基于铝掺杂碳点的荧光探针用于环烷酸的定量检测

doi:10.16085/j.issn.1000-6613.2024-1509

摘要/Abstract

摘要：

开发了一种基于铝掺杂碳点（Al-CDs）的荧光探针，用于1-金刚烷羧酸作为模型环烷酸的定量检测方法。首先以L-精氨酸为碳源和氢键受体、乙二醇为氢键供体形成二元低共熔溶剂（B-DES），再添加AlCl₃‧6H₂O为铝源，合成三元低共熔溶剂（T-DES），最后T-DES经过水热法合成了Al-CDs。结果表明，通过低共熔溶剂（DES）合成Al-CDs，一方面可以使制备的Al-CDs尺寸分布均匀且结构稳定，另一方面可以有针对性地将目标官能团在Al-CDs表面进行修饰，同时实现了铝元素的成功掺杂。所制备的Al-CDs具有优异的荧光稳定性，对模型环烷酸具有良好的荧光响应，在0.5~20mmol/L的模型环烷酸浓度范围内呈线性关系，检出限0.163mmol/L，检测是通过Al-CDs和模型环烷酸之间发生配位作用产生的静态淬灭机制实现的，将Al-CDs应用于加标废水的检测，检测结果与气相色谱法结果一致。本工作为碳点在石化工业中的荧光检测提供了新的见解，拓宽了碳点在有机污染物检测中的应用。

关键词: 铝掺杂碳点, 荧光探针, 环烷酸, 静态淬灭机制, 稳定性, 选择性, 低共熔溶剂, 粒度分布

Abstract:

A fluorescent probe based on aluminum-doped carbon dots (Al-CDs) was developed for the quantitative detection of 1-adamantanecarboxylic acid as a model naphthenic acid. Firstly, the binary deep eutectic solvent (B-DES) was formed by using L-arginine as the carbon source and hydrogen bond acceptor, and ethylene glycol as the hydrogen bond donor. Then, the ternary deep eutectic solvents (T-DES) was synthesized by adding AlCl₃‧6H₂O as the aluminum source, and finally Al-CDs were synthesized from T-DES by hydrothermal method. The results showed that by synthesizing Al-CDs with deep eutectic solvent (DES), on the one hand, the size distribution of the prepared Al-CDs could be uniform and the structure was stable, on the other hand, the target functional groups could be modified on the surface of Al-CDs and the successful doping of aluminum elements could be achieved. The prepared Al-CDs had excellent fluorescence stability and good fluorescence response to the model naphthenic acid, showing a linear relationship within the concentration range of 0.5—20mmol/L of the model naphthenic acid with the detection limit of 0.163mmol/L. The detection was realized by the static quenching mechanism generated by the coordination between Al-CDs and the model naphthenic acid. Al-CDs was applied to the detection of labeled wastewater and the detection results were consistent with results of gas chromatography. The present work provided new insights into the fluorescence detection of carbon dots in the petrochemical industry and broadened the application of carbon dots in the detection of organic pollutants.

Key words: aluminum-doped carbon dots, fluorescence probe, naphthenic acids, static quenching mechanism, stability, selectivity, deep eutectic solvents, size distribution

中图分类号:

TE991

王平, 宋卫余, 任红威, 段二红, 陈春茂. 基于铝掺杂碳点的荧光探针用于环烷酸的定量检测[J]. 化工进展, 2025, 44(11): 6674-6687.

WANG Ping, SONG Weiyu, REN Hongwei, DUAN Erhong, CHEN Chunmao. A fluorescence probe based on aluminum-doped carbon dots for the quantitative detection of naphthenic acid[J]. Chemical Industry and Engineering Progress, 2025, 44(11): 6674-6687.

图/表 18

图1 Al-CDs的合成路线

图2 Al-CDs的TEM和粒径分布

表1 Al-CDs的粒径分布数据

粒径分布/nm	平均值/nm	质量分数/%
1~1.3	1.15	3.3
1.3~1.6	1.45	19.3
1.6~1.9	1.75	26.0
1.9~2.2	2.05	22.7
2.2~2.5	2.35	14.7
2.5~2.8	2.65	9.7
2.8~3.1	2.95	3.7
3.1~3.4	3.25	0.3
3.4~3.7	3.55	0.3
3.7~4	3.85	0

图3 Al-CDs形成过程的FT-IR谱图

图4 Al-CDs的核磁共振氢谱和碳谱

图5 Al-CDs的XPS谱图和拉曼光谱图

图6 Al-CDs的光学性质

图7 不同因素对Al-CDs荧光稳定性的影响

图8 Al-CDs在酸性条件下的稳定性

图9 不同干扰物对Al-CDs荧光淬灭程度

图10 Al-CDs对1-金刚烷羧酸的荧光检测

图11 Al-CDs检测真实废水中的环烷酸

表2 加标废水检测结果（n=1~5）

项目	n
项目	1	2	3	4	5
环烷酸的浓度/mmol·L^-1	5.58	5.56	5.58	5.55	5.57
平均浓度/mmol·L^-1	5.57
气相色谱法平均浓度/mmol·L^-1	5.52

图12 Stern-Volmer拟合方程和检测前后的荧光寿命

图13 Al-CDs与1-金刚烷羧酸溶液混合前后XPS高分辨光谱

图14 Al-CDs与1-金刚烷羧酸混合前后UV-vis吸收光谱

图15 Al-CDs的荧光吸收谱、荧光发射谱和1-金刚烷羧酸的UV-vis吸收光谱

图16 Al-CDs检测环烷酸的机制

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