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[碳点专辑]碳点发光标记材料的制备及其在水样中亚硝酸盐专一检测的应用

王长莹1,2,张大伟1,2,陈冠吉1,4,张镇威1,萧卫泓1,王  4,陈奇丹1,2,杨  2,3   

  1. 1.珠海科技学院生命科学学院

    2.吉林大学珠海研究院

    3.吉林大学化学学院,超分子结构与材料国家重点实验室 4.中国科学院广州化学研究所

  • 收稿日期:2024-11-27 修回日期:2025-02-04 出版日期:2025-02-14 发布日期:2025-02-14
  • 通讯作者: 陈奇丹 E-mail:qidanchen@jlu.edu.cn
  • 基金资助:
    广东省普通高校重点科研平台和项目(重点领域专项)基金(批准号:2021GCZX010, 2020ZDZX2036)、珠海市基础与应用基础课题研究项目(批准号:ZH22017003200015PWC)和珠海科技学院三个层次人才建设工程资助

Preparation of carbon dots fluorescent marker and the application in NO2- specific detection

WANG Changying1,2, ZHANG Dawei1,2, CHEN Guanji1,4, ZHANG Zhenwei1, XIAO Weihong1, WANG Bin4, CHEN Qidan1,2*, YANG Bai2,3   

  1. 1. School of Life Sciences, College of Zhuhai Science and Technology

    2. Zhuhai Institute, Jilin University

    3. State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry 4. Guangzhou Institute of Chemistry, Chinese Academy of Sciences

  • Received:2024-11-27 Revised:2025-02-04 Online:2025-02-14 Published:2025-02-14
  • Contact: Qidan Chen E-mail:qidanchen@jlu.edu.cn
  • Supported by:
    Supported by the Scientific Research Platforms and Projects (Special Foundation for the Major Program) of Guangdong Provincial Higher Education, China(Nos.2021GCZX010, 2020ZDZX2036), the Zhuhai Basic and Applied Basic Research Foundation, China(No.ZH22017003200015PWC), and the Three Levels of Talent Project of Zhuhai College of Science and Technology

摘要: 本文以盐酸多巴胺、邻苯二胺为原料通过一步水热法制备并提纯分离后得到目标产物——发射波长为535 nm的黄绿色碳点(λex=440 nm)作为污染物标记材料进行应用探索. 通过表征分析,该碳点尺寸约为3 nm,分散性良好,有稳定的发光性能,适用pH范围宽且抗盐性强. 而饮用水中亚硝酸盐超标可导致人类高铁血红蛋白血症,有潜在的致癌性. 应用该碳点对水样中常见污染物检测,筛选实验结果表明,该碳点标记材料对亚硝酸根具有高选择性专一响应,检出限为0.1166 μg·mL-1(S/N =3,n =3),满足我国国标对生活饮用水中NO2-限定标准(≤1 μg·mL-1)的要求. 在0~60 μg·mL-1内符合Stern-Volmer方程,其中在0~10 μg·mL-1(y=0.02x+0.000876,R2=0.9868)以及12~60 μg·mL-1范围内(y=0.011x+0.198,R2=0.9937),均有良好的线性响应,此外,通过3种不同水样加标实验验证,回收率在90.8 % ~100.8 %(RSD=0.03 %~0.86 %,n=3). 该碳点发光标记材料合成方法快速简便,成本低,在微痕量亚硝酸盐污染物检测中有较大的应用潜力,可作为水源地水质监测的重要补充手段.

关键词: 一步水热法, 碳点, 亚硝酸根, 水质监测

Abstract: In this paper, the yellow-green carbon dots (λex=440 nm) with a fluorescence emission wavelength of 535 nm were prepared by a one-step hydrothermal method using dopamine hydrochloride and o-phenylenediamine as raw materials, and then used as fluorescent marker materials for NO2- detection in water samples after purified and separated. The size of the carbon dots is about 3 nm with good dispersion, excellent salt resistance, stable fluorescence under a broad pH value. However, nitrite contaminants in water sources can cause methemoglobinemia disease and has potential carcinogenic risk. The results of the selectivity of the yellow-green carbon dots prepared to detect common contaminants in water samples showed that the carbon dots had a highly specific response to nitrite, and the detection limit was 0.1166 μg·mL-1 (S/N=3, n=3), which meets the requirements of Chinese national standards for determination of NO2-in drinking water (≤1 μg·mL-1). The detection range of 0~60 μg·mL-1 fits the Stern-Volmer equation, and the range of 0~10 μg·mL-1 (y=0.02x+0.000876, R2=0.9868) and 12~60 μg·mL-1 (y=0.011x+0.198, R2=0.9937) have good linear responses. In addition, the recoveries of three spiked water samples are from 90.8% to 100.8% (RSD=0.03 %~0.86 %, n=3) for the validation test. The method of the fluorescent carbon dots marker for contaminants developed in this work is fast and simple, low-cost and has greatly potential in trace nitrite analysis and can be an effective supplementary method for the monitoring of drinking water sources quality.

Key words: One-step hydrothermal method, Carbon dots, NO2-, Water quality monitoring

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