CN103496693B - Method for preparing Fe3O4 nanoparticle/graphene composite material by sol electrostatic self-assembly process and application thereof - Google Patents
Method for preparing Fe3O4 nanoparticle/graphene composite material by sol electrostatic self-assembly process and application thereof Download PDFInfo
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- CN103496693B CN103496693B CN201310433900.0A CN201310433900A CN103496693B CN 103496693 B CN103496693 B CN 103496693B CN 201310433900 A CN201310433900 A CN 201310433900A CN 103496693 B CN103496693 B CN 103496693B
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Abstract
The invention discloses a method for preparing a Fe3O4 nanoparticle/graphene composite material by a sol electrostatic self-assembly process, which comprises the following steps: (1) preparing a Fe(OH)3 sol solution of which the surface is positively charged; (2) preparing a graphene oxide sol of which the surface is negatively charged; and (3) mixing the graphene oxide sol and the Fe(OH)3 sol, magnetically stirring to generate a brownish black precipitate, separating, pouring out the supernate to obtain a Fe(OH)3/graphene oxide composite, and reducing the composite at 300-800 DEG C in a nitrogen atmosphere to obtain the Fe3O4/graphene nano composite material. The composite of the Fe(OH)3 colloidal particles and graphene oxide is performed in the water solution, and thus, the method has the advantages of low cost, energy saving, environment friendliness and simple technique, and can easily implement industrial mass production; and the preparation process of the Fe(OH)3 colloidal particle/graphene oxide composite material has obvious solution variation, and the solution becomes turbid from clear and finally precipitates, so that the supernate can be directly poured out.
Description
Technical field
The present invention relates to a kind of colloidal sol electrostatic self-assembled method and prepare Fe
3o
4the method of nano particle and graphene composite material and purposes.
Background technology
As the matrix material that Graphene and the metal oxide nanoparticles compound of two-dimensional sheet structured material produce, there is unique texture and character and receive and pay close attention to widely.The main method of the graphene-based matrix material of current acquisition has: mechanically mixing and directly grow other material composition matrix material by chemical process on graphene film.Although but the mechanical blending method matrix material homogeneity causing preparing because Graphene phase is different with metal oxide particle density simple to operate is bad; Graphene film grows the chemical production processes of the second material require complexity and the composition of matrix material is handling bad.
Summary of the invention
The object of the invention is customer service the deficiencies in the prior art, provide a kind of colloidal sol electrostatic self-assembled to prepare Fe
3o
4the method of nano particle and graphene composite material and purposes.
Technical scheme of the present invention is: a kind of colloidal sol electrostatic self-assembled method prepares Fe
3o
4the method of nanoparticle/graphene composite material, its step is as follows:
(1), under room temperature, configuration quality concentration is the FeCl of 15-30%
3the aqueous solution, when magnetic agitation, by FeCl
3the aqueous solution is added dropwise in the water of boiling, FeCl
3the mass ratio of water-soluble drop and water is 1:1-5, boils 1-5 minute again after dropwising, and obtains presenting brick-red transparence solution, and this kind of solution is the Fe (OH) of surface with positive charge
3sol solution;
(2) adopt Hummers method to prepare graphene oxide, be distributed in water by graphene oxide under ultrasound condition, the mass volume ratio of graphene oxide and water is 1:10-20, obtains the graphene oxide colloidal sol of surface with negative charge;
(3) by graphene oxide colloidal sol and Fe (OH)
3colloidal sol mixes, graphene oxide colloidal sol and Fe (OH)
3the mass ratio of colloidal sol is 1:1-1:50, occurs that brownish black precipitates under magnetic agitation, is separated, outwells supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture 300-800 DEG C, reduce under nitrogen atmosphere, prepare Fe
3o
4/ graphene nanocomposite material.
Colloidal sol electrostatic self-assembled method prepares Fe
3o
4nanoparticle/graphene composite material is applied to the dye, rhodamine B in absorption waste water.
Colloidal sol electrostatic self-assembled method prepares Fe
3o
4nanoparticle/graphene composite material is applied to electrode material for super capacitor.
Colloidal sol electrostatic self-assembled method prepares Fe
3o
4nanoparticle/graphene composite material is applied to lithium ion battery negative material.
