CN108441982A - A kind of preparation method of graphene/metal organic frame composite fibre - Google Patents
A kind of preparation method of graphene/metal organic frame composite fibre Download PDFInfo
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- CN108441982A CN108441982A CN201810148855.7A CN201810148855A CN108441982A CN 108441982 A CN108441982 A CN 108441982A CN 201810148855 A CN201810148855 A CN 201810148855A CN 108441982 A CN108441982 A CN 108441982A
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Abstract
The invention discloses a kind of preparation methods of graphene/metal organic frame composite fibre, the graphene/metal organic frame composite fibre is graphene oxide and MOF crystal powders by compound obtained graphene/metal organic frame composite fibre, and steps are as follows：Take a concentration of 0.1 ~ 100 mg/mL graphene oxide dispersion and MOF crystal powders in mixing under confined conditions, stir evenly to obtain spinning solution, spinning solution passes through wet spinning, it is prepared into a diameter of 20 ~ 50 microns of graphene oxide/MOF composite fibres, i.e., described graphene/metal organic frame composite fibre.The mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (0.1~10)：1.Preparation method of the present invention is easy to operate, mild condition, pattern is adjustable, structure-controllable, uniform component distribution, remains the structural intergrity of graphene oxide and MOF crystal, has had both graphene oxide and the excellent properties of MOF, being capable of mass or industrialized production.
Description
Technical field
The present invention relates to composite materials to synthesize field, more particularly, to a kind of graphene/metal organic frame composite fibre
Preparation method.
Background technology
Graphene fiber refers to graphene continuous assembled material made of close ordered arrangement in an axial direction.It has been developed at present
One-dimensional limited hydro-thermal construction from part, template auxiliary chemical vapor deposition method, wet spinning process, dry spinning method, film twisting method etc.
Method prepares graphene fiber.Wherein, wet spinning has many advantages, such as that easy to operate, efficient, continuity is good, easy amplification,
It is to prepare the most classical method of graphene fiber.
Metal-organic framework materials (Metal-organic frameworks, MOF) are a kind of periodically porous bones
Frame material is mainly coordinated with organic ligand by complexing by metal ion/ion cluster.MOF materials gas store,
Chemical Decomposition, selective catalysis and drug conveying etc. great potential.In addition, the porous gold prepared using MOF as presoma
Category oxide, porous carbon composite etc. are also widely used for clean energy resource storage and conversion system, such as fuel cell are super
Capacitor and lithium battery.
Graphene has high conductivity, high theoretical surface, is ideal electrode material.In recent years, flexible electronic device
It receives significant attention, it is also more important to the research and development of flexible electrode material.It is multiple compared to traditional two dimension, three-dimensional grapheme
Condensation material, graphene composite fibre have the characteristics that high strength, high conductivity and high-flexibility, are a kind of great attraction
The novel carbon based fibers of power.Graphene/MOF composite fibres can have both the structural advantage of each component, while have fibrous material
Architectural characteristic, have a good application prospect in fields such as the energy, environment, flexible devices.Therefore, a kind of simple, temperature of exploitation
With pervasive method, pattern and structure-controllable are constructed, the uniform graphene of composite distribution/MOF composite fibres have important meaning
Justice.
Invention content
The present invention is to overcome the above-mentioned graphene composite material of two and three dimensions in the prior art mechanical strength, electric conductivity
And the problem that flexibility is not high, a kind of preparation method of graphene/metal organic frame composite fibre is provided, compared to tradition
Two dimension, three-dimensional graphene composite material, graphene composite fibre has high strength, high conductivity and high-flexibility etc.
Feature.
To achieve the goals above, the present invention uses following technical scheme：
A kind of preparation method of graphene/metal organic frame composite fibre, the graphene/metal organic frame composite fibre
Pass through compound obtained graphene/metal organic frame composite fibre for graphene oxide and MOF crystal powders.The present invention for
All MOF crystal are almost all suitable for, and the preparation method of MOF crystal can be obtained by Literature Consult, such as Fe-MOF, ZIF-8,
Co-MOF, Ni-MOF, Cu-MOF crystal can be synthesized by the method for solvent heat；During being mixed with graphene oxide,
A kind of MOF can be added, two or more MOF can also be added.
