CN106749348A - 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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- CN106749348A CN106749348A CN201611025336.9A CN201611025336A CN106749348A CN 106749348 A CN106749348 A CN 106749348A CN 201611025336 A CN201611025336 A CN 201611025336A CN 106749348 A CN106749348 A CN 106749348A
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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
- 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
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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 material and preparation method and application, it is related to metal-organic framework material synthesis technical field, and in particular to application of the one kind based on 2,6 naphthalenedicarboxylic acid fluorescent type metal-organic framework materials alternatively property fluorescence probe.Compound chemical formula is expressed as:C15H14ZnN6O4, with 2,6 naphthalenedicarboxylic acids are main part, are assistant ligand to aminotetrazole, and using solvent-thermal method, solvent is the mixed liquor of N, N dimethylformamides and ethanol, three-dimensional structure of the synthesis with dual IPN.The material has good chemical stability, and have studied the functional characteristic that explosive nitrobenzene is detected as a kind of efficient fluorescence probe.The preparation method that the present invention is provided is simple and easy to apply, and detection process sensitivity is high, and the reaction time is short, high recycling rate, is a kind of preferable fluorescence probe material.
Description
Technical field
The present invention relates to metal-organic framework material synthesis technical field, and in particular to one kind is glimmering based on NDA
The application of light type metal-organic framework material alternatively property fluorescence probe.
Background technology
Metal organic frame (MOFs) material is by being self-assembly of by metal ion (or metal cluster) and organic ligand
A class there is the frame material of periodicity pore passage structure.As a kind of new solid porous material, metal organic frame material
Expect that the aspect such as conducting in the adsorbing separation of gas, catalysis, fluorescence sense and proton has potential application value, 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 part,
The property of metal center and part directly affects the final performance applications of compound.Compared to other some luminescent materials,
The advantage of MOFs materials is that it can neatly be combined together inorganic component and organic component, so as 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
Sensitivity is high, and selectivity is good, and the reaction time is short, the advantage such as recycling rate of waterused is high, 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.
The content of the invention
It is an object of the invention to the performance study of fluorescent type metal-organic framework material p-nitrophenyl detection, there is provided a kind of
The preparation method of metal-organic framework material.The compound has the three-dimensional structure of dual IPN, and its structure has change higher
Stability is learned, compound can keep stable fluorescent emission in being scattered in different solvents.The metal-organic framework material pair
Nitrobenzene has sensitive selectivity fluorescence response, has good application prospect in material science.
Technical scheme：
A kind of metal-organic framework material, chemical formula is C15H14ZnN6O4, it is main part with NDA, to amino four
Nitrogen azoles is assistant ligand, and using solvent-thermal method, solvent is the mixed liquor of DMF and ethanol, and synthesis has dual mutual
The three-dimensional structure worn.In this compound, zinc ion is the tetrahedral configuration of four-coordination, with the carboxyl in two naphthalenedicarboxylic acid parts
Nitrogen-atoms coordination in oxygen atom and two different Aminotetrazole parts.Aminotetrazole and metal zinc ion are matched somebody with somebody in the compound
Position, forms zigzag one-dimensional chain, then connect to form three-dimensional structure by naphthalene diacid.The three-dimensional structure is deposited on a axles, b direction of principal axis
In one-dimensional channels, and dimethylamine ion is filled with duct, dimethylamine ion plays balancing charge in the compound
Effect.Duct size along b direction of principal axis isAfter solvent molecule in removal duct, PLATON program calculated results
Show that porosity is 40.5%.Its topological structure is diamond-type topological structure.Compound is crystallized in monoclinic system, P21/ c is empty
Between group, cell parameter is 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, comprises the following steps：
1) by organic ligand NDA and aminotetrazole, and zinc nitrate hexahydrate is placed in solvent for N, N- bis-
In the mixed liquor of NMF and ethanol, the volume ratio of DMF and ethanol is 4 in the mixed solvent：1,
It is well mixed；
2) above-mentioned gained mixed liquor is transferred in the reactor of polytetrafluoroethylene (PTFE), carries out constant temperature after sealing at 120 DEG C
Solvent thermal reaction, the reaction time is 72 hours, and faint yellow bulk crystals are obtained after naturally cooling to room temperature；
3) above-mentioned light yellow crystal is washed with N,N-dimethylformamide and ethanol respectively, dry after can be prepared by the gold
Category organic framework materials.
