CN112375227A - 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 PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011148 porous material Substances 0.000 title abstract description 16
- 239000002360 explosive Substances 0.000 claims abstract description 22
- 239000007850 fluorescent dye Substances 0.000 claims abstract description 6
- 239000002090 nanochannel Substances 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims description 40
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 28
- 238000001514 detection method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 7
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- -1 salt zinc nitrate hexahydrate Chemical class 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000013110 organic ligand Substances 0.000 claims description 5
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- 239000002184 metal Substances 0.000 claims description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 8
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract 1
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 18
- 238000002189 fluorescence spectrum Methods 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 229950002929 trinitrophenol Drugs 0.000 description 5
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- IZUKQUVSCNEFMJ-UHFFFAOYSA-N 1,2-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1[N+]([O-])=O IZUKQUVSCNEFMJ-UHFFFAOYSA-N 0.000 description 2
- WDCYWAQPCXBPJA-UHFFFAOYSA-N 1,3-dinitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC([N+]([O-])=O)=C1 WDCYWAQPCXBPJA-UHFFFAOYSA-N 0.000 description 2
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
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- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G—PHYSICS
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
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Abstract
本发明公开了一种具有纳米孔道结构的三维金属有机骨架材料的制备及应用。使用发光配体4,4′,4″‑三甲酸三苯胺在溶剂热条件下合成了一例具有纳米通道的金属有机骨架材料[(Zn4O)(H2O)2(TPA)2]·8DMA，制得的材料是具有一维纳米级方形孔道的(3,6)连接的三维网络。该材料可以作为有效的荧光探针，快速高效地检测硝基芳香族爆炸物，特别是苦味酸。此外材料可以通过简单的离心分离回收，实现循环再利用。本发明可获得一种具有纳米孔道结构的三维金属有机框架材料，合成方法简单。
The invention discloses the preparation and application of a three-dimensional metal-organic framework material with nano-pore structure. An example of a metal-organic framework with nanochannels [(Zn 4 O)(H 2 O) 2 (TPA) 2 ] was synthesized using the luminescent ligand 4,4′,4″-triphenylamine-tricarboxylate under solvothermal conditions. 8DMA, the obtained material is a (3,6) connected three-dimensional network with one-dimensional nanoscale square pores. The material can be used as an effective fluorescent probe to rapidly and efficiently detect nitroaromatic explosives, especially picric acid In addition, the material can be recovered by simple centrifugal separation to realize recycling. The present invention can obtain a three-dimensional metal-organic framework material with nano-pore structure, and the synthesis method is simple.
Description
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 by researchers due to their unique and interesting structures, chemical diversity and their potential widespread use in gas storage, separation, optical materials, drug delivery, heterogeneous catalysis, and the like. 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 great 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 nano-meterThe three-dimensional metal organic framework material with the pore channel structure has a chemical formula of [ (Zn)4O)(H2O)2(TPA)2]8DMA, wherein H3TPA 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 P21C; unit cell parameter of
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 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, in step 2), the reaction temperature is 100-; 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 and reusing are 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 therein3Solid 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 detection of crystals of the invention dispersed in 800ppm of a DMA solution of NB; FIG. 6(b) is a bar graph of fluorescence quenching efficiency of 6 cycles of 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 cycles of detection of crystals of the invention dispersed in 200ppm of 1,3-DNB in DMA solution; FIG. 6(d) is a bar graph of fluorescence quenching efficiency for 6 cycles of cycle detection with crystals of the invention dispersed in a DMA solution of 20ppm PA.
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' -triphenylamine tricarboxylate (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 autoclave in an oven, heating the stainless steel high-pressure autoclave from room temperature to 100 ℃ at a temperature of 10 ℃ per hour, reacting for 3 days at the temperature of 100 ℃, cooling to room temperature, repeatedly washing and separating by using 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)4O)(H2O)2(TPA)2]8DMA, wherein H3TPA is 4, 4' -triphenylamine tricarboxylate, DMA is N, N-dimethylacetamide; the crystal system is monoclinic; space group is P21C; unit cell parameter of
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 Zn4(μ4-O) cluster consisting of four Zn2+Ion, one μ4-O atom and two deprotonated TPA3-And (3) ligand composition. In Zn4(μ4-O) cluster, Zn3 adopts a hexa-coordinated octahedral geometry, whereas Zn1, Zn2 and Zn4 have a tetrahedral coordination geometry. One Zn4(μ4O) clusters are derived from two H3Six carboxylic acid groups of the TPA ligand are encapsulated. As shown in fig. 1Symmetry code is: #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
(FIGS. 2a, 2b and 2 d). From a topological point of view, each H3The TPA ligand can be viewed as a 3 point of attachment, each Zn4(μ4O) clusters can be seen as one 6 connection point, thus forming a (3,6) connected topology (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 was performed at room temperature using a Jasco FP-8600 spectrometer. As shown in FIG. 4, the synthesized crystal has an emission peak position at 440nm under 365nm wavelength excitation, and ligand H3The 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 show, from top to bottom, fluorescence of 5mg crystals in DMA solutions of NB at 0ppm, 50ppm, 100ppm, 200ppm, 400ppm, 600ppm, 800ppm and 1000ppm, respectivelyLight emission spectrum; 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-NO2The number decreases with increasing number, and therefore, it is inferred that the following-NO2The 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.
Further, the detected crystal samples were centrifuged, washed and recovered with DMA repeatedly, and the recovered samples were reused to detect these nitro compounds in a circulating manner. 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)/I0X 100% is determined, wherein I0Is 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 the cycle 1-6 is not obviously changed, which shows that the crystal of the invention has good recycling performance and stability in detection application. 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 (10)
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Citations (4)
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| CN103920158A (en) * | 2014-04-24 | 2014-07-16 | 青岛大学 | Chitosan-functionalized metal organic framework materials as well as preparation method and application thereof |
| CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of water-stable methylene blue adsorption material and preparation method and application thereof |
| CN109776813A (en) * | 2019-02-28 | 2019-05-21 | 重庆师范大学 | A red fluorescent zinc organic supramolecular, its preparation method and application |
| CN110975912A (en) * | 2019-10-21 | 2020-04-10 | 长春理工大学 | Preparation and application of a cobalt-nitrogen-doped catalyst derived from bimetallic MOFs |
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