Preferably, a kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：It takes dense
The graphene oxide dispersion and MOF crystal powders that degree is 0.1 ~ 100 mg/mL stir evenly to spin in mixing under confined conditions
Silk liquid, spinning solution pass through wet spinning, are prepared into a diameter of 20 ~ 50 microns of graphene oxide/MOF composite fibres, i.e., described
Graphene/metal organic frame composite fibre.；Wherein, the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is
(0.1~10)：1.Using technique and wet spinning is simply mixed, adjustable pattern, structure-controllable, uniform component distribution are prepared
Graphene oxide/MOF composite fibres, the preparation method of the composite fibre is easy to operate, mild condition, agents useful for same instrument source
It extensively, being capable of mass or industrialized production；Technical solution of the present invention uses wet spinning process, only by being stirred MOF
With two kinds of materials of graphene or graphene oxide, wet spinning can be realized；Solvent used in the present invention is in laboratory or work
It can be obtained in the production of industry metaplasia, cheap, derive from a wealth of sources, used experimental facilities is easy to operate, also, in building-up process
In remain the structural intergrity of graphene oxide and MOF crystal, graphene oxide sheet and MOF can effectively be prevented by being one kind
Method of agglomeration.
Preferably, the graphene oxide dispersion is graphene oxide water solution or graphene oxide DMF solution,
Preferably graphene oxide DMF solution.
Preferably, surface of graphene oxide and MOF crystal powders in the graphene/metal organic frame composite fibre
Complex method be that graphene oxide coats MOF crystal powders or MOF crystal powder uniform loads in surface of graphene oxide
One or two, specifically depending on MOF crystal powders nature and addition.
Preferably, the MOF crystal powders are selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [K2Sn2
(bdc)3](H2O)XOne or more of.Two kinds or more of MOF crystal can be added simultaneously, there are many being contained
The graphene oxide of MOF crystal/MOF composite fibres.
Preferably, the wet spinning includes the following steps：The spinning solution is continuously injected into injection by syringe
Into coagulating bath, wherein the syringe needle internal diameter of syringe is 0.2-0.22 mm, and outer diameter is 0.2-0.6 mm, length 10-15
Mm, then through vacuum filtration, spontaneously dry, obtain the graphene oxide/MOF composite fibres.
Preferably, the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is（1~2）:1；The oxidation stone
Black alkene is sheet, and lateral dimension is 0.1 ~ 100 μm, preferably between 40 ~ 50 μm；Graphene oxide dispersion a concentration of 6 ~ 10
mg/mL。
Preferably, the coagulating bath is selected from 5 %wt CaCl2Aqueous solution, ethyl alcohol, the ethanol solution for being saturated potassium hydroxide
Or any one in ethyl acetate.
Preferably, the coagulating bath is ethyl acetate.
A kind of graphene/metal that the preparation method of graphene/metal organic frame composite fibre is prepared has machine frame
Application of the frame composite fibre in the energy, environment or flexible device field.
It is theoretical based on classical colloid liquid crystal by the property of graphene oxide liquid crystal using technical solution of the present invention, lead to
It crosses and different types of MOF crystal is added, wet spinning prepares one-dimensional graphene oxide/metal organic frame composite fibre, the fibre
The graphene oxide prepared by MOF crystal/metal organic frame composite fibre tool is uniformly adhered on the graphene oxide sheet surface of dimension
There is porous structure, in the synthesis process, remains the structural intergrity of graphene oxide and MOF crystal, have both graphene and MOF
The excellent properties of crystal can play the excellent of both graphene and MOF simultaneously in the fields such as catalysis, energy storage, sensing, absorption
Performance, and graphene oxide/metal organic frame composite fibre has certain flexibility, has light in flexible electronic device
Application prospect
Therefore, the present invention has the advantages that：（1）Preparation method is easy to operate, mild condition, pattern is adjustable, structure can
Control, uniform component distribution；（2）It being capable of mass or industrialized production；（3）Preparation method remains graphene oxide and MOF is brilliant
The structural intergrity of body has had both graphene oxide and the excellent properties of MOF.
