CN107880279A - Metal fullerene porous polymer composite and preparation method thereof - Google Patents
Metal fullerene porous polymer composite and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of preparation method of metal fullerene porous polymer composite, and in an inert atmosphere, under the conditions of existing for oxidant, organic solvent, fully oxidation reaction generation fullerene porous polymer occurs for contact between fullerene monomer molecule；In an inert atmosphere, under the conditions of organic solvent is existing, fullerene porous polymer fully contacts the generation composite of porous polymer containing metal fullerene with metal complex；Wherein, fullerene monomer molecule is the fullerene organic molecule of more carbazoles substitution, and the metal complex is the one or more in four (triphenylphosphines) conjunction palladium, vinyl two (triphenylphosphine) conjunction platinum, carbonyl three (triphenylphosphine) hydrogenation Rh.The porous material obtained by the preparation method of the present invention has certain BET specific surface area, and contain metal fullerene so that porous material of the invention can be used for being catalyzed, gas storage, organic photoelectrical material, molecule separate, the carrier of clean energy resource etc..
Description
Technical field
The present invention relates to field of composite material preparation, and in particular to a kind of metal fullerene porous polymer composite and
Its preparation method.
Background technology
Application prospect of the porous polymer in terms of catalysis, gas storage, molecule separation, cause the pole of chemist
Big interest.Traditional porous material include Inorganic crystal structure (such as zeolite) and unbodied network structure (such as silica,
Activated carbon).In recent years, faster development is achieved as a kind of organic porous material, poromeric synthesis, such as covalently had
The synthesis of machine frame frame material, conjugation capillary copolymer material turns into focus.Covalent organic frame material be by organic molecule by
It polymerize the porous polymer with stable crystal form to be formed according to certain spatial orientation.Compared with inorganic porous material, covalently have
The advantage of machine frame is that structure is all made up of light element, stable to air, organic solvent, and hole is adjustable.With covalently it is organic
Frame material is compared, and conjugation capillary copolymer material is simply made up of carbon-carbon bond, C-H bond, so chemically stable is more preferable.Although
It is unbodied to be conjugated capillary copolymer material structure, but can regulate and control polymer orifices by changing rigid connection molecule
The size in footpath and the size of specific surface area.
Fullerenes metal has become important a member in fullerene family, and as the research of international fullerene
Great advanced subject, because it is possible to have important application prospect in superconductor, ferromagnetic material, optical material etc.,
A brand-new research field is opened up for subjects such as chemistry, physics, material science.To the various novelties of fullerenes metal
The announcement of unique chemistry, physical characteristic, it is the emphasis of work at present.Why research to fullerenes metal causes
The broad interest of scientists from all over the world, result from its property and its tempting application prospect：The metallic atom of calking doping can be very
Change the electric conductivity of fullerene in big degree, or even superconductor can be made；The f electronic shell of metal underfill in cage, due to
Surrounding carbon atom rolls into a ball the influence of crystalline field, and energy level changes, and optical transition occurs, and base has been established for the appearance of new pattern laser material
Plinth；Electric charge transfer between metal and carbon cage controls for the optics of their charge states and realizes that optical storage provides possibility, can
For information, optoelectronic areas and nonlinear optical material；In addition, it is surrounded by the fullerene metal bag of the rare earth metal of specific use
Compound can be used for the every field such as medicine, electromagnetism, laser, the energy, information, be with a wide range of applications.
The content of the invention
The present invention in order to overcome be difficult in the prior art synthesize the composite of porous polymer containing metal fullerene the shortcomings that,
There is provided a kind of preparation method of metal fullerene porous polymer composite with higher BET specific surface area and by this
Metal fullerene porous polymer composite prepared by method.
The present invention provides a kind of preparation method of metal fullerene porous polymer composite, comprises the following steps：
Step 1: in an inert atmosphere, under the conditions of existing for oxidant, organic solvent, between fullerene monomer molecule
Fully oxidation reaction generation fullerene porous polymer occurs for contact；
Step 2: in an inert atmosphere, under the conditions of organic solvent is existing, fullerene porous polymer and metal complex
The fully contact generation composite of porous polymer containing metal fullerene；
Wherein, fullerene monomer molecule is the fullerene organic molecule of more carbazoles substitution, and the metal complex is four (three
Phenylphosphine) close palladium, vinyl two (triphenylphosphine) closes platinum, the one or more in carbonyl three (triphenylphosphine) hydrogenation Rh.
