CN106749348B - A kind of metal-organic framework material and preparation method and application - Google Patents
A kind of metal-organic framework material and preparation method and application Download PDFInfo
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- CN106749348B CN106749348B CN201611025336.9A CN201611025336A CN106749348B CN 106749348 B CN106749348 B CN 106749348B CN 201611025336 A CN201611025336 A CN 201611025336A CN 106749348 B CN106749348 B CN 106749348B
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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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic System
- C07F3/06—Zinc compounds
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- C—CHEMISTRY; METALLURGY
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- 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
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- 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"
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- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
Abstract
The invention discloses a kind of metal-organic framework materials and preparation method and application, are related to metal-organic framework material synthesis technical field, and in particular to a kind of application based on 2,6-naphthalenedicarboxylic acid fluorescent type metal-organic framework material alternatively property fluorescence probe.Compound chemical formula is expressed as:C15H14ZnN6O4, it is assistant ligand to aminotetrazole with 2,6-naphthalenedicarboxylic acid for main ligand, using solvent-thermal method, solvent is the mixed liquor of n,N-Dimethylformamide and ethyl alcohol, synthesizes the three-dimensional structure with dual interpenetrating.The material has good chemical stability, and has studied the functional characteristic that explosive nitrobenzene is detected as a kind of efficient fluorescence probe.Provided by the invention preparation method is simple, and detection process high sensitivity, the reaction time is short, high recycling rate, is a kind of ideal fluorescence probe material.
Description
Technical field
The present invention relates to metal-organic framework material synthesis technical fields, and in particular to one kind is glimmering based on 2,6-naphthalenedicarboxylic acid
The application of light type metal-organic framework material alternatively property fluorescence probe.
Background technology
Metal organic frame (MOFs) material is by metal ion (or metal cluster) and organic ligand by being self-assembly of
One kind there is the frame material of periodical pore passage structure.As a kind of novel solid porous material, metal organic frame material
Material has potential application value in the adsorbing separation of gas, catalysis, fluorescence sense and proton conduction etc., referring to：
Allendorf, M.D.；Bauer,C.A.；Bhakta,R.K.,Houk,R.J.T.,Chem.Soc.Rev.2009,38,1330；
Burtch,N.C.；Jasuja,H.；Walton,K.S.,Chem.Rev.2014,114,10575.；Li,J.R.；Sculley,
J.；Zhou, H.C., Chem.Rev.2012,112,869. this kind of crystalline materials are rich and varied for the selection of metal and ligand,
The property of metal center and ligand directly affects the final performance applications of compound.Compared to some other luminescent materials,
The advantage of MOFs materials is that it can neatly be combined together inorganic component and organic component, to show to be different from
The characteristics of luminescence of traditional organic or inorganic material.The good MOFs materials of optical property often have in fluorescence detection
High sensitivity, selectivity is good, and the reaction time is short, the advantages such as recycling rate of waterused height, therefore this material is in terms of fluorescence sense
Using having become popular research direction.Referring to：Zhang,C.Y.；Che,Y.K.；Zhang,Z.X.；Yang,X.M.；Zang,
L.Chem.Commun.2011,47,2336；Liu,X.L.；Li,Y.S.；Ban,Y.J.；Peng,Y.；Jin,H.；Bux,H.；
Xu,L.Y.；Caro,J.；Yang,W.S.Chem.Commun.2013,49,9140.；Jayaramulu,K.；Kanoo,P.；
George,S.J.；Maji,T.K.Chem.Commun.2010,46,7906.
Invention content
It is an object of the invention to the performance studies of fluorescent type metal-organic framework material p-nitrophenyl detection, provide one kind
The preparation method of metal-organic framework material.There is the compound three-dimensional structure of dual interpenetrating, structure to have higherization
Stability is learned, compound, which is scattered in different solvents, can keep stable fluorescent emission.The metal-organic framework material pair
Nitrobenzene has sensitive selective fluorescence response, has good application prospect in materials science field.