Description of the drawings
Fig. 1:Graphene oxide/metal organic frame composite fibre pictorial diagram in the present invention.
Fig. 2: Fe-MOF（a,b）Crystal scanning electron microscope (SEM) photograph.
Fig. 3:Co-MOF（a,b）Crystal scanning electron microscope (SEM) photograph.
Fig. 4:The scanning electron microscope (SEM) photograph of graphene oxide/Fe-MOF composite fibres, constituent mass ratio are Fe-MOF:GO=3:2
(a,b)。
Fig. 5:The scanning electron microscope (SEM) photograph of graphene oxide/Co-MOF composite fibres, constituent mass ratio are Fe-MOF:GO=3:2
(a,b)。
Fig. 6:The scanning electron microscope (SEM) photograph of graphene oxide/Fe-MOF/Co-MOF composite fibres, constituent mass ratio are Fe-MOF:
Co-MOF:GO=3:3:4(a,b)。
Fig. 7:Graphene oxide/metal organic frame composite fibre preparation technology flow chart
Specific implementation mode：
With reference to specific embodiments and the drawings, the present invention is described in further detail, but embodiments of the present invention are not
It is only limitted to this.Agents useful for same of the present invention is routine experiment or acquisition purchased in market.
Embodiment 1：
A kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：
（1）The preparation of Fe-MOF crystal powders：At room temperature, the N of 50 mL, N- dimethyl methyls are added in the reaction bulb of 100 mL
The anhydrous ferric chloride of 0.83 g terephthalic acid (TPA)s and 1.215 g is added in amide under magnetic stirring, after it is completely dissolved,
12 h are reacted under 100 DEG C of oil bath.After reaction, through low-speed centrifugal（15 min, room temperature, 4000 rpm）, remove supernatant
Liquid, with ethyl alcohol repeated washing, centrifugation 3 times.Products therefrom finally obtains Fe-MOF crystal powders after 60 DEG C are dried in vacuo 24 h
End；
（2）The preparation of graphene/metal organic frame composite fibre sequentially adds graphite oxide in the centrifuge tube of 5 mL sizes
Alkene DMF solution, Fe-MOF crystal powders, the initial rate of charge for controlling each raw material are as follows：Graphene oxide solution, concentration 6.7
Mg/mL, graphene oxide sheet lateral dimension are 50 microns；30 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF are brilliant
The dispensing mass ratio of body powder is 2:3；Gained mixture is obtained in persistently mixing 2 min through magnetic agitation under confined conditions
GO/Fe-MOF plural gels, i.e. spinning solution, spinning solution is further through wet spinning, specially：Spinning solution is continuous by syringe
It is injected into ethyl acetate coagulating bath, then through vacuum filtration, spontaneously dries, obtain a diameter of 25 microns of graphene oxide/MOF
Composite fibre.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows:
Fig. 2（A, b）It is the SEM figures of the Fe-MOF crystal powders obtained in embodiment 1, from Fig. 2（b）As can be seen that the Fe- obtained
MOF crystal is polygon spindle, and lateral dimension is hundreds of nanometers.Fig. 4（A, b）It is the oxidation stone obtained in embodiment 1
The surface topography of black alkene/metal organic frame composite fibre, Fig. 4（a）Illustrate the whole pattern of fiber, it can be seen that one-dimensional knot
Structure is to be formed by a large amount of GO oblique cut graftings, and uniformly adhere to Fe-MOF crystal above, and fiber thickness is 25 microns；Fig. 4（b）It is
Fig. 4（a）Partial enlarged view, from（b）This it appears that GO pieces are transparent, illustrate that GO pieces are not reunited, further demonstrate,proves
The porous structure of this bright self-supporting is constructed by a large amount of single layer GO pieces；Fe-MOF crystal all spreads on GO pieces surface
It is full, and without finding Fe-MOF agglomerations, Fe-MOF crystal and GO pieces are intuitively demonstrated by uniform compound, and successfully
Obtain one dimension fibre structure.