Preferably, the mol ratio of the fullerene monomer molecule and the oxidant is 1:8~1:36.Receive under this condition
Rate highest.
Preferably, the mol ratio of the fullerene monomer molecule and the metal complex is 1:2~1:8.In the condition
Lower yield highest.
Preferably, of carbazole substituent in the fullerene organic molecule that more carbazoles substitute in the fullerene monomer molecule
Number is 2~12.
Preferably, the oxidant is ferric trichloride.
Preferably, the organic solvent is dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetone, acetonitrile, two
The ring of oxygen six, benzene,toluene,xylene, trimethylbenzene, chlorobenzene, dichloro-benzenes or trichloro-benzenes.
Preferably, the temperature of the oxidation reaction is 20~150 DEG C, and the reaction time is 12~36h.Yield under this condition
Highest.
The operation principle and its advantage of this programme：Can be different types of by adding in the preparation method of the present invention
Metal complex, adjust the structural behaviour and related application of material.The porous material obtained by the preparation method of the present invention has
There is higher BET specific surface area, and there is metallic catalyst and fullerene so that porous material of the invention can be used for urging
Change, gas storage, organic photoelectrical material, molecule separation, chemistry or biology sensor, the carrier etc. of clean energy resource.
The metal fullerene porous polymer composite prepared by the above method.
The aperture of the metal fullerene porous polymer composite is 0.6~3nm.
The BET specific surface area of the metal fullerene porous polymer composite is 200~600m2/g。
The pore size of the porous material obtained by the preparation method of the present invention is logical in nanoscale, its pore structure
Cross covalent key connection and construct what is formed, therefore pore structure is relatively stable.Moreover, it can pass through in the preparation process in accordance with the present invention
Add porosity of different types of fullerene monomer molecule in interior regulation material in a big way.
Brief description of the drawings
Fig. 1 is metal fullerene composite porous material structural representation；
Fig. 2 is two (carbazyl phenyl) methanofullerene Ful-Cz hydrogen nuclear magnetic resonance spectrogram；
Fig. 3 is two (carbazyl phenyl) methanofullerene Ful-Cz mass spectrogram；
Fig. 4 is FulCPOP solid-state nuclear magnetic resonance carbon spectrogram；
Fig. 5 is FulCPOP-Pd electro microscope energy spectrum figure；
Fig. 6 is the photoelectron spectroscopy figure of element Pd in FulCPOP-Pd；
Fig. 7 is FulCPOP-Rh electro microscope energy spectrum figure；
Fig. 8 is the photoelectron spectroscopy figure of element Rh in FulCPOP-Rh；
Fig. 9 is FulCPOP, FulCPOP-Pd and FulCPOP-Rh nitrogen adsorption desorption isothermal curve figure；
Figure 10 is FulCPOP, FulCPOP-Pd and FulCPOP-Rh graph of pore diameter distribution.
Embodiment
Below by the further details of explanation of embodiment：
Embodiment 1
Two (carbazyl phenyl) methanofullerene Ful-Cz preparation
Carbazyl benzophenone (1.27mmol) (the Sa grace chemical technologies of 0.65g 4,4 '-two are added in 250mL round-bottomed flasks
Co., Ltd), 1.64g unifor (8.8mmol) (Sa En chemical technologies Co., Ltd), 50mL toluene and 50mL first
Alcohol.12h is stirred at reflux under nitrogen protection, reacts and system is cooled to 25 DEG C after terminating, filtering, solid is washed with 50mL methanol
After obtain 0.7g bis- (carbazyl phenyl) Tosylhydrazone intermediate (1).Then, it is dissolved in 10mL pyridines, adds 0.0767g
Sodium methoxide (1.42mmol) (Sa En chemical technologies Co., Ltd), under nitrogen protection stirring at normal temperature 15 minutes.Then add
0.516g fullerenes (0.721mmol) (Sa En chemical technologies Co., Ltd), are concentrated, color after being stirred at reflux 8h under nitrogen protection
Spectrum purifying obtains two (carbazyl phenyl) methanofullerene Ful-Cz 0.35g, yield 40%.
