CN107602872B - Preparation of novel luminescent porous metal organic framework material and detection method of novel luminescent porous metal organic framework material on trace nitro explosives - Google Patents
Preparation of novel luminescent porous metal organic framework material and detection method of novel luminescent porous metal organic framework material on trace nitro explosives Download PDFInfo
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Abstract
The invention discloses a novel luminescent porous metal organic framework material and a detection method thereof for trace nitro explosives. The material is prepared by taking zirconium salt and an organic carboxylic acid ligand containing an amide group as raw materials and synthesizing the raw materials by a solvothermal method in the presence of a benzoic acid regulator, and can realize efficient sensing detection of trace nitro explosives in water. The material is simple to prepare, has good stability, and has the advantages of rapidness, simplicity, convenience, good selectivity, high sensitivity, cyclic regeneration and the like in the aspect of nitro explosive detection.
Description
Technical Field
The invention belongs to the field of metal organic framework materials, and particularly relates to a preparation method of a novel luminescent porous metal organic framework material and a detection method of the novel luminescent porous metal organic framework material on trace nitro explosives.
Background
Nitro explosives such as 2,4, 6-Trinitrophenol (TNP), 2,4, 6-trinitrotoluene (TNT), cyclotrimethylenetrinitramine (RDX), 2, 4-dinitrotoluene (2,4-DNT) and the like have the characteristics of mature preparation method, good dullness, convenience in carrying and the like, and are widely applied to military production and industrial blasting. The compound not only has great explosive power, but also has great toxicity, difficult degradation and strong carcinogenic capacity, and can cause vomit, twitch, nervous system disorder and even death after invading human bodies, so the development of the rapid trace detection technology of the nitro explosives has important significance for preventing terrorist attacks, maintaining public safety and guaranteeing human health. At present, the detection technology aiming at trace nitro explosives mainly comprises a mass spectrometry method, a surface acoustic wave method, an ion migration method, a thermal oxidation reduction method and the like; however, most of the methods have the problems of expensive instruments, inconvenient carrying, complex operation, long time consumption and the like. Compared with the prior art, the fluorescence sensing detection method achieves the purpose of analysis and detection by using the change of fluorescence signals (such as wavelength, intensity and the like), and has the advantages of high response speed, high sensitivity, simple and convenient operation, strong anti-electromagnetic interference capability and the like. Professor Swager et al, MIT, usa, made a breakthrough progress in detecting trace amounts of nitro explosives using fluorescence sensing technology (Swager t.m. et al, j.am.chem.soc.,1998,120,11864); based on this result, Nomadics corporation in the united states further developed a series of Fido "optic dog nose" products for rapid detection of trace explosives, which are currently considered to be the most internationally sensitive explosive detectors. The research on the fluorescent sensing detection of explosives in China is relatively late, and the research on technical equipment, particularly materials, mostly depends on foreign import, so that the development of a new material for rapidly detecting trace nitro explosives becomes one of the important problems which need to be solved urgently in the field in China.
Luminescent porous metal organic frame Materials (MOFs) are novel crystalline luminescent materials with periodic grid structures formed by connecting metal ions and organic ligands. The fluorescent material has the advantages of high luminous intensity, good stability, large specific surface area, adjustable pore size and shape and the like, and has good application prospect in the aspect of chemical sensing detection. Li et al have reported a zirconium light-emitting porous metal organic framework material, and the results of fluorescence sensing detection studies show that although this material can detect nitro-explosives, several nitro-explosives have little difference in the fluorescence quenching degree of this material and do not have specific recognition ability (see: Li J. -R. et al, J.Am.chem.Soc.,2016,138,6204). A sample of terbium luminescent porous metal organic framework material was reported by Zang et al, and the results showed that the material has a very good selective detection capability for TNP, but no study of its cyclic regeneration performance was carried out (see: Zang S. -Q. et al, chem. Eur. J.2015,21,15705). Gunn "design, synthesis and performance research based on rigid aromatic carboxylic acid ligands MOFs" discloses a Cd-MOF material based on N, N' -bis (3, 5-dicarboxyphenyl) -1, 4-naphthalamide ligand, which can be used for detecting nitroaromatic compounds, but cannot meet the requirement of specific selective sensing and identification of TNP in water.
