CN107602872A - A kind of preparation of luminous porous metals organic frame new material and its detection method to trace nitro explosive - Google Patents
A kind of preparation of luminous porous metals organic frame new material and its detection method to trace nitro explosive Download PDFInfo
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- CN107602872A CN107602872A CN201710807529.8A CN201710807529A CN107602872A CN 107602872 A CN107602872 A CN 107602872A CN 201710807529 A CN201710807529 A CN 201710807529A CN 107602872 A CN107602872 A CN 107602872A
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Abstract
The invention discloses a kind of luminous porous metals organic frame new material and its detection method to trace nitro explosive.The material is using zirconates and the organic carboxyl acid part containing amide group as raw material, under the conditions of existing for benzoic acid conditioning agent, the luminous porous metals organic frame new material of solvent structure, the efficient sensing detection to the nitro explosive in water can be realized, and have studied sensing detection performance of the material to nitro explosive.Material preparation is simple, stability is good, has the advantages that quick, easy, selectivity is good, high sensitivity, recyclable regenerative in terms of nitro explosive detection.
Description
Technical field
The invention belongs to metal-organic framework material field, in particulars relate to a kind of luminous porous metals organic frame green wood
The preparation of material and its detection method to trace nitro explosive.
Background technology
Nitro explosive, such as 2,4,6- trinitrophenols (TNP), TNT (TNT), ring trimethylene three
Nitramine (RDX), 2,4- dinitrotoluene (DNT)s (2,4-DNT) etc., have the characteristics that preparation method is ripe, insensitiveness is good, is easy to carry, quilt
It is widely used in military production and industrial explosion.Not only brisance is big for such compound, and toxicity is big, difficult degradation, cause
Cancer ability is strong, can cause vomiting, twitch after intrusion human body, nerve problems even death etc., therefore developing nitro explosive
Quick trace detection technology, to prevent the attack of terrorism, safeguard public safety and ensure human health it is significant.Mesh
Before, mainly there are chromatogram mass spectrography, surface acoustic wave method, ionic migration method, thermal oxide for the detection technique of trace nitro explosive
Reducing process etc.;But there is the problems such as expensive equipment, inconvenient to carry, complex operation, time-consuming in these methods mostly.By comparison,
Fluorescence sense detection method is to reach the purpose of analysis detection using the change of fluorescence signal (such as wavelength, intensity), and it has
Fast response time, high sensitivity, it is easy to operate, anti-electromagnetic interference capability is strong the advantages that.Professor Swager of america's MIT is waited in profit
With achieve in terms of fluorescence sense technology for detection trace nitro explosive breakthrough progress (Swager T.M. etc.,
J.Am.Chem.Soc.,1998,120,11864);Based on this achievement, the Nomadics companies in the U.S. further developed a system
Arrange Fido " optics dog nose " product for quick detection trace explosive, it is considered to be most sensitive explosive is visited in the world at present
Survey device.China is relatively later to the detection research starting of the fluorescence sense of explosive, technical equipment especially on material mostly according to
Rely external import, therefore develop the new material for fast detection of trace nitro explosive, it has also become needed badly in the field in China
One of major issue of solution.
Luminous porous metals organic framework materials (MOFs), it is a kind of to be formed by connecting using metal ion and organic ligand
Novel crystalline luminescent material with grid-structure.They have luminous intensity is high, stability is good, specific surface area is big,
The advantages that duct size and shape is adjustable, there is good application prospect in chemical sensitisation context of detection.Li etc. once reports one
The luminous porous metals organic framework materials of zirconium, although to show that the material can detect nitro quick-fried for fluorescence sense detection result of study
Fried thing, but fluorescent quenching degree difference of several nitro explosives for the material is little, without single-minded recognition capability (ginseng
See:Li J.-R. etc., J.Am.Chem.Soc., 2016,138,6204).Zang etc. once reports the luminous porous gold of a terbium
Belong to organic framework materials, result of study shows that the material has good selective enumeration method ability to TNP, but does not carry out its circulation
Regenerability research (referring to:Zang S.-Q. etc., Chem.Eur.J.2015,21,15705).Geng's love is net《Based on rigid virtue
Fragrant Carboxylic acid ligand MOFs design, synthesis and performance study》Disclose a kind of detection, base available for nitroaromatic
In N, the Cd-MOF materials of N '-two (3,5- dicarboxyphenyi)-Isosorbide-5-Nitrae-aphthalimide part, but it can not meet in water
TNP carries out the requirement of single-minded selectivity sensing identification.
