CN112375227B - Three-dimensional metal organic framework material with nano-pore structure and preparation method and application thereof - Google Patents

Three-dimensional metal organic framework material with nano-pore structure and preparation method and application thereof Download PDF

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CN112375227B
CN112375227B CN202011285813.1A CN202011285813A CN112375227B CN 112375227 B CN112375227 B CN 112375227B CN 202011285813 A CN202011285813 A CN 202011285813A CN 112375227 B CN112375227 B CN 112375227B
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谢伟
姚婵
徐广娟
张姝然
许彦红
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Abstract

The invention discloses a preparation method and application of a three-dimensional metal organic framework material with a nano-pore structure. Using a luminescent ligand 4, 4'4' -triphenylamine tricarboxylate synthesizes a metal-organic framework material [ (Zn) with a nano-channel under the solvothermal condition 4 O)(H 2 O) 2 (TPA) 2 ]8DMA, the material produced is a (3,6) connected three-dimensional network with one-dimensional nanoscale square channels. The material can be used as an effective fluorescent probe to quickly and efficiently detect nitroaromatic explosives, in particular picric acid. In addition, the material can be recovered through simple centrifugal separation, and recycling is realized. The invention can obtain the three-dimensional metal organic framework material with the nanometer pore canal structure, and the synthesis method is simple.

Description

Three-dimensional metal organic framework material with nano-pore structure and preparation method and application thereof
Technical Field
The invention relates to the technical field of porous materials, in particular to preparation and application of a three-dimensional metal-organic framework material with a nano-pore structure.
Background
Metal-organic frameworks (MOFs) materials have attracted considerable attention from researchers due to their unique and interesting structures, chemical diversity and their potential widespread use in gas storage, separation, optical materials, drug delivery and heterogeneous catalysis. As the name implies, MOFs are a class of novel porous materials with periodic network structure formed by coordination bonds of metal ions/clusters and organic ligands. In recent years, fluorescent MOFs have attracted much interest because of their diverse applications in chemical sensing, photochemistry, and electro-optical displays. The organic ligand for constructing the MOFs material usually contains aromatic or conjugated pi parts, so that light emission or photoluminescence can be easily caused under excitation, and in addition, the material has the advantages of unique and adjustable porous structure, high specific surface area, good physical and chemical stability, molecular design diversity, post-synthesis modification and the like, so that an excellent platform is provided for fluorescence sensing detection. Therefore, porous MOFs materials are elected as excellent candidates for chemical sensing applications.
The rapid, efficient and reliable detection of explosives has attracted more and more attention, and is extremely important for site safety, homeland safety, environmental safety and humanitarian significance. Currently, a variety of detection techniques have been developed to detect explosives, including gas chromatography, raman spectroscopy, cyclic voltammetry, and fluorescence sensing techniques, among others. Among them, fluorescence detection shows considerable advantages due to its simplicity, sensitivity, low cost, short response time, etc. In this regard, some new molecules, polymers and nanoscale materials have been designed to be used as fluorescent detection materials, but some disadvantages such as stability, toxicity, sensitivity and biodegradability still exist. Therefore, there is an urgent need to design and synthesize a novel fluorescent material for detecting explosives with high selectivity and high efficiency.
Disclosure of Invention
The invention aims to overcome the problems and needs in the prior art and provides a preparation method and application of a three-dimensional metal organic framework material with nanopores.
The invention provides a three-dimensional metal organic framework material with a nano-pore channel structure, and the chemical formula of the three-dimensional metal organic framework material with the nano-scale tetragonal channel structure is [ (Zn) 4 O)(H 2 O) 2 (TPA) 2 ]8DMA, wherein, H 3 TPA was 4, 4', 4 "-trimethylamine triphenylamine 4, and DMA was N, N-dimethylacetamide.
In one embodiment according to the present invention, the three-dimensional metal-organic framework material crystal system is monoclinic; space group is P2 1 C; unit cell parameter of
Figure BDA0002782278620000021
Figure BDA0002782278620000022
α＝90°，β＝109.500°，γ＝90°。
The invention also provides a preparation method of the three-dimensional metal organic framework material, which comprises the following steps:
1) preparing a reaction solution: dissolving a proper amount of metal salt zinc nitrate hexahydrate and an organic ligand 4, 4' -triphenylamine tricarboxylate into N, N-dimethylacetamide to obtain a reaction solution;
2) and adding the reaction solution into a high-pressure reaction kettle, gradient heating to 100-110 ℃, cooling to room temperature after the reaction is finished, repeatedly washing with N, N-dimethylacetamide, and separating to obtain light yellow blocky crystals, namely the three-dimensional metal organic framework material with the nano-channel structure.
