CN110452692B - 一种离子液体修饰的荧光碳点的制备和应用 - Google Patents
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Abstract
本发明属于纳米材料制备和光学传感检测领域，具体为一种离子液体修饰的荧光碳点的制备和应用。主要包括以下步骤：（1）4‑甲氨基吡啶与柠檬酸混合后，在一定温度下，经脱水缩合得到吡啶修饰的荧光碳点材料；（2）1,6‑二溴己烷与步骤1中制备的荧光碳点反应得到离子液体修饰的功能性荧光碳点材料；（3）1‑溴十二烷与步骤1中制备的荧光碳点反应得到两亲性荧光碳点材料；（4）步骤2，3中所得功能性碳点实现对亚铁离子选择性检测。本发明的有益效果是：制备方法简单，成本低廉，所得功能性荧光碳点材料具有良好的稳定性，对Fe2+检测有良好的选择性和较高的灵敏度。
Description
技术领域
本发明属于纳米材料制备和光学传感检测领域，具体为一种离子液体修饰的荧光碳点的制备和应用。
背景技术
近年来，碳量子点(CDs)、石墨烯量子点、多环芳烃等发光材料受到了广泛的关注，且已广泛应用于传感器和生物成像领域。其中，荧光碳点材料不再仅限于由共轭基团或凝聚基团组成的发射源，它表现出特殊的物理化学和光学特性。在CDs的合成中，常用柠檬酸作为碳源，通过聚合或热裂解与胺类低聚物反应，得到目标荧光材料。前期研究表明，选择不同化学结构的胺前驱体，可以获得可调控的光学性能。然而，现有的制备方法和相关应用也存在着一定的缺陷，主要是选择的胺前驱体结构单一和所得荧光材料应用范围有限。
此外，大多数制备的荧光碳点材料对不同pH值溶液敏感，稳定性较差，容易产生荧光猝灭，极大地限制其在某些领域的进一步应用。鉴于此，对现有的合成方法进行改进具有重要的实际价值和研究意义。
本发明的目的是在于提供一种离子液体修饰的荧光碳点的制备方法和应用研究。本发明的技术任务之一：提供一种制备方法简单，成本低廉的合成方法。
本发明的技术任务之二：所得功能性荧光碳点材料应具有良好的稳定性，对Fe2+检测有良好的选择性和较高的灵敏度。
为实现上述目的，本发明采用的技术方案如下：
1. 一种离子液体修饰的荧光碳点的制备，步骤如下：
（1）在耐压试管中依次称取加入2.10-4.20g柠檬酸，3.24-6.48 g 4-甲氨基吡啶和20-40 mL乙醇，在一定温度下搅拌，反应完全后即可获得荧光碳点材料CDs-1；
（2）将步骤1中制备的CDs-1与3.66-7.32 g 1,6-二溴己烷混合，在一定温度下搅拌，减压除去溶剂，20-30 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点材料CDs-2；
（3）将步骤1中制备的CDs-1与7.47-1.494 g 1-溴十二烷混合，在一定温度下搅拌，减压除去溶剂，用20-30 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点材料CDs-3。
进一步地，步骤（1）中反应温度为155 ℃，磁力搅拌转速为300-500 r/min，反应完全时间为8 h。
进一步地，步骤（2）中反应温度为85 ℃，磁力搅拌转速为300-500 r/min，反应完全时间为24 h。
进一步地，步骤（3）中反应温度为85 ℃，磁力搅拌转速为300-500 r/min，反应完全时间为24 h。
2. 如上1所述的制备方法制备的碳点复合材料CDs-2和CDs-3用于荧光信号检测Fe2+的应用，步骤如下：
（4）分别称取100-200 mg CDs-2和100-200 mg CDs-3溶于50-100 mL去离子水，配制成相应溶液，取1 mL上述溶液对不同浓度的 Fe2+水溶液进行荧光强度检测，记录相应荧光强度的变化。
进一步地，步骤（4）中Fe2+检测所用激发波长为350 nm，波长范围为360-675 nm，Fe2+浓度范围为 0.08-1.5 μM。
本发明的有益效果是：制备方法简单，成本低廉，所得功能性荧光碳点材料具有良好的稳定性，对Fe2+检测有良好的选择性和较高的灵敏度等优势。
具体实施方式
现在结合具体实施例对本发明做进一步说明，以下实施例旨在说明本发明而不是对本发明的进一步限定。
实施例一：一种离子液体修饰的荧光碳点的制备
（1）在耐压试管中依次称取加入2.10柠檬酸，3.24g 4-甲氨基吡啶和20 mL乙醇，升温至155 ℃，300 r/min磁力搅拌，反应8 h后即可获得荧光碳点材料4.88 g CDs-1。
（2）将步骤1中制备的CDs-1与3.66 g 1,6-二溴己烷混合，升温至85 ℃，300 r/min磁力搅拌，反应24 h后，减压除去溶剂，20 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点材料CDs-2，产率为82%。
（3）将步骤1中制备的CDs-1与7.47 g 1-溴十二烷混合，升温至85 ℃，300 r/min磁力搅拌，反应24 h后，减压除去溶剂，20 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点材料CDs-3，产率为86%。
实施例二：Fe2+检测
分别称取100 mg实施例一中步骤（2）和（3）制备的 CDs-2和CDs-3，溶于溶于50 mL去离子水，配制成相应溶液，取1 mL上述溶液对1 μM Fe2+水溶液进行荧光强度检测，检测过程中所用激发波长为350 nm，检测波长范围为360-675 nm，记录相应荧光强度的变化。实验结果表明，CDs-2作为荧光探针时，Fe2+对其荧光强度影响较小；CDs-3作为荧光探针时，Fe2+对其荧光强度影响较大，发生明显的荧光猝灭现象。通过两者信号差异的比较，可以有效排除其他金属离子的干扰，确定了对Fe2+的专一性检测。同时在0.08-1.5 μM范围内保持良好的线性关系，相关系数在0.994以上，检测限为0.01 μM。
Claims (3)
1.一种离子液体修饰的荧光碳点检测水中亚铁离子的应用，其特征在于包括以下步骤：
（1）在耐压试管中依次称取加入2.10-4.20g柠檬酸，3.24-6.48 g 4-甲氨基吡啶和20-40 mL乙醇，在155 ℃下搅拌，反应8小时后，即可获得荧光碳点CDs-1；
（2）将步骤1中制备的CDs-1与3.66-7.32 g 1,6-二溴己烷混合，在85 ℃下搅拌，反应24小时后，减压除去溶剂，20-30 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点CDs-2；
（3）将步骤1中制备的CDs-1与7.47-1.494 g 1-溴十二烷混合，在85 ℃下搅拌，反应24小时后，减压除去溶剂，用20-30 mL正己烷洗涤产物，真空干燥，即可获得离子液体修饰的功能性荧光碳点CDs-3；
（4）分别称取100-200 mg CDs-2和100-200 mg CDs-3溶于50-100 mL去离子水，配制成相应溶液，取1 mL上述溶液对不同浓度 Fe2+水溶液进行荧光强度检测，记录相应荧光强度的变化。
2.根据权利要求1所述的一种离子液体修饰的荧光碳点检测水中亚铁离子的应用，其特征是：所述步骤（4）中亚铁离子水溶液浓度范围为0.08-1.5 μM。
3.根据权利要求1所述的一种离子液体修饰的荧光碳点检测水中亚铁离子的应用，其特征是：所述步骤（4）中亚铁离子检测限为0.01 μM。
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