In summary, in the prior art for for the luminous porous metals organic frame of nitro explosive detection in water
Single-minded selective enumeration method problem and recycling problem, still lack effective solution.
The content of the invention
In order to solve the above problems, the invention provides a kind of luminous porous metals organic frame new material and its preparation side
Method, a kind of luminous porous metals organic frame material of zirconium is synthesized using the organic carboxyl acid part of zirconium ion and phosphinylidyne-containing amine group
Material, and have studied sensing detection performance of the material to nitro explosive, the results showed that:The material not only preparation method it is simple,
Stability is good, and has quick, easy, selective good, high sensitivity, recyclable regenerative etc. excellent in terms of nitro explosive detection
Point.
To achieve these goals, the present invention adopts the following technical scheme that:
A kind of luminous porous metals organic framework materials of zirconium, the metal-organic framework material by zirconium ion and N- (3,
5- carboxyl phenyls) -4- carboxyl -1- naphthalenecarboxamides are built-up.
In order to solve existing luminous porous metals organic framework materials to different nitro explosive fluorescent quenching degree phases
Poor little, sensing identifies the problems such as single-minded selectivity is not high;The good water stability of zirconium metal-organic framework material is utilized simultaneously
Realize the detection to nitro explosive in water.The present invention using N- (3,5- carboxyl phenyls) -4- carboxyl -1- naphthalenecarboxamides from it is different
Zirconates assembling, obtained the zirconium metal-organic framework material with good water stability, result of study shows:The MOF materials
Good single-minded selectivity sensing recognition capability is shown to the TNP in water.This mainly due to N- (3,5- carboxyl phenyls)-
4- carboxyl -1- naphthalenecarboxamides have greatly with the zirconium ion assembling gained emission spectrum of MOF materials and TNP absorption spectrum
It is overlapping, make effective Resonance energy transfer (RET) can occur between the two;And lighted porous gold with existing most of zirconium
Category organic framework materials only identify that sensing nitro compound is different by pi-pi bond effect, the acyl in part used herein
Amine groups can form strong hydrogen bond with the oh group in nitro explosive TNP again, further enhance fluorescent quenching efficiency, carry
The sensitivity and selectivity of high sensing, so as to realize high sensitivity and the selectivity detection to nitro explosive such as TNP.
Present invention also offers a kind of system for the luminous porous metals organic frame new material for detecting trace nitro explosive
Preparation Method, with zirconates and N- (3,5- carboxyl phenyl) -4- carboxyl -1- naphthalenecarboxamides for raw material, under the conditions of existing for benzoic acid,
The luminous porous metals organic frame new material of solvent structure.
Preferably, the zirconates is zirconium chloride, zirconium oxychloride or five water zirconium nitrates.
Preferably, the present invention is used as conditioning agent using benzoic acid.In zirconium MOF materials synthesis, the introducing of conditioning agent not only may be used
The crystallinity of MOF materials is improved, and the pattern and size of MOF materials can be controlled.Generally, acid stronger conditioning agent is introduced
(such as formic acid, hydrochloric acid) is readily obtained the MOF crystal of reduced size;And introduce acid relatively weak conditioning agent (such as benzoic acid)
The MOF crystal of large-size can be then obtained, to meet the requirement of X-ray monocrystalline test.But alkaline regulation can not be introduced in testing
Agent, because according to NBO (NBO) theoretical OH–The NBO electric charges of middle oxygen atom are -1.403, are far longer than carboxylic acid in part
Electric charge -0.74 of upper coordinating oxygen atoms, therefore OH–Easily it is coordinated with Zr (IV), Zr-MOFs is hydrolyzed in aqueous slkali and collapse
Collapse, the MOFs materials that can not be stablized.Therefore, selection adds a certain amount of benzoic acid in present invention design, to obtain chi
Very little larger, constitutionally stable Zr-MOF materials.
Preferably, the mol ratio of the zirconates and N- (3,5- carboxyl phenyl) -4- carboxyl -1- naphthalenecarboxamides is 1.5~6:
4。
Suitable reaction temperature can not only provide required energy for reaction, but also can avoid making because temperature is too low
Reaction can not be smoothed out or temperature is too high to produce excessive side reaction;Reaction time is same outstanding for solvent-thermal process method
To be important, pass that short reaction is incomplete, and overlong time may then cause yield to reduce the time.Therefore, currently preferred solvent heat
The reaction condition of method is:24~72h is reacted at 90~110 DEG C, so that reaction is smoothed out, improves yield.