Further, the mol ratio of the NDA, aminotetrazole and zinc nitrate hexahydrate is 1:2:2.
Further, the volume ratio of DMF and ethanol is 4 in the mixed solvent：1,2,6- naphthalene diacid
It it is 0.15 mM with the amount ratio of mixed solvent：7.5 milliliters.
A kind of application of the metal-organic framework material, for the fluorescent sensing material as detection nitrobenzene, is used for
The fluorescent sensing material of nitrobenzene is detected, method is that the suspension of compound is prepared using fluorescent liquid detection means, 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
Thing 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 chemistry higher
Stability and good fluorescent emission performance.The compound is during nitrobenzene is detected, it is high to show sensitivity, selectivity
It is good, and the excellent feature such as can reuse, had a good application prospect in material science.
Brief description of the drawings
Fig. 1 is the metal organic frame connected mode 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 embodiment
Example：
A kind of preparation method of the metal-organic framework material, comprises the following steps：
1) by NDA (65mg), aminotetrazole (25mg), zinc nitrate hexahydrate (80mg) is added to poly- four
In the reactor of PVF, 7.5mL DMFs/ethanol (v is added:V=4:1) mixed solution.
2) the constant temperature 72h at 120 DEG C, by 48h programmed coolings to 30 DEG C, is obtaining block light yellow crystal, and yield is about
It is 50%.
3) above-mentioned light yellow crystal is washed with N,N-dimethylformamide and ethanol, dry after can be prepared by the metal and have
Machine frame frame material.
Gained metal-organic framework material chemical formula is C15H14ZnN6O4, it is main part with NDA, to amino
Tetrazole is assistant ligand, and solvent is DMF 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.As in accompanying drawing 1, scheme comprising a figures and b in structure
Two kinds of pore passage structures, porosity is 40.5%；Illustrate that prepared sample purity is very high in accompanying drawing 2, the decomposition temperature of co-ordinating backbone is
300℃。
To the sign of obtained metal-organic framework material：
Crystal structure determination
The monocrystalline of suitable size is chosen under the microscope, with the Mo-K through graphite monochromator monochromatization on single crystal diffractometer
Alpha ray, temperature is 293K, and diffraction data is collected in ω-φ modes.All diffraction datas carry out absorption school using SADABS programs
Just.Cell parameter is determined with least square method.Data convert and structure elucidation are completed using SAINT and SHELXTL programs respectively.
First determine whole non-hydrogen atom coordinates with difference function method and least square method, and the hydrogen of main body framework is obtained with theoretical hydrogenation method
Atom site, then 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 research
First it is, by the 3mg compound crystal grind into powders, to be dispersed in 3mL solvents, then ultrasonic vibration 15min.
Liquid fluorescent is determined and shown, under the excitation wavelength of 320nm, suspension has stronger fluorescence emission peak at 418nm.Accompanying drawing 3
In, it is separately added into 20 μ L DMFs, DMA, methyl alcohol, ethanol, 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 can fluorescence response when nitrobenzene 10ppm is added, the concentration of nitrobenzene arrives
During 160ppm, the fluorescent quenching rate of solution has reached 82.6%, the result shows compound p-nitrophenyl is very sensitive, the change
Compound can be as a kind of fluorescence probe of efficient detection nitrobenzene.XRF 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 only the preferred embodiment of the present invention, the present invention is only explained, not thereby limited
System the scope of the claims of the present invention.It is only obvious to belonging to the technology of the present invention design to change, equally in present invention protection model
Within enclosing.
Claims (5)
1. a kind of metal-organic framework material, it is characterised in that：Chemical formula is C15H14ZnN6O4, matched somebody with somebody based on NDA
Body, is assistant ligand to aminotetrazole, and solvent is DMF 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, and porosity is 40.5%；The gold
Category organic framework materials crystal belongs to trigonal system, P21/ c space groups, cell parameter is respectively： α=γ=90 °, β=92.13 °；Coordination
The decomposition temperature of skeleton is 300 DEG C.
