两类荧光可调碳点的制备及在防伪油墨上的应用

doi:10.7503/cjcu20140559

高等学校化学学报 ›› 2015, Vol. 36 ›› Issue (2): 293.doi: 10.7503/cjcu20140559

两类荧光可调碳点的制备及在防伪油墨上的应用

聂辉, 李敏杰(), 鞠博, 张晓安()

吉林大学超分子结构与材料国家重点实验室, 长春 130012

收稿日期:2014-06-20 出版日期:2015-02-10 发布日期:2015-01-15
作者简介:联系人简介: 李敏杰, 女, 博士, 副教授, 主要从事超分子自组装体的仿生功能及光电显示与传感方面的研究.E-mail: liminjie@jlu. edu. cn张晓安, 男, 博士, 教授, 博士生导师, 主要从事刺激响应材料及在光显示和传感方面的应用研究.E-mail: seanzhang@jlu.edu.cn
基金资助:
国家自然科学基金(批准号: 51001020, 21072025)资助.

Two Types of Carbon Dots with Excitation-dependent Emissions and Their Application as Anti-counterfeit Ink^†

NIE Hui, LI Minjie^*(), JU Bo, ZHANG Sean Xiaoan^*()

State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, China

Received:2014-06-20 Online:2015-02-10 Published:2015-01-15
Contact: LI Minjie,ZHANG Sean Xiaoan E-mail:liminjie@jlu. edu. cn;seanzhang@jlu.edu.cn
Supported by:
Supported by the National Natural Science Foundation of China(Nos. 51001020, 21072025).

摘要/Abstract

摘要：

以不同的氯代烃和胺类为反应原料, 在相同反应条件下制备了2类荧光发射波长随激发波长变化而变化的碳点. 其中一类碳点的荧光强度随着激发波长的红移呈现类似于高斯曲线的变化趋势(类型Ⅰ), 另一类碳点的荧光强度随激发波长变化不规律(类型Ⅱ). 通过荧光光谱、透射电子显微镜、 X射线光电子能谱和红外光谱对2类碳点的结构和性质进行了表征和比较. 考察了类型Ⅱ碳点作为一种新型的荧光油墨在多重防伪领域的应用性能.

关键词: 碳点, 荧光, 表面态, 防伪油墨

Abstract:

Carbon dots with excitation-dependent emission were prepared using different chlorohydrocarbon and amine as reactants under the same reaction condition. The carbon dots 1 and carbon dots 2 had selective emissions in a range of 423—556 nm and 460—555 nm, respectively, in addition, their fluorescence intensity changes could be modeled by a Gaussian-like curve with the red shift of excitation wavelengths(denoted as type Ⅰ carbon dots). The carbon dots 3 had emissions in a broad color range over the entire visible region(407—670 nm), moreover, their fluorescence intensities had irregular change with the excitation wavelengths(denoted as type Ⅱ carbon dots). Then, fluorescence spectroscopy, transmission electron microscopy, X-ray photoelectron spectroscopy and infrared spectroscopy were explored to analyze their structural and spectral characteristics in detail. For the type Ⅱ carbon dots, except for the size effect, the surface functional groups, such as C=O and C=N, could efficiently introduce new energy levels for electron transitions and result in the continuously adjustable full color emissions. Further, the type Ⅱ carbon dots were demonstrated as ideal candidates for high security anti-counterfeit purpose.

Key words: Carbon dot, Fluorescence, Surface-state, Anti-counterfeiting ink

中图分类号:

TrendMD:

聂辉, 李敏杰, 鞠博, 张晓安. 两类荧光可调碳点的制备及在防伪油墨上的应用. 高等学校化学学报, 2015, 36(2): 293.

NIE Hui, LI Minjie, JU Bo, ZHANG Sean Xiaoan. Two Types of Carbon Dots with Excitation-dependent Emissions and Their Application as Anti-counterfeit Ink^†. Chem. J. Chinese Universities, 2015, 36(2): 293.

图/表 7

Fig.1 UV-Vis absorption spectra(A) and fluorescence spectra of the C dots 1(B), C dots 2(C) and C dots 3(D) in ethanol under different excitation wavelength

Fig.2 TEM images of C dots 1(A), C dots 2(B) and C dots 3(C) Inset: HRTEM images of three C dots.

Table 1 Element contents in C dots 1, C dots 2, C dots 3 and F-C dots

Sample	Atomic ratio(%)
Sample	C	N	O	Cl
C dots 1	86.43	5.38	7.75	0.44
C dots 2	75.2	17.88	6.63	0.29
C dots 3	72.51	6.27	14.76	6.46
F-C dots	75.03	4.34	18.47	2.15

Fig.3 High-resolution XPS spectra of the C1s(A) and N1s(B) peaks for C dots 1, C dots 2, C dots 3 and F-C dots

Table 2 XPS analysis of C1s in C dots 1, C dots 2, C dots 3 and F-C dots

Sample	C—C(%)	C—N(%)	C—O(%)	C O/C N(%)
C dots 1	85.0	6.7	4.3	4.0
C dots 2	70.5	6.8	19.6	3.1
C dots 3	68.2	10.3	20.9	8.8
F-C dots	67.3	9.8	13.7	9.2

Fig.4 FTIR spectra of C dots 1(a), C dots 2(b), C dots 3(c) and F-C dots(d)

Fig.5 Photoluminescent patterns using C dots 3 solution as anti-counterfeiting inks by inkjet printing (A) Illustration of C dots 3 as ink on a ￥5 RMB practice note printed with security pattern; fluorescence microscope images of security pattern excited under UV(B), blue(C) and green(D) light, respectively.

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	hui (Ed.: P, H, F, K)

两类荧光可调碳点的制备及在防伪油墨上的应用

Two Types of Carbon Dots with Excitation-dependent Emissions and Their Application as Anti-counterfeit Ink^†

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两类荧光可调碳点的制备及在防伪油墨上的应用

Two Types of Carbon Dots with Excitation-dependent Emissions and Their Application as Anti-counterfeit Ink†

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被引次数

摘要/Abstract

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Two Types of Carbon Dots with Excitation-dependent Emissions and Their Application as Anti-counterfeit Ink^†