CN106397467A - Metal-organic skeleton functionalized fluorescent material, preparation method and application thereof - Google Patents

Metal-organic skeleton functionalized fluorescent material, preparation method and application thereof Download PDF

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Publication number
CN106397467A
CN106397467A CN201610791662.4A CN201610791662A CN106397467A CN 106397467 A CN106397467 A CN 106397467A CN 201610791662 A CN201610791662 A CN 201610791662A CN 106397467 A CN106397467 A CN 106397467A
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metal
organic framework
fluorescence material
functional fluorescence
europium
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CN106397467B (en
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黄宏亮
衣鹏达
仲崇立
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • 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"
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/18—Metal complexes
    • C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide

Abstract

The invention provides a metal-organic skeleton functionalized fluorescent material, and the structural formula of the fluorescent material is [Eu12(FUM)18](H2O)8. The metal-organic skeleton functionalized fluorescent material employs europium as a central atom, and has high specific surface area, and at the same time, the fluorescent material has excellent fluorescence properties: distinct colors, long fluorescent lifetime, larger Stokes shift, and the like. The material is applied to identification and detection of explosive micromolecules, and can be used for selectively identifying TNP explosive micromolecules; more importantly, the material has higher sensitivity, and can respond 10<-8>M explosive micromolecules. The material can be used as a detection probe and can be recycled.

