溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe3+检测中的应用

doi:10.7503/cjcu20170115

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (9): 1556.doi: 10.7503/cjcu20170115

溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe³⁺检测中的应用

战岩¹, 俎鸿儒¹, 黄棣¹, 刘应亮²(), 胡超凡^1,²()

1. 太原理工大学力学学院, 太原 030024
2. 华南农业大学材料与能源学院, 广州 510624

收稿日期:2017-02-25 出版日期:2017-09-10 发布日期:2017-07-12
作者简介:联系人简介: 胡超凡, 男, 博士, 讲师, 主要从事碳材料的制备和生物方面的研究. E-mail: hcf0000@126.com;刘应亮, 男, 博士, 教授, 博士生导师, 主要从事生物炭及发光材料方面的研究. E-mail: tliuyl@scau.edu.cn
基金资助:
国家自然科学基金(批准号: 51402207, 11502158)和山西省高等学校创新项目(批准号: 2015129)资助

Synthesis of Fluorescent Graphitic Carbon Nitride Quantum Dots by Solvothermal Ions Intercalation Method for Fe(Ⅲ) Detection^†

ZHAN Yan¹, ZU Hongru¹, HUANG Di¹, LIU Yingliang^2,^*(), HU Chaofan^1,^2,^*()

1. College of Mechanics, Taiyuan University of Technology, Taiyuan 030024, China
2. College of Materials and Energy, South China Agricultural University, Guangzhou 510624, China

Received:2017-02-25 Online:2017-09-10 Published:2017-07-12
Contact: LIU Yingliang,HU Chaofan E-mail:tliuyl@scau.edu.cn;hcf0000@126.com
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.51402207, 11502158) and the Scientific and Technological Innovation Programs of Higher Education Institutions in Shanxi Province, China(No.2015129)

摘要/Abstract

摘要：

利用溶剂热法, 基于氢氧化钾的插层作用制备了荧光氮化碳量子点(g-C₃N₄ QDs). 所获得的氮化碳量子点具有良好的水溶性和荧光稳定性. 透射电子显微镜(TEM)照片显示, 氮化碳量子点的粒径约为2.3 nm; X射线光电子能谱(XPS)和红外光谱(FTIR)结果表明, 氮化碳量子点表面存在大量的亲水基团; 荧光发射光谱(PL)结果表明, 氮化碳量子点具有激发波长依赖性. 基于三价铁离子(Fe³⁺)对荧光氮化碳量子点荧光的猝灭现象, 构建了一种用于检测Fe³⁺的荧光传感器, 在Fe³⁺浓度为5~100 μmol/L范围内, 检测体系表现出良好的线性关系, 检出限约为0.5 μmol/L, 实现了对Fe³⁺的高效、灵敏、选择性检测.

关键词: 离子插层, 氮化碳量子点, 三价铁离子, 荧光传感器

Abstract:

As a new kind of two dimensional nanomaterials, graphitic carbon nitride(g-C₃N₄) has extensively attracted interests due to the similar performance with grapheme. A solvothermal method of preparing fluorescent graphitic carbon nitride quantum dots(g-C₃N₄QDs) in the presence of KOH intercalation was developed in this paper. The obtained g-C₃N₄ QDs exhibited excellent water dispersity and fluorescence stability. Transmission electron microscopy(TEM) image showed the diameter of g-C₃N₄QDs was about 2.3 nm. There were large amounts of hydrophilic groups on the surface of g-C₃N₄QDs exhibited by X-ray photoelectron spectroscopy(XPS) and Fourier transform infrared(FTIR) spectrum analysis. Excitation-dependent photoluminescence behavior was observed by photoluminescence(PL) spectra. Owing to the phenomenon in which Fe³⁺ ions has great influence on the fluorescence quenching of g-C₃N₄ QDs, we proposed one fluorescent sensor for the detection of Fe³⁺ ions, and the detection system exhibited excellent liner relationship with the concentration of 5—100 μmol/L Fe³⁺ ions, the detection limit for Fe³⁺ ions was about 0.5 μmol/L, making a highly efficient and sensitive selection for Fe³⁺ ions.

Key words: Ions intercalation, Graphitic carbon nitride quantum dots, Ferric iron ion, Fluorescence senor

中图分类号:

O657

TrendMD:

战岩, 俎鸿儒, 黄棣, 刘应亮, 胡超凡. 溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe³⁺检测中的应用. 高等学校化学学报, 2017, 38(9): 1556.

ZHAN Yan, ZU Hongru, HUANG Di, LIU Yingliang, HU Chaofan. Synthesis of Fluorescent Graphitic Carbon Nitride Quantum Dots by Solvothermal Ions Intercalation Method for Fe(Ⅲ) Detection^†. Chem. J. Chinese Universities, 2017, 38(9): 1556.