In summary, in the prior art, an effective solution is not yet available for the problem of the specific selective detection and the recycling of the luminescent porous metal organic framework for detecting the nitro explosives in water.
Disclosure of Invention
In order to solve the problems, the invention provides a novel luminescent porous metal organic framework material and a preparation method thereof, wherein a zirconium luminescent porous metal organic framework material is synthesized by using zirconium ions and organic carboxylic acid ligands containing amide groups, the sensing and detecting performance of the material on nitro explosives is researched, and the result shows that: the material is simple in preparation method and good in stability, and has the advantages of being rapid, simple, convenient, good in selectivity, high in sensitivity, capable of being recycled and regenerated and the like in the aspect of nitro explosive detection.
In order to achieve the purpose, the invention adopts the following technical scheme:
a luminescent porous metal organic framework material of zirconium is constructed by zirconium ions and N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide.
The problems that the fluorescence quenching degree of the existing luminescent porous metal organic framework material to different nitro explosives is not large, the specific selectivity of sensing identification is not high and the like are solved; meanwhile, the detection of nitro explosives in water is realized by utilizing the good water stability of the zirconium metal organic framework material. According to the invention, N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and different zirconium salts are assembled to obtain the zirconium metal organic framework material with good water stability, and research results show that: the MOF material shows good specific selective sensing and recognition capability on TNP in water. This is mainly due to the fact that the emission spectrum of the MOF material assembled by N- (3, 5-carboxyphenyl) -4-carboxy-1-naphthamide and zirconium ions overlaps with the absorption spectrum of TNP to a greater extent, enabling efficient Resonance Energy Transfer (RET) between the two; and different from most of the existing zirconium luminescent porous metal organic framework materials which only recognize the sensing nitro compounds through pi-pi bond action, the amide group in the ligand used by the invention can form strong hydrogen bond with the hydroxyl group in the nitro explosive TNP, further enhance the fluorescence quenching efficiency, and improve the sensitivity and specificity of sensing, thereby realizing the high sensitivity and specificity detection of the nitro explosive such as TNP.
The invention also provides a preparation method of the novel luminescent porous metal organic frame material for detecting trace nitro explosives, which takes zirconium salt and N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide as raw materials to synthesize the novel luminescent porous metal organic frame material by a solvothermal method in the presence of benzoic acid.
Preferably, the zirconium salt is zirconium tetrachloride, zirconium oxychloride or zirconium nitrate pentahydrate.
Preferably, the present invention uses benzoic acid as a regulator. In the synthesis of zirconium MOF materials, the introduction of the regulator can not only improve the crystallinity of the MOF materials, but also control the morphology and size of the MOF materials. In general, the introduction of more acidic modifiers (e.g., formic acid, hydrochloric acid, etc.) readily results in smaller sized MOF crystals; and the introduction of a relatively weak acidity regulator (such as benzoic acid) can obtain MOF crystals with larger size so as to meet the requirement of X-ray single crystal test. However, basic regulators cannot be introduced in the experiments, since OH is based on the Natural Bond Orbital (NBO) theory–The NBO charge of the middle oxygen atom is-1.403, which is much greater than the charge of the coordinating oxygen atom on the carboxylic acid in the ligand-0.74, thus OH–The complex is easier to be coordinated with Zr (IV), so that the Zr-MOFs is hydrolyzed and collapsed in alkali solution, and the stable MOFs material cannot be obtained. Therefore, a certain amount of benzoic acid is selected and added in the design of the invention, so that the Zr-MOF material with larger size and stable structure is obtained.
