N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe3+检测

doi:10.16085/j.issn.1000-6613.2022-1911

化工进展 ›› 2023, Vol. 42 ›› Issue (9): 4799-4807.DOI: 10.16085/j.issn.1000-6613.2022-1911

N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测

雷伟¹(), 姜维佳²^,³(), 王玉高¹(), 和明豪¹, 申峻¹

^1.太原理工大学化学工程与技术学院，山西太原 030024
^2.山西中医药大学基础医学学院，山西晋中 030619
^3.山西大学环境科学研究所，山西太原 030006

收稿日期:2022-10-14 修回日期:2022-12-04 出版日期:2023-09-15 发布日期:2023-09-28
通讯作者: 姜维佳,王玉高
作者简介:雷伟（1996—），男，硕士研究生，研究方向为碳量子点制备及应用。E-mail：2799108581@qq.com。
基金资助:
国家自然科学基金青年基金(21706172);山西省基础研究计划(20210302123167)

Synthesis of N,S co-doped coal-based carbon quantum dots by electrochemical oxidation and its application in Fe³⁺ detection

LEI Wei¹(), JIANG Weijia²^,³(), WANG Yugao¹(), HE Minghao¹, SHEN Jun¹

^1.College of Chemical Engineering and Technology, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.College of Basic Medical Sciences, Shanxi University of Chinese Medicine, Jinzhong 030619, Shanxi, China
^3.Institute of Environmental Sciences, Shanxi University, Taiyuan 030006, Shanxi, China

Received:2022-10-14 Revised:2022-12-04 Online:2023-09-15 Published:2023-09-28
Contact: JIANG Weijia, WANG Yugao

摘要/Abstract

摘要：

异质元素掺杂可以有效改善碳量子点的荧光性能，被广泛应用于碳量子点的改性。选取昭通褐煤为碳源，氯化钠溶液为电解液，硫脲为助剂，采用电化学氧化法完成N、S共掺杂碳量子点（N,S-CQD）的制备，荧光量子产率为1.60%。采用多种表征方法研究了N,S-CQD的结构、组成和光学特性。首先在结构组成方面，N,S-CQD是一类球形颗粒，尺寸分布均匀，平均粒径为1.66nm，其中主要存在C、O元素，还存在部分N和S元素；其次在光学性质方面，N,S-CQD在紫外光区吸收明显，荧光分析显示其最佳激发波长为280nm，最佳发射波长为313nm。最后基于Fe³⁺对N,S-CQD的荧光猝灭效应，将N,S-CQD应用于痕量Fe³⁺的检测，N,S-CQD对15~150μmol/L浓度范围内Fe³⁺的检测表现出较高的选择性和灵敏度，通过计算得出最低检出限L=1.22μmol/L，表明N,S-CQD可应用于痕量Fe³⁺的检测。

关键词: 褐煤, 掺杂碳量子点, 电化学氧化法, Fe³⁺检测

Abstract:

Heterogeneous element doping is widely used in the modification of carbon quantum dots (CQDs) due to improving the fluorescence properties of CQDs. In this study, the nitrogen and sulfur co-doped carbon quantum dots (N,S-CQD) was prepared by electrochemical oxidation, in which Zhaotong lignite was selected as the carbon source, sodium chloride solution as the electrolyte and thiourea as the auxiliary respectively. The fluorescence quantum yield was 1.60%. The structure, composition and optical properties of N,S-CQD were studied by a variety of spectroscopic methods. N,S-CQDs were spherical particles with uniform size distribution and an average particle size of 1.66nm, in which C and O elements dominated as well as a certain amount of N and S elements. N,S-CQDs significantly absorbed in the UV region, and fluorescence analysis indicated that their optimum excitation wavelength and the emission wavelength located at 280nm and 313nm, respectively. N,S-CQDs were then applied to the detection of trace Fe³⁺ based on the quenching effect of Fe³⁺ on the fluorescence intensity. N,S-CQDs exhibited high selectivity and sensitivity for Fe³⁺ with the concentration range of 15—150μmol/L, and the minimum detection limit (L) was calculated to be 1.22μmol/L, indicating that N,S-CQDs could be utilized as a reliable candidate material for detecting trace Fe³⁺.