As shown in Figures 2 and 3, product meets two (carbazyl phenyl) methylenes by proton nmr spectra and mass spectral characteristi
Base fullerene Ful-Cz architectural feature.
Embodiment 2
The FulCPOPP of organic porous material containing fullerene preparation
(carbazyl phenyl) the methanofullerene Ful-Cz of 200mg bis- (0.18mmol) are dissolved in 30mL anhydrous three chloromethane
In alkane.In 100mL round-bottomed flasks, under nitrogen protection, this solution is instilled into 1.02g ferric trichlorides (6.30mmol) (traditional Chinese medicines collection
Chemical reagent Co., Ltd of group) the anhydrous chloroform solns of 20mL in.Under nitrogen protection 18h is reacted under normal temperature.Question response
Terminate, add 50mL methanol, continue stirring one hour, filter solid, filter cake is washed with methanol, filter cake is air-dried.Then will
Solid is placed in 10mL concentrated hydrochloric acid and stirs 2h, adds 100mL methanol, stirring, filters solid, filter cake is successively with methanol, two
Chloromethanes, tetrahydrofuran washing.Then solid is washed with methanol, tetrahydrofuran successively with the method for surname extraction.Most
After obtain 190mg solids FulCPOP.
Solid-state nuclear magnetic resonance inspection is carried out to solid FulCPOP with nuclear magnetic resonance spectrometer (BRUKER AVANCE III 400)
Survey, as shown in figure 4, meeting FulCPOP architectural feature.
With full-automatic specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2020M+C) to solid
FulCPOP carries out specific surface area and porosity detection, and as shown in Figure 9 and Figure 10, it is 590m to measure BET specific surface area2/ g, density
The aperture for the FulCPOP that Functional Theory calculates is 0.7~0.95nm.
Embodiment 3
The porous polymer composite of fullerene containing palladium FulCPOP-Pd preparation
By 53.2mg Pd (PPh3)4(lark prestige Science and Technology Ltd.) is dissolved in 10mL toluene, then carries out two to the system
Secondary Fruit storage, afterwards by the system under nitrogen protection, 0.0490g FulCPOP are added, 24h is stirred at room temperature.Reaction
After end, ether is added, filtering, solid is washed with ether, 60mg composites FulCPOP-Pd is obtained after drying.
Solid FulCPOP-Pd is entered with photoelectron spectroscopy XPS with SEM power spectrum (Hitachi S-4800)
Row element composition characterizes, as shown in Figure 5 and Figure 6, it was demonstrated that palladium complex is combined into the FulCPOP of organic porous material containing fullerene
Work(.
With full-automatic specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2020M+C) to solid
FulCPOP-Pd carries out specific surface area and porosity detection, and it is 250m to measure BET specific surface area2/ g, as shown in Figure 9 and Figure 10,
The FulCPOP-Pd of Density function theory aperture is 0.88nm.
Embodiment 4
Rhodium-containing fullerene porous polymer composite FulCPOP-Rh preparation
By 121mg RhH (CO) (PPh3)3(lark prestige Science and Technology Ltd.) is dissolved in 10mL toluene, and then the system is entered
Capable Fruit storage twice, afterwards by the system under nitrogen protection, 0.0534g FulCPOP are added, 24h is stirred at room temperature.
After reaction terminates, ether is added, filtering, solid is washed with ether, 80mg composites FulCPOP-Rh is obtained after drying.
Solid FulCPOP-Rh is entered with photoelectron spectroscopy XPS with SEM power spectrum (Hitachi S-4800)
Row element composition characterizes, as shown in Figure 7 and Figure 8, it was demonstrated that rhodium complex is combined into the FulCPOP of organic porous material containing fullerene
Work(.