Technical scheme of the present invention：
A kind of metal-organic framework material, chemical formula C15H14ZnN6O4, with 2,6-naphthalenedicarboxylic acid for main ligand, to amino
Tetrazole is assistant ligand, and using solvent-thermal method, solvent is the mixed liquor of n,N-Dimethylformamide and ethyl alcohol, and synthesis has double
The three-dimensional structure of weight interpenetrating.In this compound, zinc ion is the tetrahedral configuration of four-coordination, in two naphthalenedicarboxylic acid ligands
Carboxyl oxygen atom and two different Aminotetrazole ligands in nitrogen-atoms coordination.Aminotetrazole and metallic zinc in the compound
Ion coordination forms zigzag one-dimensional chain, then connects to form three-dimensional structure by naphthalene diacid.The three-dimensional structure is in a axis, b axis directions
On there are one-dimensional channels, and dimethylamine ion is filled in duct, dimethylamine ion plays balance in the compound
The effect of charge.Duct size along b axis directions isAfter removing the solvent molecule in duct, PLATON programs calculate
The result shows that porosity is 40.5%.Its topological structure is diamond-type topological structure.Compound is crystallized in monoclinic system, P21/
C space groups, cell parameter are respectively： α
=γ=90 °, β=92.13 °；The decomposition temperature of co-ordinating backbone is 300 DEG C.
The preparation method of the metal-organic framework material, includes the following steps：
1) it is N, N- bis- organic ligand 2,6-naphthalenedicarboxylic acid and aminotetrazole and zinc nitrate hexahydrate to be placed in solvent
In the mixed liquor of methylformamide and ethyl alcohol, the volume ratio of the in the mixed solvent n,N-Dimethylformamide and ethyl alcohol is 4：1,
It is uniformly mixed；
2) above-mentioned gained mixed liquor is transferred in the reaction kettle of polytetrafluoroethylene (PTFE), carries out constant temperature after sealing at 120 DEG C
Solvent thermal reaction, reaction time are 72 hours, and faint yellow bulk crystals are obtained after cooled to room temperature；
3) above-mentioned light yellow crystal washed with N,N-dimethylformamide and ethyl alcohol respectively, can be prepared by the gold after drying
Belong to organic framework materials.
Further, the molar ratio of the 2,6-naphthalenedicarboxylic acid, aminotetrazole and zinc nitrate hexahydrate is 1:2:2.
Further, the in the mixed solvent n,N-Dimethylformamide and the volume ratio of ethyl alcohol are 4：1,2,6- naphthalene diacid
Amount ratio with mixed solvent is 0.15 mM：7.5 milliliter.
A kind of application of the metal-organic framework material is used for for the fluorescent sensing material as detection nitrobenzene
The fluorescent sensing material of nitrobenzene is detected, method is to use fluorescent liquid detection means, prepares the suspension of compound, selectivity
P-nitrophenyl fluorescent quenching.When the concentration of nitrobenzene is to 160ppm, the fluorescent quenching rate of solution has reached 82.6%, chemical combination
Object can be as a kind of fluorescence probe of efficient detection nitrobenzene.
It is an advantage of the invention that：The metal-organic framework material is easily prepared, and raw material is simple, and compound has higher chemistry
Stability and good fluorescent emission performance.The compound shows high sensitivity during detecting nitrobenzene, selectivity
It is good, and the excellent feature such as can reuse, it has a good application prospect in materials science field.
Description of the drawings
Fig. 1 is the metal organic frame connection type figure and three-dimensional net structure figure.
Fig. 2 is the powder diagram of the metal organic frame.
Fig. 3 is the fluorescence response figure of the compound p-nitrophenyl.
Fig. 4 is the titration curve figure of the compound p-nitrophenyl.
Specific implementation mode
Example：
A kind of preparation method of the metal-organic framework material, includes the following steps：
1) by 2,6-naphthalenedicarboxylic acid (65mg), aminotetrazole (25mg), zinc nitrate hexahydrate (80mg) is added to poly- four
In the reaction kettle of vinyl fluoride, 7.5mL n,N-Dimethylformamide/ethyl alcohol (v is added:V=4:1) mixed solution.
2) the constant temperature 72h at 120 DEG C is being cooled to 30 DEG C by 48h programs, is obtaining blocky light yellow crystal, yield is about
It is 50%.
