一种可用于检测水中Cu2+的锌配位聚合物荧光传感器

doi:10.16085/j.issn.1000-6613.2024-0613

化工进展 ›› 2024, Vol. 43 ›› Issue (10): 5686-5692.DOI: 10.16085/j.issn.1000-6613.2024-0613

• 材料科学与技术 • 上一篇

一种可用于检测水中Cu²⁺的锌配位聚合物荧光传感器

白羽婷¹(), 魏晓阳², 尤雪瑞¹, 张志超¹, 韩美荣³, 郭湘⁴, 赵艺妍⁴()

^1.山西能源学院能源化学与材料工程系，山西晋中 030600
^2.山西大学分子科学研究所，山西太原 030006
^3.山西工程职业学院现代化工系，山西太原 030001
^4.山西白求恩医院(山西医学科学院同济山西医院)山西医科大学第三医院，山西太原 030032

收稿日期:2024-04-11 修回日期:2024-05-20 出版日期:2024-10-15 发布日期:2024-10-29
通讯作者: 赵艺妍
作者简介:白羽婷（1994—），女，博士，讲师，研究方向为配合物的制备及在光催化和传感方面的应用。E-mail：baiyt@sxie.edu.cn。
基金资助:
山西省基础研究计划(202203021222348);山西省高等学校科技创新项目(2023L406);山西能源学院院级科研基金(ZB-2023006)

A zinc coordination polymer fluorescence sensor for detecting Cu²⁺ in water

BAI Yuting¹(), WEI Xiaoyang², YOU Xuerui¹, ZHANG Zhichao¹, HANG Meirong³, GUO Xiang⁴, ZHAO Yiyan⁴()

^1.Department of Energy Chemistry and Materials Engineering, Shanxi Institute of Energy, Jinzhong 030600, Shanxi, China
^2.Institute of Molecular Science, Shanxi University, Taiyuan 030006, Shanxi, China
^3.Department of Modern Chemical Engineering, Shanxi Engineering Vocational College, Taiyuan 030001, Shanxi, China
^4.Shanxi Bethune Hospital, Shanxi Academy of Medical Sciences, Tongji Shanxi Hospital, Third Hospital of Shanxi Medical University, Taiyuan 030032, Shanxi, China

Received:2024-04-11 Revised:2024-05-20 Online:2024-10-15 Published:2024-10-29
Contact: ZHAO Yiyan

摘要/Abstract

摘要：

铜离子（Cu²⁺）作为一种重金属在人体中起着关键作用，但是过量的Cu²⁺会诱发各种疾病，危害人体健康。因此，开发快速、灵敏检测Cu²⁺的新型荧光传感器非常重要。本文以1,4-双(3,5-二羧基苯氧基)苯（H₄L）为主配体，邻菲啰啉（phen）为辅配体通过水热法成功制备了一维链状锌配位聚合物（Zn-CP），可作为高效检测水中Cu²⁺的荧光传感器。该Zn-CP具有优异的荧光特性，可通过荧光猝灭作用特异、灵敏地检测水溶液中的Cu²⁺。在0~0.8×10^-6mol/L的范围内，Cu²⁺浓度与传感器的荧光衰减呈现良好的线性关系，检出限为1.22×10^-8mol/L，低于美国环境保护署规定的限值（2.05×10^-5mol/L）。此外，Zn-CP在Cu²⁺检测中的猝灭机理可归因于配位聚合物与Cu²⁺之间形成新的化学键。这项工作为构建具有水稳定系的配位聚合物类荧光传感器提供了一种新的策略。

关键词: 配位聚合物, 过渡金属, 水热, 制备, 荧光探针, 环境

Abstract:

