CN105622645A - Metal-organic framework compound-metal fullerene compound and preparation method thereof - Google Patents
Metal-organic framework compound-metal fullerene compound and preparation method thereof Download PDFInfo
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Abstract
The invention provides a metal-organic framework compound-metal fullerene compound and a preparation method thereof. The method is characterized in that a metal-organic framework compound material is immersed into a metal fullerene organic solution to obtain a mixing system of the metal-organic framework compound-metal fullerene compound. The metal-organic framework compound material takes organic carboxylic acid as an organic ligand and takes transition metal as a node for constitution; the metal fullerene is selected from at least one of the followings: M@C2n, M2@C2n, M3N@C2n, M3CN@C2n, M2C2@C2n, M3C2@C2n,and M2@C79N, wherein M is Sc, Y and lanthanide metals, and n is 30-50. The metal-organic framework compound is used for absorbing metal fullerene, and a metal fullerene structure with monodispersity under a solid state.
Description
Technical field
The invention belongs to metal fullerene field of compound material, be specifically related to a kind of metal organic framework compound-metal fullerene complex and preparation method thereof.
Background technology
At present, embedded metal fullerene molecule is paid attention to nested structure and the excellent physicochemical properties extremely people of its uniqueness, has become as the critical function material in the fields such as current physics, chemistry, material and life sciences. Metal fullerene and derivant thereof have a wide range of applications in magnetic material, quantum information process, solar energy receptor, NMR contrast agent, antitumor drug, optical dynamic therapy medicine etc.
The application of metal fullerene is also faced with some problems, and the bulk metal fullerene-based material of such as ordered structure has a potential application on quantum information storage, but the more difficult acquisition of its monocrystalline. Metal fullerene block structure also has application potential in absorbing material etc. Therefore, to prepare metal fullerene ordered structure block materials significant in exploration.
Metallic organic framework (metal-organicframework, MOF) compound-material is a kind of three-dimensional netted loose structure, have that specific surface area is big, porosity is high, various structures, prepare the advantages such as simple, all have a wide range of applications at numerous areas such as ionic adsorption, gas storage, chemical catalysis, sensing, biomedicines. The mono-crystalline structures of MOF makes its duct be uniformly distributed, and has extraordinary long-range order characteristic.
Metal organic framework compound adsorbing metal fullerene is utilized to obtain under solid monodispersed metal fullerene structure currently without report.
Summary of the invention
It is an object of the invention to provide a kind of metal organic framework compound-metal fullerene complex and preparation method thereof. Described method utilizes metallic framework compound adsorbing metal fullerene, it is thus achieved that monodispersed metal fullerene structure under solid-state.
Metal organic framework compound provided by the present invention-metal fullerene complex is prepared by the method comprising the following steps: be immersed in the organic solution of metal fullerene by metal organic framework compound material, obtains the mixed system containing metal organic framework compound-metal fullerene complex.
In said method, the shortest dimension in the duct of described metal organic framework compound is 0.5nm, and full-size is less than 10nm, and this size includes major part metal fullerene molecule, and metal fullerene molecule can be distributed in each duct single dispersing.
Described metal organic framework compound material is with organic carboxyl acid for organic ligand, and transition metal is the metal organic framework compound material that node is constructed;
Described organic carboxyl acid concretely p-phthalic acid (H2BDC), benzenetricarboxylic acid (H3And derivant BTC); Described transition metal is selected from following at least one: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
Described metal-organic framework materials is concretely: Zn4O(BDC)3(MOF-5)��Al(OH)(BDC)(MIL-53)��Zn4O(BTB)2And Cr (MOF-177)3F(H2O)2O(BDC)2(MIL-101)��
The synthetic method concretely hydro-thermal method of above-mentioned metal organic framework compound material, solvent-thermal method, microwave method, ultrasonic method, electrochemical process etc.
In the building-up process of described metal organic framework compound material, the solvent of employing is selected from following at least one: DMF, N, N-diethylformamide, triethylamine, second alcohol and water.
In said method, in the organic solution of described metal fullerene, solute is metal fullerene, and solvent is the organic solvent that can dissolve metal fullerene.