The invention has the beneficial effects as follows: Fe (OH)
3the mixture of colloidal solid and graphene oxide carries out in aqueous, with low cost and energy-conserving and environment-protective, and technique is simple, is easy to industrial volume production; Fe (OH)
3have obvious solution to change in the preparation process of colloidal solid and graphene oxide composite material, solution colour becomes muddy to finally there is precipitation from clarification, directly outwells supernatant liquor; Fe
3o
4generation and the reduction of Graphene can concentrate on same heat treatment step; Fe
3o
4the composition conveniently regulating and controlling of nano particle and graphene composite material.
Method of the present invention is eco-friendly, simple and flexible, utilizes electrostatic self-assembled method to prepare uniform Fe
3o
4the matrix material of nano particle and Graphene laminate structure.Assemble method simple possible in the aqueous solution under this room temperature, is applicable to the requirement that industrialization big area is produced, and reduce while realizing two components in reduction step, energy saving economy is environmental protection again.
Accompanying drawing illustrates:
Fig. 1 is obtained Fe
3o
4nanoparticle/graphene composite material transmission electron microscope photo;
Fig. 2 is obtained Fe
3o
4nanoparticle/graphene composite material Raman figure;
Fig. 3 is obtained Fe
3o
4the schematic diagram of nanoparticle/graphene composite material absorbing dye;
Fig. 4 is obtained Fe
3o
4nanoparticle/graphene composite material cyclic voltammogram.
Embodiment
Embodiment 1
Under room temperature, configuration 40mL concentration is the FeCl of 10%
3the aqueous solution; Get beaker and load 200mL distilled water, by the FeCl configured
3the aqueous solution drip enter in the water of boiling, after dropwising, then boil 2 minutes, gained solution is bolarious transparent aqueous solution, and solution presents steady state, is Fe (OH)
3water-sol system.Adopt Hummers method to prepare graphene oxide, surface is with negative charge; 0.1mg/mL is reached by making the concentration of graphene oxide in graphene oxide ultrasonic disperse to water.By the Fe (OH) of surface with positive charge
3colloidal sol 10.7mL joins in graphene oxide colloidal sol, occurs that brownish black precipitates under magnetic agitation, is separated, removes supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture at 500 DEG C, reduce under inert atmosphere, prepare Fe
3o
4/ graphene composite material.
In colloidal solid and graphene oxide recombination process, Fe (OH)
3colloidal sol is brick-red, and graphene oxide colloidal sol is golden yellow, after two kinds of colloidal sol mixing, slowly occurs brown precipitation.In heat treatment process, Graphene and Fe
3o
4generate simultaneously.Whole change in process is obvious, simple to operate, is conducive to industrial applications.Preparation-obtained Fe
3o
4the transmission electron microscope of nano particle and graphene composite material as shown in Figure 1, shows that it forms uniform network structure; Fig. 2 is Fe
3o
4the X-ray diffractogram of nano particle and graphene composite material, show its really by Fe
3o
4the matrix material that nano particle and Graphene form; By Fe
3o
4nano particle and graphene composite material 50mg throw in that to enter containing concentration be 10
-5the water of Mmol dye, rhodamine B is used as sorbent material, and after 6 minutes, upper solution becomes transparent, obtains Fig. 3 after tested, and mixture self has good magnetic, is separated obtains by externally-applied magnetic field, convenient recovery and recycle; By Fe
3o
4nano particle and graphene composite material are used for electrochemistry cyclic voltammetry, obtain Fig. 4, result shows, and cyclic voltammetric has good rectangle, show that mixture is suitable as electrode material activity thing, can be used as the electrode preparing ultracapacitor and lithium ion battery.
Embodiment 2
Under room temperature, configuration 40mL concentration is the FeCl of 10%
3the aqueous solution; Get beaker and load 200mL distilled water, by the FeCl configured
3the aqueous solution drip enter in the water of boiling, after dropwising, then boil 2 minutes, gained solution is bolarious transparent aqueous solution, presents steady state, is Fe (OH)
3water-sol system.Adopt Hummers method to prepare graphene oxide, surface is with negative charge; 0.1mg/mL is reached by making the concentration of graphene oxide in graphene oxide ultrasonic disperse to water.By the Fe (OH) of surface with positive charge
3colloidal sol 5mL joins in graphene sol, occurs that brownish black precipitates under magnetic agitation, and upper solution is faint yellow, is separated, removes supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture at 500 DEG C, reduce under inert atmosphere, prepare Fe
3o
4/ graphene composite material.