As a heavy metal, copper ion (Cu²⁺) plays a key role in human bodies, but excessive Cu²⁺ can induce various diseases and endanger human health. Therefore, it is important to develop new fluorescent sensors to detect Cu²⁺ rapidly and sensitively. One-dimensional chain zinc coordination polymer (Zn-CP) was successfully prepared by hydrothermal method using 1,4-bis(3,5-dicarboxy phenoxy) benzene (H₄L) as the primary ligand and 1,10-phenanthroline (phen) as the secondary ligand, which can be used as a fluorescence sensor for the efficient detection of Cu²⁺ in water. The Zn-CP possessed excellent fluorescent properties and can selectively and sensitively detect Cu²⁺ in aqueous solutions through luminescence quenching. In the range of 0—0.8×10^-6mol/L, the Cu²⁺ concentration showed a good linear relationship with the fluorescence attenuation of the sensor and the detection limit was 1.22×10^-8mol/L, which was lower than the limit set by the US Environmental Protection Agency (2.05×10^-5mol/L). In addition, the quenching mechanism of Zn-CP in Cu²⁺ detection may be attributed to the formation of new chemical bonds between the coordination polymers and the Cu²⁺. This work provided a new strategy for the construction of coordination polymer-based fluorescence sensors with water-stable systems.

Key words: coordination polymers, transition metals, hydrothermal, preparation, fluorescent probes, environment

中图分类号:

O625

白羽婷, 魏晓阳, 尤雪瑞, 张志超, 韩美荣, 郭湘, 赵艺妍. 一种可用于检测水中Cu²⁺的锌配位聚合物荧光传感器[J]. 化工进展, 2024, 43(10): 5686-5692.

BAI Yuting, WEI Xiaoyang, YOU Xuerui, ZHANG Zhichao, HANG Meirong, GUO Xiang, ZHAO Yiyan. A zinc coordination polymer fluorescence sensor for detecting Cu²⁺ in water[J]. Chemical Industry and Engineering Progress, 2024, 43(10): 5686-5692.