In one embodiment according to the invention, in step 1), the molar ratio of zinc nitrate hexahydrate to triphenylamine 4, 4', 4 "-tricarboxylate is: 4-8: 1.
the preparation method of the three-dimensional metal organic framework material comprises the following steps of: the dosage ratio of the 4, 4' -triphenylamine tricarboxylate to the N, N-dimethylacetamide is 1: 120-180.
In one embodiment according to the present invention, in step 2), the gradient temperature rise is a temperature rise at a rate of 10 ℃/hour.
In one embodiment according to the present invention, the reaction temperature is 100-110 ℃ and the reaction time is 3 days in step 2); preferably, the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle.
The invention also provides the three-dimensional metal organic framework material with the nanometer pore structure, or the application of the three-dimensional metal organic framework material prepared by the preparation method in detecting explosives.
In one embodiment according to the invention, the application is in the detection of nitroaromatic explosives.
The invention further provides a detection reagent for detecting explosives, which comprises a fluorescent probe prepared from a three-dimensional metal organic framework material; the three-dimensional metal organic framework material is the three-dimensional metal organic framework material or the three-dimensional metal organic framework material prepared by the preparation method.
In one embodiment according to the invention, the detection reagent detects nitroaromatic explosives by fluorescence quenching.
Preferably, the nitro explosives are Nitrobenzene (NB), 1, 2-dinitrobenzene (1,2-DNB), m-dinitrobenzene (1,3-DNB) and trinitrophenol (also known as picric acid, PA).
Compared with the prior art, the invention has the beneficial effects that:
the invention designs and synthesizes a three-dimensional metal organic framework material with a nanometer pore canal structure by adopting a simple solvothermal synthesis technology. Due to the good fluorescence characteristic of the material, the material can be used as an effective fluorescent probe to efficiently detect nitroaromatic explosives in a liquid phase, is particularly sensitive to picric acid, and has a fluorescence complete quenching detection line of 30 ppm. In addition, the material can be recovered through simple centrifugal separation, and recycling is realized. Therefore, the material is an effective fluorescence detector, and can realize simple and efficient detection of nitroaromatic explosives.
Drawings
FIG. 1 is a schematic diagram of the coordination structure of the crystal of the present invention.
FIG. 2 is a structural diagram of a crystal of the present invention: wherein, FIG. 2(a) is a schematic diagram of a one-dimensional nano-square pore structure; FIG. 2(b) is a schematic diagram of a three-dimensional cell structure along [101 ]; FIG. 2(c) is a schematic diagram of the (3,6) connection topology; fig. 2(d) is a schematic diagram of a three-dimensional open network structure.
FIG. 3 is a PXRD spectrum of crystal simulation and synthesis of the present invention.
FIG. 4 shows a crystal of the present invention and a ligand H used therein 3 Solid state fluorescence emission spectrum of TPA.
FIG. 5 is a fluorescence detection spectrum of the crystal p-nitroaromatic explosive of the present invention: wherein FIG. 5(a) is a fluorescence emission spectrum of the crystal of the present invention in DMA solutions of NB at different concentrations; FIG. 5(b) is a fluorescence emission spectrum of the crystal of the present invention in DMA solutions of different concentrations of 1, 2-DNB; FIG. 5(c) is a fluorescence emission spectrum of the crystal of the present invention in DMA solutions of different concentrations of 1, 3-DNB; FIG. 5(d) is the fluorescence emission spectrum of the crystals of the present invention in DMA solutions of different concentrations of PA.
