荧光性多孔芳香骨架材料的简便制备及在硝基爆炸物检测中的应用

doi:10.7503/cjcu20190284

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (12): 2456-2464.doi: 10.7503/cjcu20190284

• 研究论文: 无机化学 • 上一篇下一篇

荧光性多孔芳香骨架材料的简便制备及在硝基爆炸物检测中的应用

夏立新¹,张红翠¹,冯彬¹,杨东奇¹,布乃顺²,赵云波¹,闫卓君^1,^*(),李樟楠³,元野³,赵晓君^4,^*()

^1. 辽宁大学化学院, 沈阳 110036
^2. 辽宁大学环境学院, 沈阳 110036
^3. 东北师范大学多酸科学教育部重点实验室, 长春 130024
^4. 海南大学理学院, 海口 570228

收稿日期:2019-05-17 出版日期:2019-12-04 发布日期:2019-12-04
通讯作者: 闫卓君,赵晓君 E-mail:zjyan@lnu.edu.cn;zhaox@hainanu.edu.cn
基金资助:
国家自然科学基金(21704037);国家自然科学基金(21671089);国家自然科学基金(31972522);沈阳市自然科学基金(F16-103-4-00);辽宁省科研基金(LT2017010);辽宁省科研基金(20170540409);辽宁省博士启动基金(20170520069);吉林省科技发展计划项目(批准号: 20180520158H)(20180J20158H);东北师范大学多酸科学教育部重点实验室开放基金资助.

Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives ^†

Lixin XIA¹,Hongcui ZHANG¹,Bin FENG¹,Dongqi YANG¹,Naishun BU²,Yunbo ZHAO¹,Zhuojun YAN^1,^*(),Zhangnan LI³,Ye YUAN³,Xiaojun ZHAO^4,^*()

^1. College of Chemistry, Liaoning University, Shenyang 110036, China
^2. School of Environmental Science, Liaoning University, Shenyang 110036, China
^3. Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal University, Changchun 130024, China
^4. School of Sciences, Hainan University, Haikou 570228, China

Received:2019-05-17 Online:2019-12-04 Published:2019-12-04
Contact: Zhuojun YAN,Xiaojun ZHAO E-mail:zjyan@lnu.edu.cn;zhaox@hainanu.edu.cn
Supported by:
? Supported by the National Natural Science Foundation of China(21704037);the National Natural Science Foundation of China(21671089);the National Natural Science Foundation of China(31972522);the Natural Science Foundation of Shenyang City, China(F16-103-4-00);the Scientific Research Fund of Liaoning Province, China(LT2017010);the Scientific Research Fund of Liaoning Province, China(20170540409);the Scientific Research Starting Foundation for Doctor of Liaoning Province, China(No.2017050069);the Project of Scientific and Technological Development of Jilin Province, China(No.20180J20158H)(20180J20158H);the Opening Project of the Key Laboratory of Polyoxometalate Science of Ministry of Education, Northeast Normal Universitity, China.

摘要/Abstract

摘要：

报道了一种简便的制备高荧光性多孔有机聚合物材料的方法, 即以1,3,6,8-四溴芘(TBrPy)与硼酸类单体为构筑基元, 通过Suzuki偶联反应制备多孔芳香骨架材料LNUs. 利用傅里叶变换红外光谱、热重分析、氮气吸附、固体紫外光谱和荧光光谱等分析方法对其结构与性能进行了系统表征. 分析结果表明, 该类多孔芳香骨架材料具有良好的热化学稳定性和较大的比表面积, 所得材料优异的荧光性能使其非常适合用于硝基爆炸物的选择性检测. 多孔芳香骨架材料LNUs在苯、溴苯、苯胺、甲苯、氯苯和苯酚等分子存在下, 荧光强度基本不变, 而在加入硝基苯、对硝基苯酚和对硝基氯苯后, 荧光几乎完全猝灭, 说明该类材料对硝基苯、对硝基苯酚和对硝基氯苯显示出专一的检测性能. 根据这一特性, 利用LNUs材料制备了一种新型便携式纸传感器, 其可以简便快速实时检测硝基爆炸物, 并在痕量检测方面展现出良好的应用前景.

关键词: 荧光性能, 多孔芳香骨架, 硝基爆炸物, 荧光猝灭, 传感器

Abstract:

