exhibited good reusability and high PFOS recoveries(95.0％—106.5％)in real water samples,suggesting its good applicability for PFOS screening in waters.
关键词
全氟辛烷磺酸/荧光传感/荧光金属-有机骨架材料/荧光开启Key words
perfluorooctane sulfonate/fluorescent sensing/luminescent metal-organic framework/turn-on引用本文复制引用
基金项目
国家重点研究计划项目(2019YFC1804201)
国家自然科学基金(42277363)
出版年
2024
NETL
NSTL
万方数据