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基于碳点@剥离层状双氢氧化物复合材料荧光探针的铜(II)离子有效检测

Effective Detection of Cu(II) Ions Based on Carbon Dots@Exfoliated Layered Double Hydroxides Composites Fluorescence Probe.

作者信息

Lu Quliang, Mei Yixian, Wu Yuting, Lin Houjun, Li YanLi

机构信息

Chengxian College, Southeast University, Nanjing, Jiangsu, 210088, P. R. China.

Institute of Chemical Industry of Forest Products, CAF, Nanjing, 210042, P. R. China.

出版信息

J Fluoresc. 2025 Mar;35(3):1441-1456. doi: 10.1007/s10895-024-03597-w. Epub 2024 Feb 15.

DOI:10.1007/s10895-024-03597-w
PMID:38358445
Abstract

A series of carbon dots@exfoliated layered double hydroxides (CDs@LDH) composites were hydrothermally fabricated by Mg/Al LDH and formamide. The results of FTIR, UV-vis, and XPS spectra in company with HRTEM images showed that crystalline nano CDs formed on the single layer of LDH by Mg-C bond. With the increase of solvothermal reaction time from 2 to 6 h, the band gap and the binding energy of aminic and graphitic N species of CDs@LDH composites decreased, whereas the crystallinity increased. The fluorescence peaks of CDs@LDH composites could be deconvoluted into short-wavelength (416 nm) and large-wavelength (443 nm) components by Gaussian function, and the fluorescence intensities of both components enhanced with the extension of the solvothermal reaction time. The simultaneous enhancements of fluorescence lifetime and quantum yield resulted from the relatively high electron density in graphitic nitrogen of CDs@LDH, whereas the reduction of nonradiative rate was due to the high crystallinity in the carbon core of CDs@LDH. A strong exciton-lattice interaction also has been validated based on the excitation and emission spectra of CDs@LDH, so the fluorescence emission of CDs@LDH composite was heavily related to its crystalline carbon core and nitrogen-containing groups. CDs@LDH with high nitrogen-containing exhibited a superior detection property for Cu ion sensing with the linear range of 26.90 ~ 192.20 μM and a limit of detection of 0.1957 μM. The photo-induced electron transfer (PET) process dominated the fluorescence quenching of CDs@LDH by Cu ion since the fluorescence lifetime decreased with the increase of Cu ion concentration.

摘要

通过镁铝层状双氢氧化物(Mg/Al LDH)和甲酰胺水热法制备了一系列碳点@剥离层状双氢氧化物(CDs@LDH)复合材料。傅里叶变换红外光谱(FTIR)、紫外可见光谱(UV-vis)和X射线光电子能谱(XPS)结果以及高分辨透射电子显微镜(HRTEM)图像表明,结晶纳米碳点通过Mg-C键在LDH单层上形成。随着溶剂热反应时间从2小时增加到6小时,CDs@LDH复合材料的带隙以及氨基和石墨氮物种的结合能降低,而结晶度增加。CDs@LDH复合材料的荧光峰可通过高斯函数解卷积为短波长(416nm)和长波长(443nm)成分,并且随着溶剂热反应时间的延长,两种成分的荧光强度均增强。荧光寿命和量子产率的同时提高源于CDs@LDH石墨氮中相对较高的电子密度,而非辐射速率的降低则归因于CDs@LDH碳核中的高结晶度。基于CDs@LDH的激发和发射光谱也验证了强烈的激子-晶格相互作用,因此CDs@LDH复合材料的荧光发射与其结晶碳核和含氮基团密切相关。高含氮量的CDs@LDH对铜离子传感表现出优异的检测性能,线性范围为26.90~192.20μM,检测限为0.1957μM。由于荧光寿命随铜离子浓度的增加而降低,光致电子转移(PET)过程主导了CDs@LDH被铜离子的荧光猝灭。

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