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

doi:10.7503/cjcu20190284

Abstract

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

CLC Number:

O613

TrendMD:

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]. Chem. J. Chinese Universities, 2019, 40(12): 2456.

Figures/Tables 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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