Key words: lignite, doped carbon quantum dots, electrochemical oxidation, Fe³⁺ detection

中图分类号:

TQ536.9

雷伟, 姜维佳, 王玉高, 和明豪, 申峻. N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测[J]. 化工进展, 2023, 42(9): 4799-4807.

LEI Wei, JIANG Weijia, WANG Yugao, HE Minghao, SHEN Jun. Synthesis of N,S co-doped coal-based carbon quantum dots by electrochemical oxidation and its application in Fe³⁺ detection[J]. Chemical Industry and Engineering Progress, 2023, 42(9): 4799-4807.

图/表 14

图1 掺杂碳量子点制备流程

表1 ZT的工业分析与元素分析（质量分数）

工业分析 /%				元素分析_daf/%					C/H^②
M_ad	A_ad	V_daf		C	H	N	S	O^①	C/H^②
7.46	14.55	55.04		66.88	5.12	1.57	0.83	25.60	1.09

图2 ZT的FTIR谱图

图3 无助剂及四种助剂掺杂后的碳量子点的QY对比

图4 N,S-CQD的TEM图及尺寸分布

图5 N,S-CQD的FTIR谱图

图6 N,S-CQD的XPS全谱及各分峰谱图

表2 N,S-CQD表面各元素相对含量 (%)

C	O	N	Cl	S
55.69	29.18	6.29	3.44	5.40

表3 N,S-CQD的C、O、N和S的吸收峰及其归属

元素峰	峰号	结合能/eV	归属	峰面积占比/%
C1s	1	284.60	C $̿$ C	39.62
	2	285.13	C—N/C—S	33.25
	3	286.29	C—O	16.38
	4	288.30	C $̿$ O	10.75
O1s	1	531.20	C $̿$ O	21.86
	2	531.80	C—O	42.58
	3	532.54	—OH	35.56
N1s	1	398.92	吡啶氮	25.52
	2	399.52	氨基氮	37.15
	3	400.12	吡咯氮	37.33
S2p	1	162.44	C—S的2p_3/2	12.15
	2	163.60	C—S的2p_1/2	8.15
	3	168.70	C—SO $3 -$	55.20
	4	169.80	C—SO $4 -$	24.50

表3 N,S-CQD的C、O、N和S的吸收峰及其归属

元素峰	峰号	结合能/eV	归属	峰面积占比/%
C1s	1	284.60	C $̿$ C	39.62
	2	285.13	C—N/C—S	33.25
	3	286.29	C—O	16.38
	4	288.30	C $̿$ O	10.75
O1s	1	531.20	C $̿$ O	21.86
	2	531.80	C—O	42.58
	3	532.54	—OH	35.56
N1s	1	398.92	吡啶氮	25.52
	2	399.52	氨基氮	37.15
	3	400.12	吡咯氮	37.33
S2p	1	162.44	C—S的2p_3/2	12.15
	2	163.60	C—S的2p_1/2	8.15
	3	168.70	C—SO $3 -$	55.20
	4	169.80	C—SO $4 -$	24.50

图7 N,S-CQD的紫外可见吸收光谱和荧光激发光谱、发射光谱

图8 不同pH下N,S-CQD的荧光强度

图9 不同N,S-CQD体系的荧光光谱和加入不同金属离子后N,S-CQD的相对荧光强度

图10 不同Fe3+浓度下N,S-CQD的荧光谱图和ΔF与Fe3+浓度的线性拟合

图11 不同N,S-CQD体系的FTIR谱图和N,S-CQD与不同含量的Fe3+混合体系的紫外光谱

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N、S共掺杂煤基碳量子点的电化学氧化法制备及用于Fe³⁺检测

Synthesis of N,S co-doped coal-based carbon quantum dots by electrochemical oxidation and its application in Fe³⁺ detection

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