Graphene oxide/MOF composite fibres are through hydrazine hydrate steam electronation（95 DEG C, 12 h）, obtain graphene/
MOF composite fibres.The electric conductivity of the fiber is up to 310S/m can be used as ultracapacitor, in three-electrode system, to GO/ MOF
Composite fibre carries out Electrochemical Characterization, as a result shows：In 10 mV s-1Sweep speed under, the highest ratio of composite fibre
Capacity reaches 329.1 F g-1.Graphene oxide/loose porous the structure of MOF composite fibres is conducive to increase material and electrolysis
Contact area between liquor realizes preferable chemical property to be conducive to the infiltration of electrolyte solution.
Embodiment 2：
A kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：The system of Fe-MOF crystal powders
Preparation Method then sequentially adds graphene oxide DMF solution, Fe-MOF crystal with embodiment 1 in the centrifuge tube of 5 mL sizes
Powder, the initial rate of charge for controlling each raw material are as follows：Graphene oxide solution, 6 mg/mL of concentration, graphene oxide sheet transverse direction ruler
Very little is 30 microns；The dispensing mass ratio of 20 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF crystal powders is 1：1；Institute
Mixture is obtained in persistently mixing 5 min through magnetic agitation under confined conditions, GO/Fe-MOF plural gels, i.e. spinning solution is obtained, spins
Silk liquid is further through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate coagulating bath by syringe, then
Through vacuum filtration, spontaneously dries, obtain a diameter of 50 microns of graphene oxides/MOF composite fibres.
Embodiment 3：
A kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：The system of Fe-MOF crystal powders
Preparation Method then sequentially adds graphene oxide DMF solution, Fe-MOF crystal with embodiment 1 in the centrifuge tube of 5 mL sizes
Powder, the initial rate of charge for controlling each raw material are as follows：Graphene oxide solution, 10 mg/mL of concentration, graphene oxide sheet are lateral
Size is 50 microns；The dispensing mass ratio of 40 mg of Fe-MOF crystal powders, graphene oxide and Fe-MOF crystal powders is 1：2；
Gained mixture obtains GO/Fe-MOF plural gels, i.e. spinning solution in persistently mixing 5 min through magnetic agitation under confined conditions,
Spinning solution is further through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate coagulating bath by syringe,
Again through vacuum filtration, spontaneously dries, obtain a diameter of 30 microns of graphene oxides/MOF composite fibres.