Description

A kind of metal-organic framework functional fluorescence material, preparation method and applications
Technical field
The present invention relates to a kind of metal aggregate and in particular to a kind of metal-organic framework materials, preparation method and its should With belonging to fluoroscopic examination field.
Background technology
With the progress of social development, science and technology, material detects in life sciences, environmental science, medical science and nuclear industry Play the role of more and more important etc. various fields.In numerous detection methods, fluoroscopic examination with its flexibly and fast, highly sensitive The feature of degree has obtained extensive concern.
Metal-organic framework materials are to be formed through Chemical self-assembly with organic ligand by inorganic metal ion or cluster, There is higher specific surface area and porosity, and regulatable pore size, it is in gas storage, adsorbing separation, catalysis, change Learn the aspect such as sensing and medicine transmission and have wide application prospect.
In the fields such as the recognition detection in explosive small molecule, not only need fluorescent material alternative identification TNP etc. quick-fried Fried thing small molecule, is more desirable to it and enables to respond in the case of low explosive little molecular concentration, that is, have high sensitivity.
In consideration of it, urgently proposing a kind of fluorescent material, achievable Selective recognition TNP explosive small molecule at present, and have There is good sensitivity.
Content of the invention
The technical problem to be solved provides a kind of achievable Selective recognition TNP explosive small molecule, and has There is the fluorescent material of good sensitivity, to meet the demand of the recognition detection of explosive small molecule etc..
In order to solve the problems, such as what prior art existed, the invention provides a kind of metal-organic framework functional fluorescence Material, the structural formula of described fluorescent material is [Eu12(FUM)18](H2O)8, hereinafter referred to as Eu-FUM.
Preferably, the duct of described fluorescent material is 1D duct.
Preferably, each metal europium ion of described fluorescent material respectively with part carboxyl on oxygen atom and hydrone Link.
Preferably, each metal europium ion nine of described fluorescent material is coordinated, respectively with 6 part carboxyls on oxygen atom And 1 moisture sublink.
It is further preferred that the on-link mode (OLM) of the oxygen atom on described metal europium ion and described part carboxyl is an oxygen Atom and an europium ion link, or, an oxygen atom and two europium ions link.
Present invention also offers the method preparing above-mentioned metal-organic framework functional fluorescence material, comprise the following steps： Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in and comprise DMF, salpeter solution Mixed solution in reacted, reaction end obtain final product.
The preparation method of described metal-organic framework functional fluorescence material, specifically includes following steps：With 2- fluorobenzene Formic acid, as regulator, fumaric acid and europium nitrate is placed in the N comprising DMF, nitric acid, N- dimethyl Reacted in formamide solution, the mixed solution of water, reaction terminates, gained mixed solution is obtained solid through filtering or being centrifuged Precipitation, is then washed to described solid precipitation with DMF, dichloromethane, last drying.
Preferably, the reaction temperature of described reaction is 100-140 DEG C, and the response time is 2-24h.
It is further preferred that the reaction temperature of described reaction is 100-140 DEG C, the response time is 2-24h；Described anti-butylene Mol ratio between diacid, 2- fluobenzoic acid, europium nitrate is (0.02-0.08)：(0.1-0.3)：(0.02-0.05)；Described N, Volume ratio between dinethylformamide, the N,N-dimethylformamide solution of nitric acid and water is：(1.2-2.4)：(0.05- 0.2)：(0.2-0.8)；The concentration of the N,N-dimethylformamide solution of described nitric acid is 1.5-4.5mol/L.
The application in detection probe field for the metal-organic framework functional fluorescence material of the present invention.
Preferably, described metal-organic framework functional fluorescence material is in the fluoroscopic examination field of explosive small molecule Application, described explosive small molecule includes one of TNP, PNP, 3-NP, 3-NT, 2-NP, 2-NT, 2,6-NT, 2,4-DNT Or it is multiple.
The present invention compared with prior art has the advantage that：
(1) metal-organic framework functional fluorescence material of the present invention, using europium as central atom, group of the lanthanides gold Belong to organic framework material and there is high-specific surface area, the fluorescent material of the present invention has excellent fluorescence property simultaneously again：There is color The features such as damp distinctness, fluorescence lifetime length, larger Stokes shift.When being applied to the recognition detection of explosive small molecule, Alternative identifies TNP explosive small molecule it is even more important that having high sensitivity, to concentration 10-8The explosive of M Small molecule still has response.
(2) metal-organic framework functional fluorescence material of the present invention, as detection probe, can be recycled.
Brief description
The structure chart of Fig. 1 functional fluorescence of the present invention material Eu-FUM；
Fluorescence intensity figure in the DMF solution of different explosive small molecules for Fig. 2 functional fluorescence material Eu-FUM；
Fig. 3 functional fluorescence material Eu-FUM immerses the fluorescence intensity figure in variable concentrations TNP solution；
Be recycled for multiple times in Fig. 4 functional fluorescence material Eu-FUM immersion TNP solution is quenched efficiency chart.
Specific embodiment
With reference to embodiments, the present invention is further described in detail, but is not limited to this.
Embodiment 1
In the present embodiment, the metal-organic framework functional fluorescence material of preparation has structural formula：[Eu12(FUM)18] (H2O)8.Hereinafter referred to as Eu-FUM (similarly hereinafter).
Its preparation method is as follows：
Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in comprise DMF, Reacted in the mixed solution of the DMF solution of nitric acid and water, wherein, described fumaric acid consumption is 0.02mmol；Described 2- fluobenzoic acid consumption is 0.3mmol；Europium nitrate consumption is 0.02mmol；Described N, N- dimethyl formyl The consumption of amine is 1.2ml；The consumption of salpeter solution is 0.05ml, and the concentration of the DMF solution of described nitric acid is 1.5mol/L；The consumption of water is 0.2ml；Reaction end obtains final product.
Embodiment 2
In the present embodiment, the metal-organic framework functional fluorescence material of preparation has structural formula：[Eu12(FUM)18] (H2O)8.
Its preparation method is as follows：
Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in comprise DMF, Reacted in the mixed solution of the DMF solution of nitric acid and water, reaction terminates, by gained mixed solution warp Filter or centrifugation obtain solid precipitation, then with DMF, dichloromethane, described solid precipitation is washed, Last drying.
Wherein, described fumaric acid consumption is 0.08mmol；Described 2- fluobenzoic acid consumption is 0.1mmol；Europium nitrate Consumption is 0.05mmol；The consumption of described N,N-dimethylformamide is 2.4ml；The consumption of salpeter solution is 0.2ml, described nitre The concentration of the N,N-dimethylformamide solution of acid is 4.5mol/L；The consumption of water is 0.8ml.
After measured, the duct of the described Eu-FUM preparing is 1D duct.
Embodiment 3
In the present embodiment, the metal-organic framework functional fluorescence material of preparation has structural formula：[Eu12(FUM)18] (H2O)8.
Its preparation method is as follows：
Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in comprise DMF, Reacted in the mixed solution of the DMF solution of nitric acid and water, reaction temperature is 100 DEG C, and the response time is 2h, reaction terminates, by gained mixed solution through filter or centrifugation obtain solid precipitation, then use DMF, two Chloromethanes wash to described solid precipitation, last drying.
Wherein, described fumaric acid consumption is 0.08mmol；Described 2- fluobenzoic acid consumption is 0.1mmol；Europium nitrate Consumption is 0.05mmol；The consumption of described N,N-dimethylformamide is 2.4ml；The consumption of salpeter solution is 0.2ml, described nitre The concentration of the N,N-dimethylformamide solution of acid is 4.5mol/L；The consumption of water is 0.8ml.
After measured, the duct of the described Eu-FUM preparing is 1D duct.
Embodiment 4
In the present embodiment, the metal-organic framework functional fluorescence material of preparation has structural formula：[Eu12(FUM)18] (H2O)8.
Its preparation method is as follows：
Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in comprise DMF, Reacted in the mixed solution of the DMF solution of nitric acid and water, reaction temperature is 140 DEG C, and the response time is 24h, reaction terminates, by gained mixed solution through filter or centrifugation obtain solid precipitation, then use DMF, two Chloromethanes wash to described solid precipitation, last drying.
Wherein, described fumaric acid consumption is 0.08mmol；Described 2- fluobenzoic acid consumption is 0.1mmol；Europium nitrate Consumption is 0.05mmol；The consumption of described N,N-dimethylformamide is 2.4ml；The consumption of salpeter solution is 0.2ml, described nitre The concentration of the N,N-dimethylformamide solution of acid is 4.5mol/L；The consumption of water is 0.8ml.
Embodiment 5
In the present embodiment, the metal-organic framework functional fluorescence material of preparation has structural formula：[Eu12(FUM)18] (H2O)8.The structure chart of functional fluorescence material Eu-FUM as described in Figure 1.
Its preparation method is as follows：
By organic ligand fumaric acid (0.06 mM), regulator 2- fluobenzoic acid (0.214 mM) and nitric acid Europium (0.0413 mM) is in N,N-dimethylformamide (2.2 milliliters), nitric acid (0.1 milliliter of 3.5 mol/L) and water (0.5 milli Rise) mixed solution in mix, reacting by heating 6h at 120 DEG C, be subsequently cooled to room temperature；By the white crystal obtaining N, N- The repeated multiple times washing of dimethylformamide, dichloromethane solvent, and room temperature drying.
Embodiment 6
The described material Eu-FUM preparing in embodiment 1-5 is carried out detecting performance test, concrete operation step is such as Under：
Take in the DMF solution containing different explosive small molecules for the material Eu-FUM immersion described in 2mg, respectively 0.001mol/L (TNP, PNP, 3-NP, 3-NT, 2-NP, 2-NT, 2,6-NT, 2,4-DNT), and detect its fluorescence intensity.
After measured, the functional fluorescence material Eu-FUM in embodiment 1-5 is in the DMF solution of different explosive small molecules It is respectively provided with stronger fluorescence intensity；Wherein it is illustrated in figure 2 the Eu-FUM prepare in embodiment 5 in little point of different explosives Fluorescence intensity figure in the DMF solution of son.
Embodiment 7
The described material Eu-FUM preparing in embodiment 1-5 is carried out detecting performance test, concrete operation step is such as Under：
Take in the solution containing variable concentrations TNP for the material Eu-FUM immersion described in 2mg, respectively 10-3,10-4,10-5,10-6,10-7,10-8Mol/L (TNP, PNP, 3-NP, 3-NT, 2-NP, 2-NT, 2,6-NT, 2,4-DNT), and detect its fluorescence intensity.
After measured, the functional fluorescence material Eu-FUM in embodiment 1-5 is respectively provided with immersion variable concentrations TNP solution Stronger fluorescence intensity；Wherein it is illustrated in figure 3 the Eu-FUM prepare in embodiment 5 in immersion variable concentrations TNP solution In fluorescence intensity figure.
Embodiment 8
The described material Eu-FUM preparing in embodiment 1-5 is carried out detecting performance test, concrete operation step is such as Under：
Take in the TNP solution that material Eu-FUM immersion described in 2mg contains, repeatedly circulate, detect being quenched of its recycling Efficiency.
After measured, the functional fluorescence material Eu-FUM in embodiment 1-5 still can have after multiple immersion TNP solution Stronger fluorescence intensity；Wherein it is illustrated in figure 4 in the Eu-FUM immersion TNP solution prepare in embodiment 5 and repeatedly circulate Use is quenched efficiency chart.
Obviously, above-described embodiment is only intended to clearly illustrate example, rather than the restriction to embodiment.For Change or the change of other multi-forms for those of ordinary skill in the art, can also be made on the basis of the above description Dynamic.There is no need to be exhaustive to all of embodiment, and the obvious change thus extended out or change Move among still in the protection domain of the invention.