FIG. 6 is a bar graph of the cycle detection efficiency of fluorescence detection of nitroaromatic explosives by crystals of the present invention: wherein FIG. 6(a) is a bar graph of fluorescence quenching efficiency of 6 cycles of cyclic detection of crystals of the invention dispersed in a DMA solution of 800ppm NB; FIG. 6(b) is a bar graph of fluorescence quenching efficiency of 6 cycles of cyclic detection of crystals of the invention dispersed in 200ppm of 1,2-DNB in DMA solution; FIG. 6(c) is a bar graph of fluorescence quenching efficiency of 6 rounds of cyclic detection of crystals of the present invention dispersed in 200ppm of 1,3-DNB in DMA solution; FIG. 6(d) is a bar graph of fluorescence quenching efficiency of 6 cycles of cyclic assays with crystals of the invention dispersed in 20ppm of PA in DMA solution.
Detailed Description
Detailed description of the preferred embodimentsthe following detailed description of the present invention will be made with reference to the accompanying drawings 1-6, although it should be understood that the scope of the present invention is not limited to the specific embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Example 1 preparation method of three-dimensional metal organic framework material with nanopore structure
The embodiment can obtain the three-dimensional metal organic framework material with the nanometer pore channel structure, and the preparation method is completed according to the following steps:
1) preparing a reaction solution: dissolving a metal salt zinc nitrate hexahydrate (0.06g,0.2mmol) and an organic ligand 4, 4' -trimethylamine triphenylamine (0.0151g,0.040mmol) in 6mLN, N-dimethylacetamide to obtain a reaction solution;
2) adding the reaction liquid into a polytetrafluoroethylene reaction kettle, then placing a stainless steel high-pressure kettle in an oven, heating to 100 ℃ from room temperature at 10 ℃ per hour, reacting for 3 days at 100 ℃, cooling to room temperature, repeatedly washing and separating with N, N-dimethylacetamide to obtain light yellow blocky crystals, namely the three-dimensional metal organic framework crystalline material with the nanometer pore structure.
The chemical formula of the three-dimensional metal organic framework material with the nanometer pore canal structure is [ (Zn) 4 O)(H 2 O) 2 (TPA) 2 ]8DMA, wherein H 3 TPA is 4, 4' -trimethylamine triphenylamine, DMA is N, N-dimethyl acetamide; the crystal system is monoclinic; space group is P2 1 C; unit cell parameter of
Figure BDA0002782278620000041
Figure BDA0002782278620000042
α is 90 °, β is 109.500 °, γ is 90 °, and the yield is 62%.
Example 2 analysis of Crystal Structure
1. Single crystal X-ray diffraction data were recorded using an ApexII single crystal diffractometer from brueck, germany, and irradiated with a molybdenum target (λ ═ 0.71069). The asymmetric unit comprising a Zn 4 (μ 4 -O) cluster consisting of four Zn 2+ Ion, one μ 4 -O atom and two deprotonated TPA 3- And (3) ligand composition. In Zn 4 (μ 4 -O) cluster, Zn3 adopts a hexa-coordinated octahedral geometry, whereas Zn1, Zn2 and Zn4 have a tetrahedral coordination geometry. One Zn 4 (μ 4 O) clusters are derived from two H 3 Six carboxylic acid groups of the TPA ligand are encapsulated. As shown in FIG. 1, Symmetry code: #1x, -0.5-y,0.5+ z; #2-x, -0.5+ y, 0.5-z; #31-x, -y, 1-z; #41-x, -0.5+ y, 0.5-z. Adjacent clusters are interconnected by ligands to form an infinite three-dimensional framework, along [101]]The dimension of one-dimensional square nanometer pore canal is observed in the direction, and the size is about
Figure BDA0002782278620000051
(FIGS. 2a, 2b and 2 d). From a topological point of view, each H 3 The TPA ligand can be viewed as a 3 point of attachment, each Zn 4 (μ 4 -O) cluster can be seen as one 6-connection point, thus forming a topology of (3,6) connections (fig. 2 c).
2. Powder X-ray diffraction (PXRD)
The tests were carried out at 293K using a Rigaku model RINT Ultima III diffractometer, the angular range of the tests being 3-50 deg.. As shown in fig. 3, the PXRD pattern of the synthesized crystal matched well with the pattern generated by the simulation, indicating that the synthesized crystal material had good phase purity.
Example 3 fluorescent Properties
Solid-state fluorescence emission spectroscopy testing using a Jasco FP-8600 spectrometer at room temperature. As shown in FIG. 4, the synthesized crystal has an emission peak position at 440nm under 365nm wavelength excitation, and ligand H 3 The solid state emission spectrum of TPA has an emission peak at 443 nm. The crystals show a significantly enhanced blue emission compared to the free ligand.