Embodiment 4：
A kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：
（1）The preparation of Co-MOF crystal powders：Take one 50 mL beakers that the mixed solution of 20 mL methanol and 20 mL ethyl alcohol is added,
The cabaltous nitrate hexahydrate of 725 mg is dissolved in mixed liquor, stirring is until be completely dissolved.It is added 20 in the beaker of another 50mL
The 2-methylimidazole of 821 mg is dissolved in the mixed liquor by the mixed solution of mL methanol and 20 mL ethyl alcohol, and stirring is until completely molten
Solution.Solution in above-mentioned two beaker is mixed evenly, reacts 24 h at room temperature.After reaction, it centrifuges（15 min, room
Temperature, 4000 rpm）, remove supernatant, after wash 3 times with methanol, products therefrom is after 60 DEG C of vacuum drying for 24 hours, final acquisition
Co-MOF crystal powders；
（2）The preparation of graphene/metal organic frame composite fibre：Graphite oxide is sequentially added in the centrifuge tube of 5 mL sizes
Alkene DMF solution, Co-MOF crystal powders, the initial rate of charge for controlling each raw material are as follows：Graphene oxide solution, concentration 6.7
Mg/mL, graphene oxide sheet lateral dimension are 50 microns；30 mg of Co-MOF crystal powders, graphene oxide and Co-MOF crystal
The dispensing mass ratio of powder is 2：3；Gained mixture obtains GO/ in persistently mixing 2 min through magnetic agitation under confined conditions
Co-MOF plural gels, i.e. spinning solution, spinning solution is further through wet spinning, specially：Spinning solution is continuously noted by syringe
It penetrates and is injected into ethyl acetate coagulating bath, then through vacuum filtration, spontaneously dry, it is multiple to obtain a diameter of 30 microns of graphene oxide/MOF
Condensating fiber.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows:Fig. 3（A, b）It is to be obtained in embodiment 4
The SEM of Co-MOF crystal powders schemes, from Fig. 2（b）As can be seen that the Co-MOF crystal obtained is gengon, lateral dimension is several
Hundred nanometers.Fig. 5（A, b）It is the surface shape of graphene oxide/metal organic frame composite fibre obtained in embodiment 4
Looks, Fig. 5（a）Illustrate the whole pattern of fiber, Fig. 5（a）Illustrate the whole pattern of fiber, it can be seen that one-dimentional structure be by
A large amount of GO oblique cut graftings form, and uniformly adhere to Co-MOF crystal above, and fiber thickness is 35 microns；Fig. 5（b）It is Fig. 5（a）
Partial enlarged view, from（b）This it appears that GO pieces are transparent, illustrate that GO pieces are not reunited, further prove this
The porous structure of self-supporting is constructed by a large amount of single layer GO pieces, and GO pieces surface is all paved with by Co-MOF crystal, and
And without finding Co-MOF agglomerations, Co-MOF crystal and GO pieces are intuitively demonstrated by uniform compound, and successfully obtain
One dimension fibre structure.
Graphene oxide/MOF composite fibres are through hydrazine hydrate steam electronation（95 DEG C, 12 h）, obtain graphene/
MOF composite fibres.The electric conductivity of the fiber can be used as ultracapacitor up to 308 S/m, in three-electrode system, to GO/ MOF
Composite fibre carries out Electrochemical Characterization, as a result shows：In 10 mV s-1Sweep speed under, the highest specific volume of composite fibre
Amount reaches 282.6 F g-1.Graphene oxide/loose porous the structure of MOF composite fibres is conducive to increase material and electrolyte
Contact area between solution realizes preferable chemical property to be conducive to the infiltration of electrolyte solution.
Embodiment 5：
A kind of preparation method of graphene/metal organic frame composite fibre, includes the following steps：In the centrifuge tube of 5 mL sizes
In sequentially add graphene oxide DMF solution, Fe-MOF crystal powders, Co-MOF crystal powders, control the initial throwing of each raw material
Expect that ratio is as follows：Graphene oxide solution, 6.7 mg/mL of concentration, graphene oxide sheet lateral dimension are 50 microns；Fe-MOF crystal
15 mg of powder 15mg, Co-MOF crystal powder, the dispensing of graphene oxide, Fe-MOF crystal powders and Co-MOF crystal powders
Mass ratio is 4:3:3；Gained mixture obtains plural gel, that is, spins in persistently mixing 2min through magnetic agitation under confined conditions
Silk liquid, spinning solution is further through wet spinning, specially：Spinning solution is continuously injected into ethyl acetate solidification by syringe
In bath, then through vacuum filtration, spontaneously dries, obtain a diameter of 25 microns of graphene oxides/MOF composite fibres.