图/表 15

参考文献 23

1	ZHANG Meng, ZHANG Jianhong, CHE Xin, et al. Biomimetic mineralization-based in situ growth of AuNCs@ZIF-8 on paper fibers for visual detection of copper ions[J]. Talanta, 2024, 268: 125364.
2	ZHANG Yibin, Jia MIU, WANG Boling, et al. A novel near-infrared fluorescent probe based on the dicyanoisophorone for the selective detection of Cu²⁺ in real water samples[J]. Journal of Molecular Structure, 2023, 1286: 135632.
3	PARK Seonmin, BONG So Yeon, SHARMA Shilpa, et al. Simple turn-on fluorescent chemosensor for ultrafast and highly selective trace-level detection of Cu²⁺ ions in aqueous solutions[J]. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 2024, 305: 123555.
4	MA Ting, LIU Mingzhu, SUN Jingran, et al. N-doped molybdenum oxide quantum dots as fluorescent probes for the quantitative detection of copper ions in environmental samples[J]. Analytical Methods, 2023, 15(45): 6239-6244.
5	董佳佳, 薛松松. 新型三苯胺类Cu²⁺荧光探针的合成及性能研究[J]. 化工新型材料, 2023, 51(S2): 659-664.
	DONG Jiajia, XUE Songsong. Synthesis and properties of novel triphenylamine Cu²⁺ fluorescent probes[J]. New Chemical Materials, 2023, 51(S2): 659-664.
6	LI Xiangqian, YANG Peiying, ZHAO Yuxin, et al. Antibiotic identification in aqueous solution by a two-dimensional cadmium-based coordination polymer with excellent fluorescence properties[J]. Polyhedron, 2024, 250: 116818.
7	WANG Yuna, ZHANG Xiaofeng, ZHAO Yanru, et al. Three novel Zn-based coordination polymers: Synthesis, structure, and effective detection of Al³⁺ and S^2- ions[J]. Molecules, 2020, 25(2): 382.
8	WANG Dan, DU Linhuan, LI Long, et al. Zn(Ⅱ)-based mixed-ligand-bearing coordination polymers as multi-responsive fluorescent sensors for detecting dichromate, iodide, nitenpyram, and imidacloprid[J]. Polymers, 2023, 15(11): 2570.
9	张艳. 一例由BMIP和1, 4-BDF混合配体构筑的Zn(Ⅱ)配位聚合物、晶体结构及其性能[J]. 化学研究与应用, 2024, 36(2): 323-330.
	ZHANG Yan. A Zn(Ⅱ)coordination polymer constructed by mixed ligands of BMIP and 1,4-BDF, crystal structure and properties[J]. Chemical Research and Application, 2024, 36(2): 323-330.
10	KLONGDEE Fatima, YOUNGME Sujittra, BOONMAK Jaursup. A luminescent sensor based on zinc(Ⅱ) 1D chain coordination polymer for effective acetone detection[J]. Polyhedron, 2020, 180: 114437.
11	ZHANG Yatong, WANG Ai, HUANG Bing, et al. A Zn-coordination polymer for the quantitative and selective colorimetric detection of residual tetracycline in aqueous solution and urine[J]. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 2023, 294: 122470.
12	YU Xiaoyan, DONG Wenwen, HAN Huimin, et al. A water-stable Zn (Ⅱ) coordination polymer as fluorescent sensor for selective and sensitive detection of antibiotics and Fe³⁺ [J]. Journal of Solid State Chemistry, 2021, 296: 122032.
13	QI Shengsheng, LI Zhang, JIA Yuejiao, et al. A Zn-coordination polymer as a multifunctional fluorescent probe for the detection of V₂O₇ ^4-, Fe³⁺, and p-nitrotoluene[J]. Physical Chemistry Chemical Physics, 2023, 25(14): 10090-10096.
14	SUN Zan, SUN Juan, XI Lu, et al. Two novel lanthanide metal organic frameworks: Selective luminescent sensing for nitrobenzene, Cu²⁺, and MnO₄ ^- [J]. Crystal Growth & Design, 2020, 20(8): 5225-5234.
15	ZHANG Xiaofei, FENG Lihui, MA Shiyu, et al. A microporous Tb-based MOF for multifunctional detection of the α-CHC, Cu²⁺ and Fe³⁺ [J]. Journal of Solid State Chemistry, 2022, 312: 123232.
16	LUO Jun, LIU Baoshu, ZHANG Yunchang, et al. A new fluorescent probe constructed by europium(Ⅲ)-organic framework (Eu-MOF) for detecting Cu²⁺ selectively and sensitively[J]. Journal of Molecular Structure, 2023, 1274: 134460.
17	WAN Xiaoyu, ZHANG Yifan, WANG Huaiwei, et al. One amino-functionalized luminescence sensor demonstrating high sensitivity and selectivity for detecting Al³⁺ and Cu²⁺ as well as its luminescent mixed matrix membranes and test papers[J]. Journal of Solid State Chemistry, 2022, 305: 122705.
18	ZHANG Ensheng, JIANG Long, Ruijiang LYU, et al. The design, synthesis and fluorescent sensing applications of a thermo-sensitive Zn-MOF[J]. Journal of Solid State Chemistry, 2021, 303: 122476.
19	HAN Meirong, DONG Wenxia, FENG Sisi, et al. An ultra-sensitive selective fluorescent sensor based on a 3D zinc-tetracarboxylic framework for the detection and enrichment of trace Cu²⁺ in aqueous media[J]. Dalton Transactions, 2021, 50(14): 4944-4951.
20	WANG Ruidong, ZHANG Wenqian, ZHOU Sihan, et al. A novel dual-functional coordination polymer for detection and ultra-effectively removal of Fe(Ⅲ) in water[J]. Journal of Molecular Liquids, 2022, 355: 118942.
21	MI Xiuna, SHENG Dafei, YU Yu’e, et al. Tunable light emission and multiresponsive luminescent sensitivities in aqueous solutions of two series of lanthanide metal-organic frameworks based on structurally related ligands[J]. ACS Applied Materials Interfaces, 2019, 11(8): 7914-7926.
22	YAO Bin, WEI Yuan, LI Ceng, et al. A mixed-ligand Zn(‍Ⅱ)-coordination polymer: Selective detection of Fe³⁺ ion and promotion activity on the flap transplantation via increasing the vascular endothelial cells proliferation[J]. Journal of the Iranian Chemical Society, 2021, 18(10): 2597-2604.
23	WANG Cong, REN Guojian, TAN Qinyue, et al. Detection of organic arsenic based on acid-base stable coordination polymer[J]. Spectrochimica Acta A: Molecular and Biomolecular Spectroscopy, 2023, 299: 122812.