Preferably, the molar ratio of the zirconium salt to the N- (3, 5-carboxyphenyl) -4-carboxy-1-naphthamide is 1.5-6: 4.
The proper reaction temperature not only can provide the required energy for the reaction, but also can avoid the phenomenon that the reaction cannot be carried out smoothly due to the over-low temperature or excessive side reactions are generated due to the over-high temperature; reaction times are likewise of particular importance for the solvothermal synthesis, too short a reaction time leading to incomplete reactions and too long a reaction time leading to a reduction in the yield. Thus, the preferred solvothermal process of the present invention has the reaction conditions: reacting for 24-72 h at 90-110 ℃ to ensure that the reaction is smoothly carried out and the yield is improved.
The invention also provides a luminescent porous metal organic framework material prepared by any one of the methods.
The invention also provides application of the luminescent porous metal organic framework material in selective detection of different nitro explosives.
The invention has the advantages of
(1) The preparation method of the luminescent metal organic framework material is simple, good in stability, high in detection efficiency, strong in practicability and easy to popularize.
(2) When the TNP, TNT, RDX, 2,4-DNT, NB and NT analytes interact with the luminescent metal organic framework material of the invention, the fluorescence intensity of the luminescent material is changed, but the change degree is different, and the specific selective recognition and detection of different nitro explosives can be realized by utilizing the change degree.
(3) The luminescent porous metal organic framework material synthesized by the invention has the advantages of rapidness, simplicity, convenience, good selectivity, high sensitivity, cyclic regeneration and the like in the aspect of detecting nitro explosives (especially TNP), and has high recycling rate.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a three-dimensional structure diagram of a light-emitting porous metal organic framework material synthesized in example 1.
FIG. 2 is a fluorescence spectrum of the luminescent porous metal organic framework material synthesized in example 1 for TNP solutions with different concentrations.
FIG. 3 shows the TNP concentration versus the fluorescence intensity F of the light-emitting porous metal organic framework material of example 10Graph of/F, inset is TNP concentration versus luminescence for example 1Fluorescence intensity F of porous metal organic framework material0Stern-Volmer Linear plot of/F ([ TNP)]≤57.0μmol/L)。
FIG. 4 is a cyclic regeneration detection curve of the synthesized luminescent porous metal organic framework material of example 1 to TNP.
FIG. 5 shows the fluorescence spectra of the luminescent porous metal organic framework material synthesized in example 1 for TNT solutions with different concentrations.
FIG. 6 shows the fluorescence spectra of the luminescent porous metal organic framework material synthesized in example 1 with different concentrations of RDX solution.
FIG. 7 shows the fluorescence spectra of the luminescent porous metal organic framework material synthesized in example 1 for different concentrations of 2,4-DNT solution.
FIG. 8 shows the fluorescence spectra of the luminescent porous metal organic framework material synthesized in example 1 with NB solutions of different concentrations.
FIG. 9 shows the fluorescence spectra of the luminescent porous metal organic framework material synthesized in example 1 for NT solutions of different concentrations.
FIG. 10 is a bar graph comparing the fluorescent response of the luminescent porous metal organic framework material synthesized in example 1 to different nitro explosives.
FIG. 11 is a graph of HOMO and LUMO energy levels of nitro-explosives.
FIG. 12 is a UV absorption spectrum of nitro explosives.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
Synthesizing a luminescent porous metal organic framework material: dissolving 17.5mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 75% yield. The structure of the resulting crystal is shown in FIG. 1.
Example 2
Synthesizing a luminescent porous metal organic framework material: dissolving 24.2mg of zirconium oxychloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant-temperature reaction at 100 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 54% yield.
Example 3
Synthesizing a luminescent porous metal organic framework material: dissolving 32.2mg of zirconium nitrate pentahydrate, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 50% yield.
Example 4
Synthesizing a luminescent porous metal organic framework material: dissolving 8.7mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 41% yield.
Example 5
Synthesizing a luminescent porous metal organic framework material: dissolving 35.0mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 60% yield.