Described metal fullerene is selected from following at least one: MC2n��M2C2n��M3NC2n��M3CNC2n��M2C2C2n��M3C2C2n��M2C79N, wherein M is Sc, Y and lanthanide series metal, n=30��50.
Described organic solvent is selected from following at least one: toluene, Carbon bisulfide, o-dichlorohenzene, o-Dimethylbenzene and benzene.
The time of described immersion is 0.5 day-7 days.
Described metal organic framework compound material is 100-1:1 with the mass ratio of metal fullerene in the organic solution of described metal fullerene, it is preferred to 20-5:1, concretely 10:1 or 5:1.
Said method also includes separating the step obtaining described metal organic framework compound-metal fullerene complex from the described mixed system containing metal organic framework compound-metal fullerene complex. Concrete operations are as follows: first filtered by the described mixed system containing metal organic framework compound-metal fullerene complex, collect solid (metal organic framework compound-metal fullerene complex), surface followed by solid described in solvent washing, finally described solid is dried, obtains described metal organic framework compound-metal fullerene complex.
The metal organic framework compound prepared by said method-metal fullerene complex falls within protection scope of the present invention.
The present invention can select the MOF structure with different-shape, size, and metal fullerene is had certain selectivity by the part of different size of duct and different functional groups, it is possible to the selective molecule adsorbing particular size particular polarity. Described metal-organic framework materials can be prepared by being used in combination of one or more in hydro-thermal method, solvent-thermal method, microwave method, ultrasonic method, electrochemical process, it is hereby achieved that the various sizes of MOF structure of different-shape.
The method of the present invention can obtain the composite of different filling proportion by regulating described metal organic framework compound material, such that it is able to play the performance advantage of metal fullerene and MOF as required to greatest extent from the proportioning of metal fullerene. In the MOF complex of metal fullerene, owing to some MOF skeleton contains aromatic radical, they with the stronger intermolecular interaction that has of metal fullerene, and can make metal fullerene arrange at MOF orderly duct interior orientation, it is thus achieved that is similar to the molecular sequences in metal fullerene monocrystalline.
Metal organic framework compound obtained by the present invention-metal fullerene complex can be applicable to the shielding of X-ray, such as Lu3NC80Molecule has the ability absorbing more by force X-ray, scattered Lu in MOF complex3NC80Molecule has great absorbing surface, and its MOF complex can serve as radiation shielding material, and protection human body exempts from radiation. Metal organic framework compound-metal fullerene complex can also be used with and prepares magnetic crystal, for instance, Y2C79N is the molecule containing single electron spin, when this molecule is embedded in the orderly duct of MOF, is equivalent to these electron spins also ordered arrangement, so that compound crystal has the character that magnetic anisotropy, paramagnetic and antiferromagnetic transition etc. are special.
Accompanying drawing explanation
Fig. 1 is the powder X-ray RD phenogram of the MOF-5 that embodiment 1 prepares.
Fig. 2 be embodiment 1 prepare adsorbed Sc3NC80The powder X-ray RD phenogram of MOF-5.
Fig. 3 is the powder X-ray RD phenogram of the porous material MIL-53 that embodiment 2 prepares.
Fig. 4 be embodiment 2 prepare adsorbed Sc3NC80The powder X-ray RD phenogram of MIL-53.
Fig. 5 be embodiment 2 prepare adsorbed Y2C79The powder X-ray RD phenogram of the MIL-53 of N.
Fig. 6 be embodiment 3 prepare adsorbed Y2C79The ESR phenogram of the powder of the MIL-53 of N.
Detailed description of the invention
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
The experimental technique used in following embodiment if no special instructions, is conventional method; Reagent used in following embodiment, biomaterial etc., if no special instructions, all commercially obtain.
Embodiment one
Being dissolved in 10mLDMF by 0.29g zinc nitrate hexahydrate and 0.13g p-phthalic acid, this solution was in reaction kettle for reaction 21 hours, and temperature is set as 120 degree, and gained solid is dry after washing three times with DMF. Take 10mg pressed powder and carry out XRD sign, as it is shown in figure 1, this structure is MOF-5 (pore size 1-2nm). Take 20mgMOF-5 powder, be immersed in the Sc of 5mL3NC80Toluene solution in (containing 2mgSc3NC80). In immersion process, the Sc of naked eyes red color visible3NC80Toluene solution color gradually become shallower as, until disappearing, simultaneously the color of MOF-5 has white gradual change to redness, and Sc is described3NC80Enter in the duct of MOF. Dry after solid taking-up being washed with toluene after 3 days, characterize.