EXAMPLE 4 fluorescence detection of nitroaromatic explosives
The detection experiment was performed as follows: a fully ground 5mg crystal sample is immersed in 3mL prepared DMA solution of nitroaromatic explosives with different concentrations, stable suspension is formed through ultrasonic treatment, and then liquid phase fluorescence spectrum test is carried out by using a Jasco FP-8600 spectrometer under the condition of room temperature. The nitroaromatic explosives selected for use in the present invention include Nitrobenzene (NB), 1, 2-dinitrobenzene (1,2-DNB), m-dinitrobenzene (1,3-DNB) and trinitrophenol (also known as picric acid PA).
The curves in FIG. 5a are the fluorescence emission spectra from top to bottom of 5mg crystals in DMA solutions of NB at 0ppm, 50ppm, 100ppm, 200ppm, 400ppm, 600ppm, 800ppm and 1000ppm, respectively; the curves in FIG. 5b show, from top to bottom, fluorescence emission spectra of 5mg crystals in DMA solutions of 0ppm, 20ppm, 40ppm, 60ppm, 80ppm, 100ppm, 200ppm and 500ppm of 1,2-DNB, respectively; the curves in FIG. 5c show, from top to bottom, fluorescence emission spectra of 5mg crystals in DMA solutions of 0ppm, 10ppm, 20ppm, 40ppm, 60ppm, 80ppm, 100ppm, 200ppm and 500ppm of 1,3-DNB, respectively; the curves in FIG. 5d show, from top to bottom, fluorescence emission spectra of 5mg crystals in DMA solutions of 0ppm, 2ppm, 4ppm, 6ppm, 8ppm, 10ppm, 20ppm and 30ppm PA, respectively. The minimum concentrations for complete quenching of NB, 1,2-DNB, 1,3-DNB and PA were 1000ppm, 500ppm and 30ppm, respectively. Notably, the crystal is most sensitive to PA, with a detection line for complete quenching of 30 ppm. The lowest concentration at which the fluorescence intensity is completely quenched with-NO 2 Decreasing with increasing number, therefore, it is inferred that with-NO 2 The increase of the group increases the electron transfer from the electron donor to the electron acceptor, so that the fluorescence quenching becomes more significant. The crystal can be used as a fluorescent probe to realize rapid identification of nitroaromatic explosives through a fluorescence quenching phenomenon.
In addition, the detected crystal sample is centrifugedAnd washing and recovering the nitro compound by using DMA repeatedly, recycling the recovered sample, and detecting the nitro compound circularly. FIG. 6a is a bar graph of fluorescence quenching efficiency for 6 cycles of cycling assays with crystals dispersed in 800ppm NB solution; FIG. 6b is a bar graph of fluorescence quenching efficiency of 6 cycles of detection with crystals dispersed in 200ppm of 1,2-DNB solution; FIG. 6c is a bar graph of fluorescence quenching efficiency for 6 cycles of detection with crystals dispersed in 200ppm of 1,3-DNB solution; FIG. 6d is a bar graph of fluorescence quenching efficiency for 6 cycles of cycling tests with crystals dispersed in 20ppm PA solution. Quenching efficiency is shown by formula (I) 0 -I)/I 0 X 100% is determined, wherein I 0 Is the fluorescence emission intensity before addition of the analyte, and I is the fluorescence emission intensity after addition of the analyte. The quenching efficiency of cycles 1-6 did not change significantly, indicating that the crystals of the invention exhibit good recycling and stability in assay applications. The crystal material can be used as a fluorescent probe to efficiently and circularly detect nitroaromatic explosives.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (16)

1. The application of the three-dimensional metal organic framework material with the nanometer pore channel structure in detecting explosives is characterized in that the chemical formula of the three-dimensional metal organic framework material with the nanometer square channel structure is [ (Zn) 4 O)(H 2 O) 2 (TPA) 2 ]8DMA, wherein H3TPA is 4, 4' -trimethylamine triphenylamine, and DMA is N, N-dimethylacetamide.
2. The use of the three-dimensional metal-organic framework material with a nanopore structure in the detection of explosives according to claim 1, wherein the crystal system of the three-dimensional metal-organic framework material is monoclinic; space group is P21/c; the unit cell parameters are α ═ 90 °, β ═ 109.500 °, γ ═ 90 °.