Three fluorescent porous aromatic framework materials donated as LNU-9, LNU-10, and LNU-11 were prepared via Suzuki coupling reactions of 1,3,6,8-tetrabromofluorene(TBrPy) with boric acid monomers. The structures and properties of the LNUs were characterized by Fourier transform infrared spectro-scopy(FTIR), thermogravimetric analysis(TGA), nitrogen adsorption-desorption, solid ultraviolet spectroscopy and fluorescence spectroscopy. The disappearance of vibration peaks at 1349, 1144, 495 cm ^-1 in FTIR spectrum is attributed to the breakage of C—Br and C—B(OH)₂ bonds, respectively, indicating the complete polymerization of building monomers into porous skeletons. Powder X-ray diffraction(PXRD) and transmission electron microscopy(TEM) images reveal all the LNUs have amorphous structure. The thermogravimetric ana-lysis results demonstrate the excellent thermal stability of LNUs. In addition, these materials exhibit high chemical stability, as verified by no dissolution or decomposition in various organic solvents such as methanol, ethanol, tetrahydrofuran, acetone, dichloromethane, chloroform, N,N'-dimethylformamide, dimethylsulfoxide, etc. Besides, their large specific surface areas in the range of 800—1500 m ²/g and excellent fluorescence properties make them suitable for the detection of specific nitro explosives. After benzene, bromobenzene, aniline, toluene, chlorobenzene and phenol were added into the methanol solution of LNUs respectively, the luminescence intensity had little change, demonstrating there is no specific interaction between porous skeleton and organic substances. On the contrast, fluorescence of LNUs was almost completely quenched in the respective solution of nitrobenzene, p-nitrophenol, and p-nitrochlorobenzene, indicating the selective detection capability for nitro compounds of the LNUs. Based on these results, we prepared a novel portable paper sensor which realized the facile and rapid real-time detection of nitro explosives, demonstrating an impressive pro-spect in trace detection.

Key words: Fluorescence property, Porous aromatic framework, Nitro explosive, Luminescence quenching, Sensor

中图分类号:

O613

夏立新,张红翠,冯彬,杨东奇,布乃顺,赵云波,闫卓君,李樟楠,元野,赵晓君. 荧光性多孔芳香骨架材料的简便制备及在硝基爆炸物检测中的应用[J]. 高等学校化学学报, 2019, 40(12): 2456-2464.

Lixin XIA,Hongcui ZHANG,Bin FENG,Dongqi YANG,Naishun BU,Yunbo ZHAO,Zhuojun YAN,Zhangnan LI,Ye YUAN,Xiaojun ZHAO. Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives ^†[J]. Chemical Journal of Chinese Universities, 2019, 40(12): 2456-2464.

图/表 14

Scheme 1 Schematic illustration of syntheses of LNU-9, LNU-10 and LNU-11

Fig.1 FTIR spectra for polymer networks(a) and respective starting materials, 1,3,6,8-tetrabromopyrene(b), tris 4-boronic acid pinacol ester phenyl amine(c1), 9,9-dimethyl-2,7-bis(boronicacid pinacol ester) fluorene(c2) and 1,3,5-benzene triboronic acid tripinacol ester(c3) from 400 cm-1 to 4000 cm-1

Fig.2 13C CP/MAS NMR spectra of LNU-9(A), LNU-10(B) and LNU-11(C)

Fig.3 PXRD patterns of LNU-9(a), LNU-10(b) and LNU-11(c)

Fig.4 SEM(A—C) and TEM(D—F) images of LNU-9(A,D), LNU-10(B,E) and LNU-11(C, F)

Fig.5 TG plots for LNU-9(a), LNU-10(b) and LNU-11(c) in air with the heat rate of 5 ℃/min

Fig.6 Nitrogen adsorption-desorption isotherms at 77 K(A) and pore size distributions(B) of LNU-9, LNU-10 and LNU-11

Fig.7 CO2 adsorption-desorption isotherms at 273 and 298 K for LNU-9(A), LNU-10(B) and LNU-11(C)

Fig.8 UV-Vis absorption spectra for the monomer TBrPy and the three LNU polymers a. LNU-9; b. LNU-10; c. LNU-11; d. TBrPy.

Fig.9 Fluorescent emission spectra of LNU-9(A), LNU-10(B) and LNU-11(C)(0.4 mg/mL in methanol) in the presence of different compounds

Fig.10 Fluorescent emission spectra of the methanol solution of LNU-9 upon addition of nitrobenzene(A), p-nitrophenol(B) and p-nitrochlorobenzene(C) at different concentrations(excited at 410 nm) Concentrations of nitrobenzene, p-nitrophenol or p-nitrochloroberzene/(mg·L-1): a. 0; b. 200; c. 1000; d. 2000;e. 5000; f. 10000; g. 15000.

Fig.11 Fluorescent emission spectra of the methanol solution of LNU-10 upon addition of nitrobenzene(A), p-nitrophenol(B) and p-nitrochlorobenzene(C) at different concentrations(excited at 410 nm) Concentrations of nitrobenzene, p-nitrophenol or p-nitrochloroberzene/(mg·L-1): a. 0; b. 200; c. 1000; d. 2000; e. 5000; f. 10000; g. 15000.

Fig.12 Fluorescent emission spectra of the methanol solution of LNU-11 upon addition of nitrobenzene(A), p-nitrophenol(B) and p-nitrochlorobenzene(C) at different concentrations(excited at 402 nm) Concentrations of nitrobenzene, p-nitrophenol or p-nitrochloroberzene/(mg·L-1): a. 0; b. 200; c. 1000; d. 2000;e. 5000; f. 10000; g. 15000.

Scheme 2 Schematic representation of paper sensor for detecting nitrobenzene vapor(Ⅰ) and solid nitrobenzene(Ⅱ)

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荧光性多孔芳香骨架材料的简便制备及在硝基爆炸物检测中的应用

Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives ^†

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荧光性多孔芳香骨架材料的简便制备及在硝基爆炸物检测中的应用

Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives †

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Facile Strategy to Prepare Fluorescent Porous Aromatic Frameworks for Sensitive Detection of Nitroaromatic Explosives ^†