3) above-mentioned light yellow crystal N,N-dimethylformamide and ethyl alcohol are washed, it is dry after can be prepared by the metal and have
Machine frame frame material.
Gained metal-organic framework material chemical formula is C15H14ZnN6O4, with 2,6-naphthalenedicarboxylic acid for main ligand, to amino
Tetrazole is assistant ligand, and solvent is n,N-Dimethylformamide and alcohol mixeding liquid.Aminotetrazole and metal zinc ion coordination,
Zigzag one-dimensional chain is formed, then connects to form three-dimensional interpenetrating structure by naphthalene diacid.In attached drawing 1, a figures and b figures are included in structure
Two kinds of pore passage structures, porosity 40.5%；Illustrate that obtained sample purity is very high in attached drawing 2, the decomposition temperature of co-ordinating backbone is
300℃。
To the characterization of metal-organic framework material obtained：
Crystal structure determination
The monocrystalline for choosing suitable size under the microscope, with the Mo-K through graphite monochromator monochromatization on single crystal diffractometer
Alpha ray, temperature 293K collect diffraction data in a manner of ω-φ.All diffraction datas carry out absorption school using SADABS programs
Just.Cell parameter is determined with least square method.Data convert and structure elucidation use SAINT and SHELXTL programs to complete respectively.
It first uses difference function method and least square method to determine whole non-hydrogen atom coordinates, theoretical hydrogenation method is used in combination to obtain the hydrogen of main body framework
Then atom site carries out refine with least square method to crystal structure.Crystallography point diffraction data collection and structure refinement
Partial parameters see the table below 1.
Table 1：The crystal parameter table of the metal organic frame
R1=Σ | | Fo|-|Fc||/Σ|Fo|；wR2=[Σ [w (Fo 2-Fc 2)2]/Σw(Fo 2)2]1/2.
Topological structure of the present invention is diamond-type topological structure.Compound is crystallized in monoclinic system, P21/ c space groups, it is brilliant
Born of the same parents' parameter is respectively：α=γ=
90 °, β=92.13 °.
3) luminescent properties are studied
It is to be dispersed in the 3mg compound crystal grind into powder in 3mL solvents, then ultrasonic vibration 15min first.
Liquid fluorescent measurement shows that under the excitation wavelength of 320nm, suspension has stronger fluorescence emission peak at 418nm.Attached drawing 3
In, it is separately added into 20 μ L n,N-Dimethylformamide, n,N-dimethylacetamide, methanol, ethyl alcohol, dioxane, acetonitrile, second
Glycol, dichloromethane, hexamethylene and nitro benzene solvent, the p-nitrophenyl fluorescent quenching that compound can be selective.P-nitrophenyl
Fluorescence titration Dependence Results show, fluorescence response can occur when nitrobenzene 10ppm is added, the concentration of nitrobenzene arrives
When 160ppm, the fluorescent quenching rate of solution has reached 82.6%, the result shows compound p-nitrophenyl is very sensitive, the change
Closing object can be as a kind of fluorescence probe of efficient detection nitrobenzene.Fluorescence Spectrometer is to the metal organic frame fluoroscopic examination
Nitrobenzene is tested, and acquired results are as shown in figure 4, use Origin Software on Drawing.
It should be noted that the foregoing is merely the preferred embodiment of the present invention, only explains the present invention, not thereby limit
System the scope of the claims of the present invention.It is only obviously changed to belonging to the technology of the present invention design, equally protects model in the present invention
Within enclosing.
Claims (5)
1. a kind of metal-organic framework material, it is characterised in that：Chemical formula is C15H14ZnN6O4, matched based on 2,6-naphthalenedicarboxylic acid
Body, aminotetrazole are assistant ligand, and solvent is n,N-Dimethylformamide and alcohol mixeding liquid, aminotetrazole and metallic zinc
Ion coordination forms zigzag one-dimensional chain, then connects to form three-dimensional interpenetrating structure by naphthalene diacid, porosity 40.5%；The gold
Belong to organic framework materials crystal and belongs to trigonal system, P21/ c space groups, cell parameter are respectively：α=γ=90 °, β=
92.13°；The decomposition temperature of co-ordinating backbone is 300 DEG C.