Fig. 2 is that MOF-5 has adsorbed Sc3NC80XRD figure spectrum afterwards, compares peak type and is more or less the same with Fig. 1, it can be seen that MOF-5 is at absorption Sc3NC80After remain its crystal structure.
Embodiment two
Being dissolved in 28.8mL water by 5.14g ANN aluminium nitrate nonahydrate and 1.66g p-phthalic acid, this solution was in reaction kettle for reaction three days, and temperature is set as 220 degree, dry after gained solids washed with water three times. Take 10mg pressed powder and carry out XRD sign, as it is shown on figure 3, this structure is MIL-53 (pore size 2.6-8.5nm). Taking 20mgMIL-53 powder and be divided into two parts, portion is immersed in 5mLSc3NC80Toluene solution (containing 2mgSc3NC80), portion is immersed in 5mLY2C79The toluene solution of N is (containing 2mgY2C79N) in. In immersion process, the Sc of naked eyes red color visible3NC80And Y2C79The toluene solution color of N all gradually becomes shallower as, until disappearing, the color of MOF-5 is by white gradual change to red simultaneously, and Sc is described3NC80And Y2C79N has entered in the duct of MOF. Dry after solid taking-up being washed with toluene after 3 days, characterize.
Fig. 4 and Fig. 5 respectively MIL-53 has adsorbed Sc3NC80And Y2C79XRD figure spectrum after N, compares peak type and is more or less the same with Fig. 3, it can be seen that MIL-53 is at absorption Sc3NC80And Y2C79Its crystal structure is remained after N.
Embodiment three
Being dissolved in 28.8mL water by 5.14g ANN aluminium nitrate nonahydrate and 1.66g p-phthalic acid, this solution was in reaction kettle for reaction three days, and temperature is set as 220 degree, dry after gained solids washed with water three times. Take 10mgMIL-53 (pore size 2.6-8.5nm) powder and be immersed in 5mLY2C79The toluene solution of N is (containing 2mgY2C79N) in. Dry after solid taking-up being washed with toluene after 3 days, characterize.
Fig. 6 is for having adsorbed Y2C79The ESR spectrogram of the MIL-53 complex of N. MIL-53 itself also has ESR signal, sees the strong peak on Fig. 6 B left side. Y2C79N its ESR spectrogram in the solution had three groups of peaks (such as Fig. 6 A) originally. Y2C79In N and MIL-53 complex, it is possible to be clearly visible Y2C79Two components of N split peak (see two groups of signals, Y on the right side of Fig. 6 B2C79Another group peak of N is covered by the signal of MIL-53). Under solid conditions, ESR wave spectrum can clearly detect Y2C79The coupling division of N, this illustrates, Y2C79N is monomolecular dispersion state (if because solids accumulation state, ESR signal will not divide) in MIL-53 duct.
Claims (9)
1. prepare metal organic framework compound-metal fullerene complex method, comprise the steps:
Metal organic framework compound material is immersed in the organic solution of metal fullerene, obtains the mixed system containing metal organic framework compound-metal fullerene complex.
2. method according to claim 1, it is characterised in that: the shortest dimension in the duct of described metal organic framework compound is 0.5nm, and full-size is less than 10nm;
Described metal organic framework compound material is with organic carboxyl acid for organic ligand, and transition metal is the metal organic framework compound material that node is constructed;
Described organic carboxyl acid is p-phthalic acid, benzenetricarboxylic acid and derivant thereof;
Described transition metal is selected from following at least one: Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn.
3. method according to claim 1 and 2, it is characterised in that: described metal-organic framework materials is: Zn4O(BDC)3��Al(OH)(BDC)��Zn4O(BTB)2Or Cr3F(H2O)2O(BDC)2��
4. the method according to any one of claim 1-3, it is characterised in that: the synthetic method of described metal organic framework compound material is selected from following at least one: hydro-thermal method, solvent-thermal method, microwave method, ultrasonic method and electrochemical process.
