Simultaneous Preparation of Pu-erh Tea-selenium-doped Carbon Quantum Dots and Elemental Selenium and Its Application in Fe3+ Detection
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摘要: 目的：为探讨普洱茶-纳米硒制备掺杂型碳量子点的可行性及其相关特性，实现水体系中Fe3+的快速检测。方法：以普洱茶水提取物稳定分散的普洱茶-硒原子为掺杂原子，采用水浴法，通过优化反应温度和时间，同时制备出普洱茶-硒掺杂碳量子点（Pu-erh tea nano-selenium doped carbon quantum dots，PT-Se-CQDs）和单质硒两种物质；采用紫外-可见吸收光谱和荧光光谱等技术表征PT-Se-CQDs的紫外-可见吸收特性和荧光强度，采用透射电子显微镜、X射线光电子能谱及X射线衍射等技术表征其形态形貌、元素组成及结构特性；并以PT-Se-CQDs为荧光探针构建荧光传感器，用于水体系中Fe3+检测。结果：当反应温度100 ℃、反应时间10 h时，可同时制备得量子产率为3.41%、平均直径约为3.1 nm的类球形PT-Se-CQDs和单质硒。Fe3+对PT-Se-CQDs具有强荧光静态猝灭效应，当Fe3+浓度为0~300 μmol/L时，比率荧光强度（F/F0）与Fe3+浓度呈良好的线性关系（R2>0.99），Fe3+的检出限低至0.2621 μmol/L；纯净水和矿泉水中Fe3+含量测定的加标回收率分别为90.93%~104.56%和84.53%~113.90%，RSD小于8.15%和4.00%。结论：本研究制备的PT-Se-CQDs对Fe3+具有高选择性和灵敏度，以此建立的检测Fe3+方法简单、快速，具有良好的应用前景。
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关键词:
- 普洱茶-纳米硒 /
- 普洱茶-硒掺杂碳量子点 /
- 单质硒 /
- 荧光传感器 /
- Fe3+
Abstract: Object: To prepare Pu-erh tea nano-selenium doped carbon quantum dots (PT-Se-CQDs) for the rapid detection of Fe3+ in the water system and to profile their characteristics. Method: In this study, PT-Se-CQDs and elemental selenium were prepared simultaneously in a water-bath by optimizing the reaction temperature and time. The ultraviolet-visible absorption and fluorescent intensity of PT-Se-CQDs were subsequently analyzed by the ultraviolet-visible absorption spectroscopy and fluorescence spectroscopy. And their morphology, elemental composition, and structural characteristics were characterized by transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, respectively. On this basis, a novel fluorescence sensor for the detection of Fe3+ in the aqueous system was constructed using PT-Se-CQDs. Result: PT-Se-CQDs in a spherical shape with a quantum yield of 3.41%, an average particle size of about 3.1 nm as well as elemental selenium were successfully prepared simultaneously via the reaction in a boiling water bath at 100 °C for 10 h. In addition, a strong static fluorescence quenching effect on PT-Se-CQDs was observed in the presence of Fe3+. Accordingly, Fe3+ in the range of 0~300 μmol/L was successfully detected using PT-Se-CQDs as a fluorescence sensor with a good linear relationship between the concentration of Fe3+ and the ratio of fluorescence intensity (F/F0) of PT-Se-CQDs (R2>0.99) and a limit of detection of 0.2621 μmol/L. When this method was applied to detect Fe3+ in real water samples, satisfactory standard recovery rates of Fe3+ in pure water and mineral water of 90.93%~104.56% and 84.53%~113.90% with the RSD less than 8.15% and 4.00% were obtained, respectively. Conclusion: The preparation of PT-Se-CQDs with high selectivity and sensitivity to Fe3+ and their application as a new fluorescence sensor for the detection of Fe3+ in aqueous systems with simple operation and fast response were explored in the present study. -
图 1 不同加热温度下普洱茶-硒掺杂碳量子点的荧光光谱
Figure 1. Fluorescence spectra of Pu-erh tea nano-selenium doped carbon quantum dots at different reaction temperatures
图 2 不同加热时间下普洱茶-硒掺杂碳量子点的荧光光谱
Figure 2. Fluorescence spectra of Pu-erh tea nano-selenium doped carbon quantum dots at different reaction time
图 3 PT-Se-CQDs透射电镜扫描图
Figure 3. TEM image of PT-Se-CQDs
注：a：200000倍放大的PT-Se-CQDs形貌；b：1500000倍放大的PT-Se-CQDs形貌；c：粒径分布图。
图 4 PT-Se-CQDs的XPS全谱图（a）和C1s高分辨图（b）
Figure 4. XPS full-spectrum （a） and C1s high-resolution spectrum （b） of PT-Se-CQDs
图 5 PT-Se-CQDs（a）及单质硒（b）的XRD图
Figure 5. XRD spectrum of PT-Se-CQDs （a） and elemental selenium （b）
图 6 PT-Se-CQDs紫外-可见吸收光谱图（a）、荧光光谱图（b）和荧光发光图（c）
Figure 6. Ultraviolet-visible spectra （a）, fluorescence spectrum （b） and 365 nm illumination under violet light （c） of PT-Se-CQDs
图 8 添加不同种类金属离子后PT-Se-CQDs的比率荧光
Figure 8. Ratio of fluorescence of PT-Se-CQDs with or without the addition of metal ions
图 9 不同金属离子与Fe3+作用于PT-Se-CQDs后的比率荧光
Figure 9. Ratio fluorescence of PT-Se-CQDs treated by Fe3+ in the presence of different metal ions
图 10 PT-Se-CQDs荧光强度随Fe3+浓度变化的荧光光谱图（a）及线性关系图（b）
Figure 10. Fluorescence spectrogram （a） of PT-Se-CQDs and the linear relationship diagram （b） between the fluorescence intensity of PT-Se-CQDs and the Fe3+ concentration
图 11 不同温度下Fe3+和PT-Se-CQDs相互作用的斯特恩-沃尔默图
Figure 11. Stern-Volmer plots for the quenching of Fe3+ by PT-Se-CQDs at different temperatures
表 1 不同荧光探针对Fe3+的检测性能比较
Table 1. Comparison of detection performance of Fe3+ by different fluorescence probes
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表 2 Fe3+与PT-Se-CQDs在不同温度下相互作用的猝灭常数Ksv
Table 2. Quenching constants Ksv for the interaction of Fe3+ by PT-Se-CQDs at different temperatures
温度（℃） Ksv·103（L/mol） R2 21 6.3928±0.8423 0.9795 31 4.7116±0.7454 0.9569 41 3.7915±0.5856 0.9754
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表 3 PT-Se-CQDs对实际样品中Fe3+的检测能力
Table 3. The detection ability of PT-Se-CQDs in the detection of Fe3+ in real samples
样品 添加值（μmol/L） 检出值（μmol/L） 回收率（%） RSD（%） 纯净水 10 10.46 104.56 8.15 100 90.93 90.93 3.28 矿泉水 10 11.39 113.90 4.00 100 84.53 84.53 1.14
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