Claims (10)

1. a kind of metal-organic framework functional fluorescence material is it is characterised in that the structural formula of described fluorescent material is [Eu12 (FUM)18](H2O)8.
2. metal-organic framework functional fluorescence material according to claim 1 is it is characterised in that described fluorescent material Duct be 1D duct.
3. metal-organic framework functional fluorescence material according to claim 1 and 2 is it is characterised in that described phosphor Material each metal europium ion respectively with part carboxyl on oxygen atom and moisture sublink.
4. metal-organic framework functional fluorescence material according to claim 3 is it is characterised in that described fluorescent material Each metal europium ion nine be coordinated, respectively with 6 part carboxyls on oxygen atom and 1 moisture sublink.
5. metal-organic framework functional fluorescence material according to claim 4 it is characterised in that described Europium Metal from The on-link mode (OLM) of the oxygen atom on sub and described part carboxyl is an oxygen atom and an europium ion links, or, an oxygen Atom and two europium ion links.
6. a kind of method of the metal-organic framework functional fluorescence material prepared described in any one in claim 1-4, its It is characterised by, comprise the following steps：Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in and comprise N, N- Reacted in dimethylformamide, the mixed solution of salpeter solution, reaction end obtains final product.
7. the preparation method of metal-organic framework functional fluorescence material according to claim 6 is it is characterised in that have Body comprises the following steps：Using 2- fluobenzoic acid as regulator, fumaric acid and europium nitrate are placed in and comprise N, N- dimethyl Reacted in Methanamide, the DMF solution of nitric acid, the mixed solution of water, reaction terminates, and gained is mixed Solution obtains solid precipitation through filtering or being centrifuged, and then with DMF, dichloromethane, described solid precipitation is entered Row washing, last drying.
8. the preparation method of metal-organic framework functional fluorescence material according to claim 7 is it is characterised in that institute The reaction temperature stating reaction is 100-140 DEG C, and the response time is 2-24h；Described fumaric acid, 2- fluobenzoic acid, europium nitrate Between mol ratio be (0.02-0.08)：(0.1-0.3)：(0.02-0.05)；Described N,N-dimethylformamide, the N of nitric acid, Volume ratio between dinethylformamide solution and water is：(1.2-2.4)：(0.05-0.2)：(0.2-0.8)；Described nitric acid N,N-dimethylformamide solution concentration be 1.5-4.5mol/L.
9. in claim 1-4 the metal-organic framework functional fluorescence material described in any one in detection probe field Application.
10. the application according to claim 9 is it is characterised in that described metal-organic framework functional fluorescence material In the application in the fluoroscopic examination field of explosive small molecule, described explosive small molecule includes TNP, PNP, 3-NP, 3-NT, 2- One or more of NP, 2-NT, 2,6-NT, 2,4-DNT.
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CN110951481A (en) * 2018-09-27 2020-04-03 天津工业大学 Application of double rare earth luminescent metal organic framework in phenolic compound detection
CN110951084A (en) * 2018-09-27 2020-04-03 天津工业大学 Application of white-light-emitting double-rare-earth metal organic framework material in detection of phenol pollutants
CN109385751A (en) * 2018-09-30 2019-02-26 武汉大学 The preparation method and applications of fluorescent nano-fiber film based on bimetallic organic backbone
CN109211863A (en) * 2018-10-26 2019-01-15 大连民族大学 Utilize Eu2+The method of f-f Transition Spectra detection explosive TNP
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CN110066401B (en) * 2019-05-16 2021-03-02 重庆师范大学 Red fluorescent rare earth europium coordination polymer and preparation method and application thereof
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CN110387547A (en) * 2019-08-26 2019-10-29 中国科学院海洋研究所 A kind of metal organic frame corrosion inhibiter hydrogel composites material and its application
CN110387547B (en) * 2019-08-26 2021-04-27 中国科学院海洋研究所 Metal organic framework corrosion inhibitor hydrogel composite material and application thereof

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