3. The application of the three-dimensional metal organic framework material with the nanopore structure in detecting explosives is characterized in that the preparation method of the three-dimensional metal organic framework material comprises the following steps:
1) preparing a reaction solution: dissolving a proper amount of metal salt zinc nitrate hexahydrate and organic ligand 4, 4' -triphenylamine tricarboxylate into N, N-dimethylacetamide to obtain a reaction solution;
2) and adding the reaction solution into a high-pressure reaction kettle, gradient heating to 100-110 ℃, cooling to room temperature after the reaction is finished, repeatedly washing with N, N-dimethylacetamide, and separating to obtain light yellow blocky crystals, namely the three-dimensional metal organic framework material with the nano-channel structure.
4. The use of the three-dimensional metal-organic framework material with a nanopore structure in detecting explosives in claim 3, wherein in the step 1), the molar ratio of zinc nitrate hexahydrate to triphenylamine 4, 4', 4 "-tricarboxylate is as follows: 4-8: 1;
and (2) in mmol: measured by mL, the 4, 4' -triphenylamine tricarboxylate and N, N-dimethylacetamide
The dosage ratio of 1: 120-180.
5. The use of the three-dimensional metal-organic framework material with a nanopore structure in the detection of explosives according to claim 3, wherein in the step 2), the gradient temperature rise is a temperature rise at a rate of 10 ℃/hour.
6. The use of the three-dimensional metal-organic framework material with a nanopore structure in detecting explosives as claimed in claim 3, wherein in the step 2), the reaction temperature is 100-110 ℃, and the reaction time is 3 days.
7. The use of the three-dimensional metal organic framework material with a nanopore structure in detecting explosives according to claim 3, wherein the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle.
8. The use of the three-dimensional metal-organic framework material with a nanopore structure according to any one of claims 1-7 in the detection of explosives, wherein the use is in the detection of nitroaromatic explosives.
9. A detection reagent for detecting explosives, comprising a fluorescent probe made of a three-dimensional metal organic framework material; wherein the three-dimensional metal organic framework material has a nano-scale tetragonal channel structure, and the chemical formula of the three-dimensional metal organic framework material is [ (Zn) 4 O)(H 2 O) 2 (TPA) 2 ]8DMA, wherein H3TPA is 4, 4' -trimethylamine triphenylamine, and DMA is N, N-dimethylacetamide.
10. The detection reagent for detecting explosives in accordance with claim 9, wherein the crystal system of the three-dimensional metal organic framework material is monoclinic; space group is P21/c; the unit cell parameters are α ═ 90 °, β ═ 109.500 °, γ ═ 90 °.
11. A detection reagent for detecting explosives, comprising a fluorescent probe made of a three-dimensional metal organic framework material; the preparation method of the three-dimensional metal organic framework material comprises the following steps:
1) preparing a reaction solution: dissolving a proper amount of metal salt zinc nitrate hexahydrate and an organic ligand 4, 4' -triphenylamine tricarboxylate into N, N-dimethylacetamide to obtain a reaction solution;
2) and adding the reaction solution into a high-pressure reaction kettle, gradient heating to 100-110 ℃, cooling to room temperature after the reaction is finished, repeatedly washing with N, N-dimethylacetamide, and separating to obtain light yellow blocky crystals, namely the three-dimensional metal organic framework material with the nano-channel structure.
12. The detection reagent for detecting explosives in accordance with claim 11, wherein in step 1), the molar ratio of the zinc nitrate hexahydrate to the triphenylamine 4, 4', 4 "-tricarboxylate is: 4-8: 1;
and (2) in mmol: measured by mL, the 4, 4' -triphenylamine tricarboxylate and N, N-dimethylacetamide
The dosage ratio of 1: 120-180.
13. The detection reagent for detecting an explosive according to claim 11, wherein in step 2), the temperature gradient is increased at a rate of 10 ℃/hr.
14. The detecting reagent for detecting explosives as claimed in claim 11, wherein in the step 2), the reaction temperature is 100 ℃ and 110 ℃, and the reaction time is 3 days.
15. The detection reagent for detecting explosives in claim 11, wherein the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle.
16. A detection reagent for detecting explosives in accordance with any of claims 9 to 15, wherein the detection reagent detects nitroaromatic explosives by fluorescence quenching.
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