图/表 7

Fig.1 SEM image of bulk g-C3N4(A), AFM image(B), TEM image(C) and size distribution(D) of g-C3N4 QDsInset of (B) is the height profile along the white line; insert of (C) is HRTEM image of g-C3N4 QDs.

Fig.2 FTIR spectrum of g-C3N4QDs(A) and XPS spectra of C1s(B), N1s(C) and O1s(D) of g-C3N4 QDs

Fig.3 UV-Vis absorption of g-C3N4 QDs(A), PL emission of g-C3N4 QDs with excitation wavelengths from 300 nm to 360 nm(B), PL excitation and emission spectra of g-C3N4 QDs(C) and photostability of g-C3N4 QDs under 310 nm excitation(D)Inserts of (A) are photographs of g-C3N4 QDs under 365 nm(left) and visible light(right).

Fig.4 Schematic illustration of the synthesis of g-C3N4QDs through solvothermal reaction in the presence of KOH

Fig.5 Fluorescence spectra of g-C3N4 QDs with the concentrations of Fe3+ from 0 to 100 μmol/L(A), relative intensity(F0-F)/F0 against Fe3+ concentration ranging from 0—100 μmol/L(B), fluorescence intensity of F/F0 in the presence of various metal ions at the concentration of 400 μmol/L(λex=310 nm)(C) and fluorescence intensity of F/F0 with 400 μmol/L different metal ions before(black bars) and after(red bars) mixing with 400 μmol/L Fe3+(D)(A) Concentration from top to bottom/(μmol·L-1): 0, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100; λex=310 nm; (C) a. blank; b. Al3+; c. Ca2+; d Cu2+; e. Fe2+; f. Hg2+; g. K+; h. Fe3+; i. Li+; j. Mg2+; k. Mn2+; l. Na+; m. Ni+; n. Zn2+. (D) a. Blank; b. Al3+; c. Ca2+; d. Cu2+; e. Fe2+; f. Hg2+; g. K+; h. Li+; i. Mg2+; j. Mn2+; k. Na+; l. Ni+; m. Zn2+.

Table 1 Comparison of the detection of Fe3+ with other fluorescent nano-probes

Detection probe	Ion detected	Linear range/(μmol·L^-1)	Detection limit/(μmol·L^-1)	Ref.
SN-CQDs	Fe³⁺	0—1000	0.10	[20]
GQDs	Fe³⁺	0—80	7.22	[30]
GO-nanosheets	Fe³⁺	14.3—143.2	17.50	[31]
NCQDs	Fe³⁺	0—50	4.67	[32]
g-C₃N₄ QDs	Fe³⁺	5—100	0.50	This work

Table 2 Detection of Fe3+ in real lake samples(n=5)

Sample	c(Fe³⁺added)/(μmol·L^-1)	c(Fe³⁺ found)/(μmol·L^-1)	Recovery(%)	RSD(%)
1	20.00	18.21	91.05	0.46
2	40.00	37.62	94.05	0.67
3	80.00	76.85	96.06	0.54