项目	值
分子式	C₄₆H₃₀Zn₂N₄O₁₂
分子量	961.48
温度/K	293
晶系	Monoclinic
空间群	C2/c
晶胞参数/Å	a=48.060 (16), b=9.901 (4), c=18.224 (5), α=90.00, β=111.216 (17), γ=90.00
体积/Å³	8084 (5)
Z	8
μ/mm^-1	1.26
晶体大小/mm³	0.23×0.18×0.12
R_int	0.176
F (000)	3920
D_c/g·cm^-3	1.580
R₁[F²>2σ(F²)]	0.076
wR₂ (F²)	0.199
S	1.10
Δρ_{max, min}/e·Å^-3	1.06, -0.60

项目	值
分子式	C₄₆H₃₀Zn₂N₄O₁₂
分子量	961.48
温度/K	293
晶系	Monoclinic
空间群	C2/c
晶胞参数/Å	a=48.060 (16), b=9.901 (4), c=18.224 (5), α=90.00, β=111.216 (17), γ=90.00
体积/Å³	8084 (5)
Z	8
μ/mm^-1	1.26
晶体大小/mm³	0.23×0.18×0.12
R_int	0.176
F (000)	3920
D_c/g·cm^-3	1.580
R₁[F²>2σ(F²)]	0.076
wR₂ (F²)	0.199
S	1.10
Δρ_{max, min}/e·Å^-3	1.06, -0.60

配位聚合物	检出限/mol·L^-1	文献
{[Eu₂(L2)₂(H₂O)₅]·3H₂O} _n	3.3×10^-6	[14]
[Tb₄(TATB)₂]	2.92×10^-6	[15]
[Eu₄(MTB)₃(DMF)₆]·2DMF	1.98×10^-6	[16]
[Zn(L1)(bpea)] _n	1.96×10^-6	[17]
[Zn(cca)_0.5(TPB)_0.5(H₂O)₂]·(NO₃)·(H₂O)₂	0.67×10^-6	[18]
[Zn₃(μ₃-Hbptc)₂(μ₂-4,4′-bpy)₂(H₂O)₄] _n ·2nH₂O	3.24×10^-8	[19]
[Zn₂(L)(phen)₂(H₂O)]·H₂O	1.22×10^-8	本工作

配位聚合物	检出限/mol·L^-1	文献
{[Eu₂(L2)₂(H₂O)₅]·3H₂O} _n	3.3×10^-6	[14]
[Tb₄(TATB)₂]	2.92×10^-6	[15]
[Eu₄(MTB)₃(DMF)₆]·2DMF	1.98×10^-6	[16]
[Zn(L1)(bpea)] _n	1.96×10^-6	[17]
[Zn(cca)_0.5(TPB)_0.5(H₂O)₂]·(NO₃)·(H₂O)₂	0.67×10^-6	[18]
[Zn₃(μ₃-Hbptc)₂(μ₂-4,4′-bpy)₂(H₂O)₄] _n ·2nH₂O	3.24×10^-8	[19]
[Zn₂(L)(phen)₂(H₂O)]·H₂O	1.22×10^-8	本工作