With full-automatic specific surface area and lacunarity analysis instrument (Micromeritics ASAP 2020M+C) to solid
FulCPOP-Rh carries out specific surface area and porosity detection, and it is 360m to measure BET specific surface area2/ g, as shown in Figure 9 and Figure 10,
The FulCPOP-Rh of Density function theory aperture is 0.63nm and 1.2nm.
Above-described is only embodiments of the invention, and known general knowledge does not describe excessively herein in scheme.It should refer to
Go out, for those skilled in the art, under the premise of not departing from the present invention, several modifications and improvements can also be made,
These should also be considered as protection scope of the present invention, these effects and practical applicability for implementing all without the influence present invention.
The scope of protection required by this application should be based on the content of the claims, and the record such as embodiment in specification can
For explaining the content of claim.
Claims (10)
1. the preparation method of metal fullerene porous polymer composite, it is characterised in that：Comprise the following steps：
Step 1: in an inert atmosphere, under the conditions of existing for oxidant, organic solvent, between fullerene monomer molecule fully
Oxidation reaction generation fullerene porous polymer occurs for contact；
Step 2: in an inert atmosphere, under the conditions of organic solvent is existing, fullerene porous polymer and metal complex are abundant
The contact generation composite of porous polymer containing metal fullerene；
Wherein, fullerene monomer molecule is the fullerene organic molecule of more carbazoles substitution, and the metal complex is four (triphenyls
Phosphine) close palladium, vinyl two (triphenylphosphine) closes platinum, the one or more in carbonyl three (triphenylphosphine) hydrogenation Rh.
2. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
The mol ratio for stating fullerene monomer molecule and the oxidant is 1:8~1:36.
3. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
The mol ratio for stating fullerene monomer molecule and the metal complex is 1:2~1:8.
4. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
The number for stating carbazole substituent in the fullerene organic molecule of more carbazole substitutions in fullerene monomer molecule is 2~12.
5. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
It is ferric trichloride to state oxidant.
6. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
Organic solvent is stated as dichloromethane, chloroform, carbon tetrachloride, tetrahydrofuran, acetone, acetonitrile, dioxane, benzene, toluene, two
Toluene, trimethylbenzene, chlorobenzene, dichloro-benzenes or trichloro-benzenes.
7. the preparation method of metal fullerene porous polymer composite according to claim 1, it is characterised in that：Institute
The temperature for stating oxidation reaction is 20~150 DEG C, and the reaction time is 12~36h.
A kind of 8. metal fullerene porous polymer composite prepared by any described method of claim 1~7.
9. metal fullerene porous polymer composite according to claim 8, it is characterised in that：The metal fowler
The aperture of alkene porous polymer composite is 0.6~3nm.
10. metal fullerene porous polymer composite according to claim 9, it is characterised in that：The metal is rich
The BET specific surface area for strangling alkene porous polymer composite is 200~600m2/g。
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109554090A (en) * | 2018-11-12 | 2019-04-02 | 安徽科创美涂料科技股份有限公司 | A kind of aqueous functional polyurethane coating of anion and preparation method thereof |
| CN110684202A (en) * | 2019-09-30 | 2020-01-14 | 汕头大学 | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof |
| CN113444255A (en) * | 2021-05-28 | 2021-09-28 | 云南大学 | Imine covalent organic framework loaded fullerene C60Material, preparation method thereof and application of supercapacitor |
| 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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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109554090A (en) * | 2018-11-12 | 2019-04-02 | 安徽科创美涂料科技股份有限公司 | A kind of aqueous functional polyurethane coating of anion and preparation method thereof |
| CN110684202A (en) * | 2019-09-30 | 2020-01-14 | 汕头大学 | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof |
| CN110684202B (en) * | 2019-09-30 | 2021-11-02 | 汕头大学 | Two-dimensional layered imidazole copper C60Material, preparation method and application thereof |
| CN113444255A (en) * | 2021-05-28 | 2021-09-28 | 云南大学 | Imine covalent organic framework loaded fullerene C60Material, preparation method thereof and application of supercapacitor |
| 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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Application publication date: 20180406 |