Present invention also offers luminous porous metals organic framework materials prepared by any above-mentioned method.
It is quick-fried in the different nitro of selective enumeration method present invention also offers above-mentioned luminous porous metals organic framework materials
Application in fried thing.
Beneficial effects of the present invention
(1) preparation method of luminescent metal organic framework materials of the present invention is simple, stability is good, detection efficiency
It is high, practical, it is easy to spread.
(2) as analyte TNP, TNT, RDX, 2,4-DNT, NB, NT and the luminescent metal organic framework materials of the present invention
During interaction, the change of luminescent material fluorescence intensity can be caused, but intensity of variation is different, utilizes the difference of this intensity of variation
The single-minded Selective recognition detection to different nitro explosives can be realized.
(3) the luminous porous metals organic framework materials that the present invention synthesizes are in nitro explosive (especially TNP) detection side
Face has quick, easy, the good, high sensitivity of selectivity, and has the advantages that recyclable regenerative, and recovery utilization rate is high.
Brief description of the drawings
The Figure of description for forming the part of the application is used for providing further understanding of the present application, and the application's shows
Meaning property embodiment and its illustrate be used for explain the application, do not form the improper restriction to the application.
Fig. 1 is the tomograph of the luminous porous metals organic framework materials synthesized by embodiment 1.
Fig. 2 is fluorescence Spectra of the luminous porous metals organic framework materials synthesized by embodiment 1 to various concentrations TNP solution
Figure.
Fig. 3 is luminous porous metals organic framework materials fluorescence intensity F of the TNP concentration to embodiment 10/ F curve map,
Illustration is luminous porous metals organic framework materials fluorescence intensity F of the TNP concentration to embodiment 10/ F Stern-Volmer lines
Property figure ([TNP]≤57.0 μm ol/L).
Fig. 4 is circular regeneration detection curve of the luminous porous metals organic framework materials synthesized by embodiment 1 to TNP.
Fig. 5 is fluorescence Spectra of the luminous porous metals organic framework materials synthesized by embodiment 1 to various concentrations TNT solution
Figure.
Fig. 6 is fluorescence Spectra of the luminous porous metals organic framework materials synthesized by embodiment 1 to various concentrations RDX solution
Figure.
Luminous porous metals organic framework materials of the Fig. 7 synthesized by embodiment 1 are to the glimmering of various concentrations 2,4-DNT solution
Spectrogram.
Fig. 8 is fluorescence Spectra of the luminous porous metals organic framework materials synthesized by embodiment 1 to various concentrations NB solution
Figure.
Fig. 9 is fluorescence Spectra of the luminous porous metals organic framework materials synthesized by embodiment 1 to various concentrations NT solution
Figure.
Luminous porous metals organic framework materials of the Figure 10 synthesized by embodiment 1 are to different nitro explosive fluorescence responses
Cylindricality comparison diagram.
Figure 11 is the HOMO and lumo energy figure of nitro explosive.
Figure 12 is the uv absorption spectra of nitro explosive.
Embodiment
It is noted that described further below is all exemplary, it is intended to provides further instruction to the application.It is unless another
Indicate, all technologies used herein and scientific terminology are with usual with the application person of an ordinary skill in the technical field
The identical meanings of understanding.
It should be noted that term used herein above is merely to describe embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singulative
It is also intended to include plural form, additionally, it should be understood that, when in this manual using term "comprising" and/or " bag
Include " when, it indicates existing characteristics, step, operation, device, component and/or combinations thereof.
Embodiment 1
The luminous porous metals organic framework materials of synthesis:By 17.5mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 75%.The structure of gained crystal is as shown in Figure 1.
Embodiment 2
The luminous porous metals organic framework materials of synthesis:By 24.2mg zirconium oxychlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 54%.
Embodiment 3
The luminous porous metals organic framework materials of synthesis:By the water zirconium nitrates of 32.2mg five, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 50%.