It chooses sample in embodiment to be characterized and analyzed, test result is as follows：
Surface topography such as Fig. 6 of graphene oxide/metal organic frame composite fibre obtained in embodiment 5（A, b）.Fig. 6
（a）Illustrate the whole pattern of fiber, it can be seen that one-dimentional structure is to be formed by a large amount of GO oblique cut graftings, and uniformly adhere to above
Co-MOF crystal and Fe-MOF crystal, fiber thickness is 40 microns.Fig. 6（b）It is Fig. 6（a）Partial enlarged view, from（b）It can be with
It is transparent for will become apparent from GO pieces, illustrates that GO pieces are not reunited, further prove the porous structure of this self-supporting be by
A large amount of single layer GO pieces are constructed.Intuitive Co-MOF crystal, Fe-MOF crystal and the GO pieces of demonstrating by uniform compound, and at
Work(obtains one dimension fibre structure.
Graphene oxide/MOF composite fibres are through hydrazine hydrate steam electronation（95 DEG C, 12 h）, obtain graphene/MOF
Composite fibre.The electric conductivity of the fiber can be used as ultracapacitor up to 320 S/m, compound to GO/MOF in three-electrode system
Fiber carries out Electrochemical Characterization, as a result shows：In 10 m V s-1Sweep speed under, the highest specific capacity of composite fibre
Reach 321.2 F g-1.Graphene oxide/loose porous the structure of MOF composite fibres is conducive to increase material and electrolyte is molten
Contact area between liquid realizes preferable chemical property to be conducive to the infiltration of electrolyte solution.
In conclusion can successfully prepare the oxidation that each component is evenly distributed, appearance structure is controllable by our method
Graphene/metal organic frame composite fibre.
Claims (10)
1. a kind of preparation method of graphene/metal organic frame composite fibre, which is characterized in that the graphene/metal has
Machine frame composite fibre is that graphene oxide and MOF crystal powders are compound by compound obtained graphene/metal organic frame
Fiber.
2. a kind of graphene dispersing solution according to claim 1 and MOF crystal powders in mixing under confined conditions, stirring is equal
It is even that spinning solution, spinning solution pass through wet spinning, be prepared into a diameter of 20 ~ 50 microns of graphene oxide/MOF composite fibres,
I.e. described graphene/metal organic frame composite fibre, wherein the quality that feeds intake of the MOF crystal powders and graphene oxide
Than for (0.1~10)：1.
3. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 2, feature exist
In the graphene oxide dispersion is graphene oxide water solution or graphene oxide DMF solution.
4. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 2, feature exist
In surface of graphene oxide and the complex method of MOF crystal powders are oxygen in the graphene/metal organic frame composite fibre
Graphite alkene coats the one or two of MOF crystal powders or MOF crystal powder uniform loads in surface of graphene oxide.
5. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 2 or 4, feature
It is, the MOF crystal powders are selected from ZIF-8, Ni-MOF, Fe-MOF, MOF-5, Co-MOF or [K2Sn2(bdc)3](H2O)XIn
One or more.
6. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 5, feature exist
In the wet spinning includes the following steps：The spinning solution is continuously injected into coagulating bath by syringe, then is passed through
Vacuum filtration spontaneously dries, obtains the graphene oxide/MOF composite fibres.
7. a kind of preparation side of graphene/metal organic frame composite fibre according to claim 2,3 or 6 any one
Method, which is characterized in that the mass ratio that feeds intake of the MOF crystal powders and graphene oxide is (1 ~ 2):1；The graphite oxide
Alkene is sheet, and lateral dimension is 0.1 ~ 100 micron；A concentration of 6 ~ 10 mg of graphene oxide dispersion/mL.
8. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 6, feature exist
In the coagulating bath is selected from 5 %wt CaCl2Aqueous solution, ethyl alcohol are saturated in the ethanol solution or ethyl acetate of potassium hydroxide and appoint
Meaning is a kind of.
9. a kind of preparation method of graphene/metal organic frame composite fibre according to claim 8, feature exist
In the coagulating bath is ethyl acetate.
10. a kind of preparation of graphene/metal organic frame composite fibre according to claim 1,3 or 9 any one
Application of the graphene that the method is prepared/metal organic frame composite fibre in the energy, environment or flexible device field.
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