溶液	Zn²⁺/%	Cu²⁺/%
Zn-CP	13.60	0.00
Zn-CP@Cu²⁺	12.70	5.13

一种可用于检测水中Cu²⁺的锌配位聚合物荧光传感器

A zinc coordination polymer fluorescence sensor for detecting Cu²⁺ in water

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 23

相关文章 15

编辑推荐

Metrics

本文评价

[1]	申纯宇, 李翠利, 汤建伟, 刘咏, 刘鹏飞, 丁俊祥, 申博, 王保明. 纳米氢氧化镁制备及其阻燃应用进展[J]. 化工进展, 2024, 43(9): 4980-4995.
[2]	吴剑扬, 王汝娜, 陈耀, 申兰耀, 于永利, 蒋宁, 邱景义, 周恒辉. 锂离子电池高镍正极材料前体的制备工艺[J]. 化工进展, 2024, 43(9): 5079-5085.
[3]	潘涵婷, 徐洪涛, 许多, 罗祝清. 低温条件下基于相变材料的锂离子电池保温特性分析[J]. 化工进展, 2024, 43(8): 4333-4341.
[4]	尹俊权, 吴寅凯, 李卫华, 孙英杰, 张闻轩, 张庆建, 马晓腾, 卞荣星, 王华伟. 垃圾焚烧典型工段灰/渣理化特性及环境风险性[J]. 化工进展, 2024, 43(8): 4714-4725.
[5]	卞维柏, 张睿轩, 潘建明. 无机金属锂离子筛材料制备方法研究进展[J]. 化工进展, 2024, 43(8): 4173-4186.
[6]	胡锐, 李先如, 朴玮玲, 冯盼, 罗磊, 罗刚, 卫皇曌, 刘振刚, 张士成. 有机废物水热转化设备与技术研究进展[J]. 化工进展, 2024, 43(7): 3672-3691.
[7]	王丽娜, 武金升. 共价有机框架材料的合成与应用研究进展[J]. 化工进展, 2024, 43(7): 3834-3856.
[8]	周爱国, 郑家乐, 杨川箬, 杨小艺, 赵俊德, 李兴春. 直接空气二氧化碳捕集技术工业化进展[J]. 化工进展, 2024, 43(6): 2928-2939.
[9]	李莹莹, 刘安, 姜乐妍, 李晖, 陈春钰, 居殿春. 过渡金属硫化物Co₉S₈的制备及电化学性能研究进展[J]. 化工进展, 2024, 43(6): 3114-3127.
[10]	李晶莹, 马龙飞, 潘一搏, 卢山, 张红娟, 徐龙, 马晓迅. 焦炉煤气脱碳法及甲烷化法制液化天然气的生命周期环境影响分析[J]. 化工进展, 2024, 43(5): 2872-2879.
[11]	张国卿, 宋舒波, 王兴瑞, 巩苗苗, 王旭, 许宇鸿, 冯继越, 张福扬, 陈汇勇. 煤固废基分子筛的制备及其应用进展[J]. 化工进展, 2024, 43(5): 2311-2323.
[12]	黄坤, 许明, 吴秀娟, 裴思佳, 刘大伟, 马晓迅, 徐龙. 生物质活性炭的制备与微结构特性调控研究进展[J]. 化工进展, 2024, 43(5): 2475-2493.
[13]	张宝, 王鹏, 安勇攀, 吕平, 蒋建良. 船舶应用燃料电池系统的设计与试验[J]. 化工进展, 2024, 43(5): 2554-2567.
[14]	李娜, 赵婉彤, 凌丽霞, 王宝俊, 章日光. RhCu催化剂中限域环境调控合成气转化生成CH _x 反应性能[J]. 化工进展, 2024, 43(5): 2684-2695.
[15]	齐亚兵, 吴子波, 杨清翠. Pickering乳液制备及稳定性研究进展[J]. 化工进展, 2024, 43(4): 2017-2030.