2. a kind of preparation method of metal-organic framework material as claimed in claim 1, it is characterised in that comprise the following steps：
1) by organic ligand NDA and aminotetrazole, and zinc nitrate hexahydrate is placed in solvent for N, N- dimethyl
In the mixed liquor of formamide and ethanol, the volume ratio of DMF and ethanol is 4 in the mixed solvent：1, mixing
Uniformly；
2) above-mentioned gained mixed liquor is transferred in the reactor of polytetrafluoroethylene (PTFE), carries out incubating solvent after sealing at 120 DEG C
Thermal response, the reaction time is 72 hours, and faint yellow bulk crystals are obtained after programmed cooling to room temperature；
3) above-mentioned light yellow crystal is washed with N,N-dimethylformamide and ethanol, 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 mol 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：In the mixed solvent
The volume ratio of N,N-dimethylformamide and ethanol is 4：1,2,6- naphthalene diacid is 0.15 mM with the amount ratio of mixed solvent：
7.5 milliliters.
5. a kind of application of metal-organic framework material as claimed in claim 1, it is characterised in that：For detecting nitrobenzene
Fluorescent sensing material, method is that the suspension of compound is prepared using fluorescent liquid detection means, and the p-nitrophenyl of selectivity 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 as one
Plant the fluorescence probe of efficient detection nitrobenzene.
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| CN107793440A (en) * | 2017-11-23 | 2018-03-13 | 秦皇岛天大环保研究院有限公司 | Fluorescence porous material, synthetic method and its application |
| CN108384026A (en) * | 2018-05-03 | 2018-08-10 | 盐城师范学院 | A kind of zinc-base metal-organic framework material and its preparation method and application |
| CN108559096A (en) * | 2018-04-25 | 2018-09-21 | 聊城大学 | The luminescent metal organic framework materials of antibiotic pollutant in a kind of detection water |
| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| 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 |
| CN109880113A (en) * | 2019-03-11 | 2019-06-14 | 北京工业大学 | A kind of metal-organic framework of Zn, preparation method and applications |
| CN112159530A (en) * | 2020-10-28 | 2021-01-01 | 何雅贵 | Preparation and application of metal organic framework material |
| CN112175193A (en) * | 2020-09-29 | 2021-01-05 | 陈燕 | Preparation method of flexible metal organic framework emitting white fluorescence |
| CN113039129A (en) * | 2018-10-05 | 2021-06-25 | 萨莱·冈茨列兹马林 | Security inspection method and kit of detachable disposable inlays with X-ray tray |
| CN113877362A (en) * | 2021-10-12 | 2022-01-04 | 西安近代化学研究所 | Selective adsorption and separation method for nitrogen and near gas |
| CN115028853A (en) * | 2022-07-29 | 2022-09-09 | 广东石油化工学院 | Construction method of phycocyanin-metal organic framework |
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| CN108593610A (en) * | 2018-04-17 | 2018-09-28 | 武汉大学 | A kind of preparation method of the Fluorescence Increasing type test paper for biomarker analyte detection based on nanometer MV-MOF |
| CN108593610B (en) * | 2018-04-17 | 2020-01-24 | 武汉大学 | Preparation method of fluorescence-enhanced test paper based on nanometer MV-MOF |
| CN108559096A (en) * | 2018-04-25 | 2018-09-21 | 聊城大学 | The luminescent metal organic framework materials of antibiotic pollutant in a kind of detection water |
| CN108384026A (en) * | 2018-05-03 | 2018-08-10 | 盐城师范学院 | A kind of zinc-base metal-organic framework material and its preparation method and application |
| 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 |
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| CN109880113B (en) * | 2019-03-11 | 2021-08-17 | 北京工业大学 | Metal-organic framework of Zn, preparation method and application thereof |
| CN109880113A (en) * | 2019-03-11 | 2019-06-14 | 北京工业大学 | A kind of metal-organic framework of Zn, preparation method and applications |
| 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 |
| CN113877362A (en) * | 2021-10-12 | 2022-01-04 | 西安近代化学研究所 | Selective adsorption and separation method for nitrogen and near gas |
| 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 |
| CN115028853A (en) * | 2022-07-29 | 2022-09-09 | 广东石油化工学院 | Construction method of phycocyanin-metal organic framework |
| 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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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 |