类钙钛矿发光材料的合成及其用于重金属离子荧光传感研究

       卤化物钙钛矿材料及其类似物， 作为一类性能优异的发光材料近几年受到科学家们的广泛关注。 这类材料的发光特性往往可通过材料组分和晶体结构调控。 近年来， 新型发光钙钛矿材料的结构设计及合成一直是发光、太阳能电池等领域的研究热点。 本课题以卤化物为原料， 合成出多种不同结构的类钙钛矿发光材料， 解析了其晶体结构， 并深入研究了它们的发光机理。 此外， 还探讨了发光卤化物类钙钛矿材料， 在荧光探测重金属离子方面的应用。 具体研究内容包括：
       一是设计合成了两种发光卤化物类钙钛矿材料， 并评估其光学性能。本课题成功合成了 Cs₃CeBr₆ 和 Cs₈AgCe₃Br₁₈ 两种发光类钙钛矿材料， 两种材料均具有优异的可见光波段荧光发射性能。 其中， Cs₃CeBr₆ 具有高达97.76%的荧光量子效率。 利用光学平台测试和第一性原理计算， 本文进一步阐明了该系列材料的发光机理， 发现两种化合物的发光， 主要来源于孤立的[CeBr₆]^3-八面体贡献， 其局部八面体聚集方式不同， 导致了其荧光发射峰位置有显著差异。
       二是评估类钙钛矿结构发光材料在重金属离子检测方面的应用。 利用发光卤化物 Ruddlesden-Popper 相类钙钛矿材料在重金属溶液中易于原位生成， 形成的器件荧光信号强度随着重金属浓度变化而改变的特点。 利用紫外-可见吸收光谱、 光致发光光谱、 荧光显微镜等技术手段， 发现在一定范围内， 所制备的传感器的荧光强度随重金属离子浓度变化而线性相关。基于此原理， 我们设计开发了用于检测水体重金属铅离子（ Pb²⁺） 浓度的荧光传感器。 并利用光学测试和第一性原理计算， 详细阐明了传感器材料的工作机理。 该传感器能够对不同程度铅污染环境水体进行定性和定量探测。

Halide perovskite materials and their analogues have been widely studied for their excellent performance as luminescent materials. The luminescence properties of these materials can be finely tuned via the composition or structure of the materials. In recent years, the structure design and synthesis of new luminescent perovskite materials have attracted enormous attention in luminescence and solar cells. In this thesis, three kinds of halide perovskite structure analogues were synthesized, and their luminescence mechanism was carefully studied. In addition, the application of luminescent halide perovskite as fluorescent sensors for heavy metal ions detection was also discussed. Specific research contents include the following two parts:

In the first part of this thesis, Cs3CeBr6 and Cs8AgCe3Br18 luminescent perovskite analogues were successfully synthesized. Both materials had excellent fluorescence emission performance in the visible light region. Especially for Cs3CeBr6, the photoluminescence quantum efficiency was up to 97.76%. The luminescence mechanism of the new luminescent materials was elucidated by optical platform characterization and density function theory (DFT) calculation. It was found that the intrinsic luminescence capability of these two compounds resulted from the isolated [CeBr6]3- octahedra. The difference in the connection mode of octahedra led to a significant difference in photoluminescence emission.

In the second part of this thesis, we evaluated the application of luminescent perovskite analogues in heavy metal ions detection. The in-situ formation of light-emitting Ruddlesden-Popper phase halide perovskite materials with different concentrations of heavy metal solutions led to the fluorescent signal change. UV-Visible absorption spectrum, photoluminescence spectrum and fluorescence microscopy were used to obtain the linear correlation of the fluorescence intensity and heavy metal ions concentrations, making it a promising fluorescence sensor for heavy metal Pb2+ detection in water. The luminescent mechanism of the sensor was elucidated by employing optical measurement and density function theory calculation. The sensor can be used for the quantitive and qualitative detection of different levels of lead pollution in environmental water.

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