5. the method according to any one of claim 1-4, it is characterised in that: in the organic solution of described metal fullerene, solute is metal fullerene, and solvent is the organic solvent that can dissolve metal fullerene;
Described metal fullerene is selected from following at least one: MC2n��M2C2n��M3NC2n��M3CNC2n��M2C2C2n��M3C2C2n��M2C79N, wherein M is Sc, Y and lanthanide series metal, n=30��50;
Described organic solvent is selected from following at least one: toluene, Carbon bisulfide, o-dichlorohenzene, o-Dimethylbenzene and benzene.
6. the method according to any one of claim 1-5, it is characterised in that: the time of described immersion is 0.5 day-7 days.
7. the method according to any one of claim 1-6, it is characterised in that: described metal organic framework compound material is 100-1:1 with the mass ratio of metal fullerene in the organic solution of described metal fullerene.
8. the method according to any one of claim 1-7, it is characterized in that: described method also includes separating the step obtaining described metal organic framework compound-metal fullerene complex from the described mixed system containing metal organic framework compound-metal fullerene complex, concrete operations are as follows: first filtered by the described mixed system containing metal organic framework compound-metal fullerene complex, collect solid, surface followed by solid described in solvent washing, finally described solid is dried, obtain described metal organic framework compound-metal fullerene complex.
9. metal organic framework compound-metal fullerene complex that method according to any one of claim 1-8 prepares.
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| CN106486239A (en) * | 2016-09-21 | 2017-03-08 | 中国科学院化学研究所 | A kind of method improving metal fullerene single molecular magnetses performance |
| CN106824103A (en) * | 2017-03-15 | 2017-06-13 | 中国科学院化学研究所 | A kind of fullerene complex and its remove flue gas in free radical application |
| CN107262045A (en) * | 2017-08-03 | 2017-10-20 | 中国科学院化学研究所 | Application of the fullerene MOF composites in volatile organic matter is removed |
| CN113825380A (en) * | 2021-10-18 | 2021-12-21 | 盐城工学院 | Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof |
| CN114735675A (en) * | 2022-03-30 | 2022-07-12 | 山东大学 | Based on fullerene C60Porous carbon material dually doped with fullerene derivative and preparation method and application thereof |
| WO2023005506A1 (en) * | 2021-07-30 | 2023-02-02 | 中国科学院化学研究所 | Metal fullerene electron spin probe and application thereof in measuring gas adsorption capacity of porous material |
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2014
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106486239A (en) * | 2016-09-21 | 2017-03-08 | 中国科学院化学研究所 | A kind of method improving metal fullerene single molecular magnetses performance |
| CN106824103A (en) * | 2017-03-15 | 2017-06-13 | 中国科学院化学研究所 | A kind of fullerene complex and its remove flue gas in free radical application |
| CN106824103B (en) * | 2017-03-15 | 2019-09-13 | 北京福纳康生物技术有限公司 | A kind of fullerene complex and its in removing flue gas free radical application |
| CN107262045A (en) * | 2017-08-03 | 2017-10-20 | 中国科学院化学研究所 | Application of the fullerene MOF composites in volatile organic matter is removed |
| WO2023005506A1 (en) * | 2021-07-30 | 2023-02-02 | 中国科学院化学研究所 | Metal fullerene electron spin probe and application thereof in measuring gas adsorption capacity of porous material |
| CN113825380A (en) * | 2021-10-18 | 2021-12-21 | 盐城工学院 | Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof |
| CN113825380B (en) * | 2021-10-18 | 2023-12-22 | 盐城工学院 | Cobalt/manganese oxide/porous graphitized carbon wave-absorbing material and preparation method thereof |
| CN114735675A (en) * | 2022-03-30 | 2022-07-12 | 山东大学 | Based on fullerene C60Porous carbon material dually doped with fullerene derivative and preparation method and application thereof |
| CN114735675B (en) * | 2022-03-30 | 2023-06-16 | 山东大学 | Fullerene C-based 60 Porous carbon material binary doped with fullerene derivative, and preparation method and application thereof |
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