Embodiment 4
The luminous porous metals organic framework materials of synthesis:By 8.7mg zirconium chlorides, 37.9mg N- (3,5- carboxyl phenyls)-
4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid are dissolved in 3.0mL DMF solvents, after ultrasonic dissolution,
Solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 100 DEG C, at the uniform velocity cooled with 5 DEG C/h
To room temperature, transparent cake crystal is obtained.Product is filtered, and washed with DMF, is dried at room temperature, is collected, production
Rate is about 41%.
Embodiment 5
The luminous porous metals organic framework materials of synthesis:By 35.0mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 60%.
Embodiment 6
The luminous porous metals organic framework materials of synthesis:By 17.5mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 90 DEG C, at the uniform velocity dropped with 5 DEG C/h
Warm to room temperature, obtain transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is collected,
Yield is about 42%.
Embodiment 7
The luminous porous metals organic framework materials of synthesis:By 17.5mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 48h at 110 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 49%.
Embodiment 8
The luminous porous metals organic framework materials of synthesis:By 17.5mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 24h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 39%.
Embodiment 9
The luminous porous metals organic framework materials of synthesis:By 17.5mg zirconium chlorides, 37.9mg N- (3,5- carboxyl benzene
Base) -4- carboxyl -1- naphthalenecarboxamides and 240mg benzoic acid be dissolved in 3.0mL DMF solvents, through ultrasonic dissolution
Afterwards, solution is placed in the stainless steel cauldron of inner liner polytetrafluoroethylene, the isothermal reaction 72h at 100 DEG C, with 5 DEG C/h at the uniform velocity
Room temperature is cooled to, obtains transparent cake crystal.Product is filtered, and washed with DMF, is dried at room temperature, is received
Collection, yield is about 56%.
Embodiment 10
The luminous porous metals organic framework materials for weighing the preparation of 0.5mg embodiments 1 are scattered in 2ml distilled water, are determined
Its emission spectrum.Afterwards successively accumulation add 20,40,60,80,100,120,140,160,180,200 μ L TNP solution (1.00 ×
10-3Mol/L), its fluorescence emission spectrum is surveyed respectively.
As shown in Fig. 2 maximum emission wavelength of the luminous porous metals organic framework materials of the present invention in water is
407nm, its fluorescence intensity are gradually reduced with the increase of TNP concentration.When TNP concentration reaches 91 μm of ol/L, degree is quenched
For 95%.
As shown in Fig. 3 illustration, F0/ F and [Q] are in good linear relationship, and obtain its Stern-Volmer and be quenched often
Number is 3.9 × 104L/mol (Stern-Volmer equations:F0/ F=1+KSV[Q], wherein, F0For the porous metals organic frame that lights
The initial fluorescent intensity of material, the fluorescence intensity of F luminous porous metals organic framework materials in the presence of being TNP, [Q] is TNP's
Concentration, KSVConstant is quenched for Stern-Volmer).Under identical experiment condition, it need to only determine and light in the presence of thing to be detected
The fluorescence intensity F of porous metals organic framework materials, and calculate F0/ F, you can obtained according to standard curve in thing to be detected
TNP concentration [Q].
Embodiment 11
By it is above-mentioned be used for detect TNP material distilled water immersion, be cleaned by ultrasonic 3 times after, dry, recovery it is stand-by.
The luminous porous metals organic framework materials after receiving are fetched, are scattered in distilled water, and accumulation adds 200 μ L successively
TNP solution (1.00 × 10-3Mol/L) in above-mentioned dispersion liquid, after finding the initial fluorescent intensity of the salvage material and adding TNP
Fluorescence intensity and freshly prepd luminous porous metals organic framework materials initial fluorescent intensity and add TNP after fluorescence it is strong
Spend nearly identical, repeat above experimentation 5 times, do not find significant change (Fig. 4), show that material of the present invention has weight
The advantages of renaturation is good, reusable edible.
Embodiment 12
The experimental program as described in embodiment 10, other nitro explosives (TNT, RDX, 2,4-DNT, NB, NT) are entered respectively
Fluorescent quenching research is gone, fluorescence emission spectrum is shown in Fig. 5~9.Figure 10 is synthesized luminous porous metals organic framework materials
To different nitro explosive fluorescence response cylindricality comparison diagrams, it can be seen from fig. 10 that material of the present invention is to different nitros
The fluorescent quenching degree of explosive is different, and wherein that most pronounced effects is TNP, it is seen that material of the present invention explodes to different nitros
Thing has selective enumeration method ability.
