锰掺杂ZnS量子点磷光体系的构建及用于Pb(Ⅱ)的传感识别  

Construction of Manganese Doped ZnS Quantum Dots Phosphorescence System and Its Application to Pb(Ⅱ)Sensing Detection

作　　者：董一帆 艾秋爽 俞熙仁 张莉[1] 梁经天 张大文[1] 邱素艳[1] DONG Yi-fan;AI Qiu-shuang;YU Xi-ren;ZHANG Li;LIANG Jing-tian;ZHANG Da-wen;QIU Su-yan(Institute for Quality&Safety and Standards of Agricultural Products Research,Jiangxi Academy of Agricultural Sciences,Nanchang330200,China)

机构地区：[1]江西省农业科学院农产品质量安全与标准研究所,江西南昌330200

出　　处：《光谱学与光谱分析》2025年第4期964-970,共7页Spectroscopy and Spectral Analysis

基　　金：江西省农业科学院基础研究与人才培养专项(JXSNKYJCRC202401);江西省科技创新高端人才(省双千培养类)项目(jxsq2023201131);国家自然科学基金项目(21964009);国家农产品质量安全风险评估项目(GJFP20220302);江西现代农业科研协同创新专项(JXXTCX202110);江西省豆类产业技术体系(JXARS-24-03)资助。

摘　　要：磷光发光寿命长,激发光谱与发射光谱之间有更宽的间距,并能有效避免来自系统和光散射的干扰,因此磷光传感技术在近几年备受关注。采用反应釜水热法合成出水溶性的Mn^(2+)掺杂ZnS量子点,对合成出的量子点进行表征,从XRD衍射结果、高倍透射电镜形貌图和TEM-mapping图中都可以得出结论,Mn^(2+)成功掺杂进ZnS晶格内部。该量子点在580 nm处出现明显的磷光发射峰,且远远高于420 nm处的荧光峰强度。同时还研究了不同反应条件下,该量子点的磷光性质,发现当前驱体溶液pH为11、反应时间为30 min和Mn^(2+)掺杂比例为4%时,其量子点磷光特征峰最高。与传统制备方法相比,该反应釜水热法能够有效将Mn^(2+)掺杂至ZnS量子点内部,而非表面,导致其主要以磷光发射为主,而非荧光,有利于提高传感技术的选择性和灵敏度。该研究还发现Pb^(2+)能够选择性猝灭Mn掺杂ZnS量子点的磷光,并考察了缓冲液pH、体系反应时间的影响,在最优条件下,建立了一种高灵敏识别Pb^(2+)离子的磷光传感技术,其线性范围为0.02~20μmol·L^(-1),检测限低至6.6 nmol·L^(-1),同时其他常见金属离子对该传感技术无明显干扰作用,对实际样品进行了加标回收实验,回收率为91.9%~114.1%,准确率在83.0%~109.8%之间,证实该传感技术可以用于湖水样品中Pb^(2+)的快速识别,具有良好的稳定性和重复性。Phosphorescence sensing technology has attracted much attention in recent years due to its long life,wider gap between the excitation spectrum and emission spectrum,and the ability to effectively avoid interference from the system and light scattering.This study synthesized water-soluble Mn-doped ZnS quantum dots in a reactor using the hydrothermal method.When synthesized quantum dots were characterized,it can be concluded from the XRD results,TEM image,and TEM-mapping image that Mn^(2+)was successfully doped into the ZnS lattice.The quantum dots exhibited an obvious phosphorescence emission peak at 580 nm,much higher than fluorescence peak at 420 nm.The phosphorescence properties of the quantum dots under different reaction conditions were also investigated.It was found that the characteristic peak of the quantum dots was the highest when the pH of the precursor solution was 11,the reaction time was 30 minutes,and the Mn doping ratio was 4%.Compared with the traditional preparation method,the hydrothermal method in the reactor can effectively dope Mn into the interior of ZnS quantum dots rather than the surface,leading to phosphorescence emission,which is conducive to improving the selectivity and sensitivity of the sensing system.In addition,this study also found that Pb^(2+)can selectively quench the phosphorescence of Mn-doped ZnS quantum dots,and investigated the effects of buffer pH and reaction time.Under the optimal conditions,a highly sensitive phosphorescence sensing system for identifying Pb^(2+)ions was established with a linear range of 0.02~20μmol·L^(-1),and the detection limit was as low as 6.6 nmol·L^(-1).At the same time,other metal ions had no obvious interference with this sensing technology.The determination of Pb^(2+)in water samples from a lake was successfully tested,the recovery rate ranged from 91.9%~114.1%,and the accuracy rate was between 83.0%~109.8%,which proved that this sensitive phosphorescence sensing system had good stability and repeatability.

关 键 词：锰掺杂硫化锌量子点 水热合成法 磷光探针 

分 类 号：O614.241[理学—无机化学]