参考文献 32

[1]	Oh J., Yoo S. Y., Lee Y. J., Kim D. W., Park S., Chem.-Eur. J., 2015, 21, 6241—6246
[2]	Chimene D., Alge D. L., Gaharwar A. K., Adv. Mater., 2015, 27, 7261—7684
[3]	Heinz T. F., Hong S. S., Huang J., Ismach A. F., ACS Nano, 2013, 7, 2898—2926
[4]	Zhang X. D., Xie X., Wang H., Zhang J. J., Pan B. C., Xie Y., J. Am. Chem. Soc., 2013, 135, 18—21
[5]	Zhang Y.H., Pan Q. W., Chai G. Q., Liang M. R., Dong G. P., Zhang Q. Y., Qiu J. R., Sci. Rep., 2013,3, 1943
[6]	Liu Q. Q., Hu C. F., Wang X. M., RSC Adv., 2016, 6, 25605—25610
[7]	Hu C. F., Liu Y. L., Cui J. H., Huang Z. R., Wang Y. L., Yang L. F., Wang H. B., Xiao Y., Rong J. H., J. Mater. Chem. B, 2013, 1, 39—42
[8]	Hu C. F., Liu Y. L., Qin J. L., Nie G. T., Lei B. F., Xiao Y., Zheng M. T., Rong J. H., ACS Appl. Mater. Interfaces, 2013, 5, 4760—4768
[9]	Rong M. C., Song X. H., Zhao T. T., Wang Y. R., Chen X., J. Mater. Chem. C, 2015, 3, 10916—10924
[10]	Zhang S. W., Li J. X., Zeng M. Y., Xu J. Z., Wang X. K., Hu W. P., Nanoscale,2014, 6, 4157—4162
[11]	Zhou Z. X., Shen Y. F., Li Y., Liu A. R., Liu S. Q., Zhang Y. J., ACS Nano, 2015, 9, 12480—12487
[12]	Wang W. J., Yu J. C., Shen Z. R., Chan D. K. L., Gu T., Chem. Commun., 2014, 50, 10148—10150
[13]	Lin Z. Z., Wang X. C., Angew. Chem. Int. Ed., 2013, 52, 1735—1738
[14]	Bu Y. Y., Chen Z. W., Xie T., Li W. B., Ao J. P., RSC Adv., 2016, 6, 47813—47819
[15]	Bai X. J., Yan S. C., Wang J. J., Wang L., Jiang W. J., Wu S. L., Sun C. P., Zhu Y. F., J. Mater. Chem. A, 2014, 2, 17521—17529
[16]	Cao X. T., Ma J., Lin Y. P., Yao B. X., Li F. M., Weng W., Lin X. C., Spectrochim Acta A, 2015, 151, 875—880
[17]	Zhuang Q. F., Cao W., Wu Q., Ni Y. N., Chem. J. Chinese Universities, 2016, 37(9), 1611—1615
	(庄欠粉, 曹伟, 吴琦, 倪永年.高等学校化学学报,2016, 37(9), 1611—1615)
[18]	He J. L., Zhang H. R., Zou J. L., Liu Y. L., Zhuang J. L., Xiao Y., Lei B. F., Biosens. Bioelectron., 2015, 79, 531—535
[19]	Yu F., Qin L. Y., Shang Z. B., Dong Z. M., Wang Y., Jin W. J., Chem. Res. Chinese Universities, 2015, 31(6), 919—924
[20]	Zhang W. Y., Chang Q., Zhou Y. F., Wei Z. J., Li K. K., Hu S. L., Chinese J. Lumin., 2016, 37(4), 410—415
	(张文宇, 常青, 周雨锋, 魏志佳, 李凯凯, 胡胜亮.发光学报,2016, 37(4), 410—415)
[21]	Barman S., Sufhakhan M., J. Mater. Chem., 2012, 22, 21832—21837
[22]	Yang P. J., Zhao J. H., Wang J., Cao B. Y., Li L., Zhu Z. P., J. Mater. Chem. A, 2015, 3, 136—138
[23]	Wang Y. P., Li Y. K., Ju W., Wang J. C., Yao H. C., Zhang L., Wang J. S., Li Z. J., Carbon,2016, 102, 477—486
[24]	Xu J., Zhang L. W., Shi R., Zhu Y. F., J. Mater. Chem. A, 2013, 1, 14766—14772
[25]	Liu N. Y., Liu J., Kong W. Q., Li H., Huang H., Liu Y., Kang Z. H., J. Mater. Chem. B, 2014, 2, 5768—5744
[26]	Huang H., Jiang S. L., Chen S. C., Li D. D., Zhang X. D., Shao W., Sun X. S., Xie J. F., Zhao Z., Zhang Q., Tian Y. P., Xie Y., Adv. Mater., 2016, 28, 6940—6945
[27]	Shen J.H., Li Y. F., Su Y. H., Zhu Y. H., Jiang H. L., Yang X. L., Li C. Z., Nanoscale, 2015, 7,2003—2008
[28]	Brandrup J., Immergut E.H., Grulke E. A., Bloch D., Polymer Handbook, 4th Edition, Wiley-interscience, New York, 1999
[29]	Lin Y. W., Wang P., Univer. Chem., 2007, 22(1), 41—44
	(林英武, 王平.大学化学,2007, 22(1), 41—44)
[30]	Ananthanarayanan A., Wang X. W., Routh P., Sana B., Lim S., Kim D. H., Lim K. H., Li J., Chen P., Adv. Funct. Mater., 2014, 24, 3021—3026
[31]	Wang D., Wang L., Dong X., Shi Z., Jin J., Carbon, 2012, 50, 2147—2154
[32]	Yu J., Xu C.X., Tian Z. S., Lin Y., Shi Z. L., New. J. Chem., 2016, 40,20283—2088

溶剂热插层法制备荧光石墨相氮化碳量子点及其在Fe³⁺检测中的应用

Synthesis of Fluorescent Graphitic Carbon Nitride Quantum Dots by Solvothermal Ions Intercalation Method for Fe(Ⅲ) Detection^†

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