MOF materials synthesized by the present invention are to nitro explosive (such as TNP, TNT, RDX, 2,4-DNT, NB, NT) table in water
Good fluorescence sense Detection results are revealed, its reason is:(1) nitro explosive has strong electrophilic nitryl group,
It is good electron acceptor, and metal-organic framework material is typically all good electron donor, therefore under illumination condition, can
To occur, from metal-organic framework material (electron donor), to the electronics transfer between nitro explosive (electron acceptor), (PET is imitated
Should), so as to cause fluorescent quenching.According to density functional theory (DFT) be calculated nitro explosive lumo energy order be
TNP>TNT>2,4-DNT>RDX>NB>NT (Figure 11), with fluorescent quenching efficiency TNP in this experiment>TNT>RDX>2,4-DNT>NB>
NT order is basically identical but not fully identical, and this shows that PET effects are not the single factors for determining fluorescent quenching efficiency.
(2) fluorescent quenching efficiency is also relevant with the number of nitro in nitro explosive molecule.Contain three in TNP, TNT and RDX molecule
Individual nitryl group, contain two nitryl groups in 2,4-DNT molecules, respectively contain a nitryl group in NB and NT molecules, therefore
Divided according to nitro number, fluorescent quenching efficiency general sequence is (TNP, TNT, RDX)>2,4-DNT>(NB, NT), this and experiment
As a result it is basically identical.
In addition, the MOF materials have the main reason for single-minded selective enumeration method to TNP:(1) TNP absorption spectrum and sheet
The emission spectrum for the metal-organic framework material reported in invention has a greater degree of overlapping, makes between the two to occur effectively
Resonance energy transfer (RET), and with the absorption spectrum of other nitro explosives is hardly overlapping or overlapping very little (Figure 12), because
This, the MOF materials show highest quenching efficiency to TNP.(2) compared with other nitro explosives, the hydroxyl in TNP molecules
Group can form strong hydrogen bond with the amide group of metal-organic framework material, effectively strengthen interaction and energy between Subjective and Objective
Amount transfer, further improves fluorescent quenching efficiency.Therefore, it is luminous synthesized by the present invention in cited nitro explosive
MOF materials not only show the fluorescent quenching efficiency of maximum to TNP, and degree is quenched apparently higher than other nitro explosives
(Figure 10), this shows that the material has single-minded selective enumeration method recognition capability to TNP.
Although above-mentioned the embodiment of the present invention is described with reference to accompanying drawing, model not is protected to the present invention
The limitation enclosed, one of ordinary skill in the art should be understood that on the basis of technical scheme those skilled in the art are not
Need to pay various modifications or deformation that creative work can make still within protection scope of the present invention.
Claims (10)
- The porous metals organic framework materials 1. a kind of zirconium lights, it is characterised in that the metal-organic framework material is by zirconium ion It is built-up with N- (3,5- carboxyl phenyls) -4- carboxyl -1- naphthalenecarboxamides.
- 2. metal-organic framework material as claimed in claim 1, it is characterised in that the zirconates and N- (3,5- carboxyl benzene Base) -4- carboxyl -1- naphthalenecarboxamides mol ratio be 1.5~6:4.
- 3. a kind of preparation method for the luminous porous metals organic frame new material for detecting trace nitro explosive, its feature exist In with zirconates and N- (3,5- carboxyl phenyl) -4- carboxyl -1- naphthalenecarboxamides for raw material, in condition existing for acidic ph modifier Under, the luminous porous metals organic frame new material of solvent structure.
- 4. method as claimed in claim 3, it is characterised in that the zirconates is zirconium chloride, zirconium oxychloride or five water zirconium nitrates.
- 5. method as claimed in claim 3, it is characterised in that the pH adjusting agent is benzoic acid.
- 6. method as claimed in claim 3, it is characterised in that the zirconates and N- (3,5- carboxyl phenyl) -4- carboxyl -1- naphthalenes The mol ratio of formamide is 1.5~6:4.
- 7. method as claimed in claim 3, it is characterised in that the reaction condition of the solvent-thermal method is:At 90~110 DEG C React 24~72h.
- 8. luminous porous metals organic framework materials prepared by the method described in claim any one of 3-7.
- 9. the luminous porous metals organic framework materials described in claim 8 are in the different nitro explosive of selective enumeration method Using.
- 10. application of the luminous porous metals organic framework materials in single-minded selective enumeration method TNP described in claim 8.
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