2. a kind of preparation method of metal-organic framework material as described in claim 1, it is characterised in that include the following steps：
1) it is N, N- dimethyl organic ligand 2,6-naphthalenedicarboxylic acid and aminotetrazole and zinc nitrate hexahydrate to be placed in solvent
In the mixed liquor of formamide and ethyl alcohol, the volume ratio of the in the mixed solvent n,N-Dimethylformamide and ethyl alcohol is 4:1, mixing
Uniformly；
2) above-mentioned gained mixed liquor is transferred in the reaction kettle of polytetrafluoroethylene (PTFE), carries out incubating solvent after sealing at 120 DEG C
Thermal response, reaction time are 72 hours, and program obtains faint yellow bulk crystals after being cooled to room temperature；
3) above-mentioned light yellow crystal N,N-dimethylformamide and ethyl alcohol are washed, it is dry after can be prepared by the metal and have machine frame
Frame material.
3. the preparation method of metal-organic framework material according to claim 2, it is characterised in that：The 2,6- naphthalenes diformazan
The molar ratio of acid, aminotetrazole and zinc nitrate hexahydrate is 1:2:2.
4. the preparation method of the metal-organic framework material according to claim 2, it is characterised in that：The in the mixed solvent
The volume ratio of N,N-dimethylformamide and ethyl alcohol is 4:The amount ratio of 1,2,6- naphthalene diacid and mixed solvent is 0.15 mM:
7.5 milliliter.
5. a kind of application of metal-organic framework material as described in claim 1, it is characterised in that：For detecting nitrobenzene
Fluorescent sensing material, method are to use fluorescent liquid detection means, prepare the suspension of compound, selective p-nitrophenyl is glimmering
Optical quenching, when the concentration of nitrobenzene is to 160ppm, the fluorescent quenching rate of solution has reached 82.6%, and compound can be used as one
The fluorescence probe of kind detection nitrobenzene.
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| CN107793440B (en) * | 2017-11-23 | 2019-08-13 | 秦皇岛天大环保研究院有限公司 | Fluorescence porous material, synthetic method and its application |
| CN108593610B (en) * | 2018-04-17 | 2020-01-24 | 武汉大学 | Preparation method of fluorescence-enhanced test paper based on nanometer MV-MOF |
| CN108559096B (en) * | 2018-04-25 | 2020-09-11 | 聊城大学 | Luminescent metal organic framework material for detecting antibiotic pollutants in water |
| CN108384026B (en) * | 2018-05-03 | 2021-03-02 | 盐城师范学院 | Zinc-based metal organic framework material and preparation method and application thereof |
| CN109351334A (en) * | 2018-09-12 | 2019-02-19 | 内蒙古大学 | A kind of methylene blue adsorption number material and its preparation method and application that water is stable |
| CN113039129B (en) * | 2018-10-05 | 2024-01-09 | 萨莱·冈茨列兹马林 | Method, kit and inlay for security inspection and use of the kit and/or inlay |
| CN109880113B (en) * | 2019-03-11 | 2021-08-17 | 北京工业大学 | Metal-organic framework of Zn, preparation method and application thereof |
| CN112175193A (en) * | 2020-09-29 | 2021-01-05 | 陈燕 | Preparation method of flexible metal organic framework emitting white fluorescence |
| CN112159530A (en) * | 2020-10-28 | 2021-01-01 | 何雅贵 | Preparation and application of metal organic framework material |
| CN113877362B (en) * | 2021-10-12 | 2023-09-12 | 西安近代化学研究所 | Method for selectively adsorbing and separating nitrogen and near gas |
| CN115028853B (en) * | 2022-07-29 | 2024-03-29 | 广东石油化工学院 | Construction method of phycocyanin-metal organic framework |
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| CN105503912A (en) * | 2016-01-04 | 2016-04-20 | 辽宁大学 | Novel Zn (II) metal organic framework and synthetic method and application thereof |
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Effective date of registration: 20201118 Address after: Liyuan Road, green chemical industrial park, Yueyang City, Hunan Province Patentee after: Hunan Tianyi new material Co., Ltd Address before: 300350 Haihe Education Park, Jinnan District, Tianjin Patentee before: NANKAI University |
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