Example 6
Synthesizing a luminescent porous metal organic framework material: dissolving 17.5mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 90 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 42% yield.
Example 7
Synthesizing a luminescent porous metal organic framework material: dissolving 17.5mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 110 ℃ for 48h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 49% yield.
Example 8
Synthesizing a luminescent porous metal organic framework material: dissolving 17.5mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 24h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 39% yield.
Example 9
Synthesizing a luminescent porous metal organic framework material: dissolving 17.5mg of zirconium tetrachloride, 37.9mg of N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide and 240mg of benzoic acid in 3.0mL of N, N-dimethylformamide solvent, placing the solution in a stainless steel reaction kettle lined with polytetrafluoroethylene after ultrasonic dissolution, carrying out constant temperature reaction at 100 ℃ for 72h, and uniformly cooling to room temperature at the speed of 5 ℃/h to obtain transparent blocky crystals. The product was filtered and washed with N, N-dimethylformamide, air dried at room temperature and collected in about 56% yield.
Example 10
0.5mg of the luminescent porous metal organic framework material prepared in example 1 was weighed out and dispersed in 2ml of distilled water, and the emission spectrum thereof was measured. Then, 20, 40, 60, 80, 100, 120, 140, 160, 180 and 200 mu L of TNP solution (1.00 multiplied by 10) are added in a cumulative way-3mol/L) and the fluorescence emission spectra thereof are respectively measured.
As shown in FIG. 2, the maximum emission wavelength of the light-emitting porous metal organic framework material of the present invention in water is 407nm, and the fluorescence intensity gradually decreases with the increase of the TNP concentration. The degree of quenching was 95% at a TNP concentration of 91. mu. mol/L.
As shown in the inset of fig. 3, F0/F and [ Q)]Has good linear relation and obtains the Stern-Volmer quenching constant of 3.9 multiplied by 104L/mol (Stern-Volmer equation: F)0/F＝1+KSV[Q]Wherein F is0Is the initial fluorescence intensity of the light-emitting porous metal-organic framework material, and F is the fluorescence intensity of the light-emitting porous metal-organic framework material in the presence of TNP, [ Q ]]Is the concentration of TNP, KSVStern-Volmer quench constant). Under the same experimental conditions, only the fluorescence intensity F of the luminescent porous metal organic framework material in the presence of the object to be detected is required to be measured, and the F is calculated0is/F, i.e. rootObtaining the concentration [ Q ] of TNP in the substance to be detected according to a standard curve]。
Example 11
Soaking the TNP detecting material in distilled water, ultrasonically cleaning for 3 times, drying, and recovering for later use.
Dispersing the recovered light-emitting porous metal organic framework material in distilled water, and sequentially adding 200 μ L of NP solution (1.00 × 10)-3mol/L) in the dispersion liquid, the initial fluorescence intensity of the recycled material and the fluorescence intensity after TNP is added are almost the same as the initial fluorescence intensity of the newly prepared luminescent porous metal organic framework material and the fluorescence intensity after TNP is added, and no obvious change is found after the experiment process is repeated for 5 times (figure 4), which shows that the material has the advantages of good repeatability and recycling.
Example 12
Fluorescence quenching studies were performed on other nitro explosives (TNT, RDX, 2,4-DNT, NB, NT) according to the protocol described in example 10, and the fluorescence emission spectra are shown in FIGS. 5-9. Fig. 10 is a bar chart comparing fluorescence responses of the synthesized luminescent porous metal organic framework material to different nitro explosives, and as can be seen from fig. 10, the fluorescence quenching degree of the material of the invention to different nitro explosives is different, wherein the most significant effect is TNP, and it can be seen that the material of the invention has selective detection capability to different nitro explosives.
The MOF material synthesized by the invention has good fluorescence sensing detection effect on nitro explosives (such as TNP, TNT, RDX, 2,4-DNT, NB and NT) in water, and the reasons are as follows: (1) the nitro-explosive has strong electron-withdrawing nitro group and is a good electron acceptor, and the metal organic framework material is generally a good electron donor, so that under the condition of illumination, electron transfer (PET effect) from the metal organic framework material (electron donor) to the nitro-explosive (electron acceptor) can occur, thereby causing fluorescence quenching. The LUMO energy level sequence of the nitro explosives, which is calculated according to the Density Functional Theory (DFT), is TNP > TNT >2,4-DNT > RDX > NB > NT (figure 11), and is basically consistent with but not completely identical to the sequence of fluorescence quenching efficiencies TNP > TNT > RDX >2,4-DNT > NB > NT in the experiment, which indicates that the PET effect is not the only factor for determining the fluorescence quenching efficiency. (2) Fluorescence quenching efficiency is also related to the number of nitro groups in the nitro explosive molecule. The TNP, TNT and RDX molecules all contain three nitro groups, the 2,4-DNT molecule contains two nitro groups, and the NB and NT molecules respectively contain one nitro group, so that the fluorescence quenching efficiency is roughly in the order of (TNP, TNT and RDX) >2,4-DNT > (NB and NT) according to the number of the nitro groups, which is basically consistent with the experimental results.
Furthermore, the main reasons for the specific selective detection of TNP by this MOF material are: (1) the absorption spectrum of TNP overlaps to a greater extent with the emission spectrum of the metal-organic framework materials reported in the present invention, enabling efficient Resonance Energy Transfer (RET) between the two, while there is little or little overlap with the absorption spectrum of other nitro-explosives (fig. 12), and thus, the MOF material exhibits the highest quenching efficiency for TNP. (2) Compared with other nitro explosives, hydroxyl groups in TNP molecules can form strong hydrogen bonds with amide groups of metal organic framework materials, interaction and energy transfer between a host and an object are effectively enhanced, and fluorescence quenching efficiency is further improved. Therefore, among the listed nitro explosives, the synthesized luminescent MOF material not only shows the maximum fluorescence quenching efficiency on TNP, but also has a quenching degree obviously higher than that of other nitro explosives (FIG. 10), which indicates that the material has specific selective detection and recognition capability on TNP.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (4)
1. A preparation method of a novel luminescent porous metal organic framework material for detecting trace nitro explosives is characterized in that zirconium salt and N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide are used as raw materials, and the novel luminescent porous metal organic framework material is synthesized by a solvothermal method in the presence of an acidic pH regulator;
the zirconium salt is zirconium chloride, zirconium oxychloride or zirconium nitrate pentahydrate;
the pH regulator is benzoic acid;
the molar ratio of the zirconium salt to the N- (3, 5-carboxyphenyl) -4-carboxyl-1-naphthamide is 1.5-6: 4;
the reaction conditions of the solvothermal method are as follows: reacting for 24-72 h at 90-110 ℃.
2. A light-emitting porous metal organic framework material prepared by the method of claim 1.
3. Use of the light-emitting porous metal organic framework material according to claim 2 for the selective detection of different nitro-explosives.
4. The use of the light-emitting porous metal organic framework material according to claim 2 for the specific selective detection of TNP.
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| CN110128674B (en) * | 2019-05-31 | 2021-05-07 | 聊城大学 | Water-stable rare earth metal organic framework material for fluorescence detection of sulfonamide antibiotics and preparation method thereof |
| CN113150306B (en) * | 2021-05-08 | 2022-12-09 | 聊城大学 | FMOF material with high water stability, preparation thereof and application thereof in sensing detection of fleroxacin in water |
| CN113912858B (en) * | 2021-10-27 | 2023-02-28 | 西京学院 | Porous polymer for detecting nitro compound and preparation method thereof |
| CN114656409B (en) * | 2022-03-17 | 2023-12-22 | 山东产研绿色与健康研究院有限公司 | Fluorescent material for rapidly detecting explosives, preparation method and application thereof |
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