Embodiment 3
Under room temperature, configuration 40mL concentration is the FeCl of 10%
3the aqueous solution; Get beaker and load 200mL distilled water, by the FeCl configured
3the aqueous solution drip enter in the water of boiling, after dropwising, then boil 2 minutes, gained solution is bolarious transparent aqueous solution, presents steady state, is Fe (OH)
3water-sol system.Adopt Hummers method prepare graphene oxide (W. S. Hummers and R. E. Offeman,
j. Am. Chem. Soc.,1958,80,1339.), surface is with negative charge; 0.1mg/mL is reached by making the concentration of graphene oxide in graphene oxide ultrasonic disperse to water.By the Fe (OH) of surface with positive charge
3sol solution 20mL joins in graphene dispersing solution, occurs that brownish black precipitates under magnetic agitation, and upper solution is light brick-red, is separated, removes supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture at 500 DEG C, reduce under inert atmosphere, prepare Fe
3o
4/ graphene composite material.
Embodiment 4
A kind of colloidal sol electrostatic self-assembled method prepares Fe
3o
4the method of nanoparticle/graphene composite material, its step is as follows:
(1), under room temperature, configuration quality concentration is the FeCl of 15%
3the aqueous solution, when magnetic agitation, by FeCl
3the aqueous solution is added dropwise in the water of boiling, FeCl
3the mass ratio of water-soluble drop and water is 1:1, boils 1 minute again after dropwising, and obtains the Fe (OH) of surface with positive charge
3colloidal sol;
(2) be distributed in water by graphene oxide under ultrasound condition, the mass volume ratio of graphene oxide and water is 1:10, obtains the graphene oxide colloidal sol of surface with negative charge;
(3) by graphene oxide colloidal sol and Fe (OH)
3colloidal sol mixes, graphene oxide colloidal sol and Fe (OH)
3the mass ratio of colloidal sol is 1:1, occurs that brownish black precipitates under magnetic agitation, is separated, outwells supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture 300 DEG C, reduce under nitrogen atmosphere, obtain Fe
3o
4/ graphene nanocomposite material.
Embodiment 5
A kind of colloidal sol electrostatic self-assembled method prepares Fe
3o
4the method of nanoparticle/graphene composite material, its step is as follows:
(1), under room temperature, configuration quality concentration is the FeCl of 30%
3the aqueous solution, when magnetic agitation, by FeCl
3the aqueous solution is added dropwise in the water of boiling, FeCl
3the mass ratio of water-soluble drop and water is 1:5, boils 5 minutes again after dropwising, and obtains the Fe (OH) of surface with positive charge
3colloidal sol;
(2) be distributed in water by graphene oxide under ultrasound condition, the mass volume ratio of graphene oxide and water is 1:20, obtains the graphene oxide colloidal sol of surface with negative charge;
(3) by graphene oxide colloidal sol and Fe (OH)
3colloidal sol mixes, graphene oxide colloidal sol and Fe (OH)
3the mass ratio of colloidal sol is 1:50, occurs that brownish black precipitates under magnetic agitation, is separated, outwells supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture 800 DEG C, reduce under nitrogen atmosphere, obtain Fe
3o
4/ graphene nanocomposite material.
Embodiment 6
A kind of colloidal sol electrostatic self-assembled method prepares Fe
3o
4the method of nanoparticle/graphene composite material, its step is as follows:
(1), under room temperature, configuration quality concentration is the FeCl of 20%
3the aqueous solution, when magnetic agitation, by FeCl
3the aqueous solution is added dropwise in the water of boiling, FeCl
3the mass ratio of water-soluble drop and water is 1:3, boils 3 minutes again after dropwising, and obtains the Fe (OH) of surface with positive charge
3colloidal sol;
(2) be distributed in water by graphene oxide under ultrasound condition, the mass volume ratio of graphene oxide and water is 1:15, obtains the graphene oxide colloidal sol of surface with negative charge;
(3) by graphene oxide colloidal sol and Fe (OH)
3colloidal sol mixes, graphene oxide colloidal sol and Fe (OH)
3the mass ratio of colloidal sol is 1:20, occurs that brownish black precipitates under magnetic agitation, is separated, outwells supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture 500 DEG C, reduce under nitrogen atmosphere, obtain Fe
3o
4/ graphene nanocomposite material.
Claims (1)
1. a colloidal sol electrostatic self-assembled method prepares Fe
3o
4the method of nanoparticle/graphene composite material, is characterized in that its step is as follows:
(1), under room temperature, configuration quality concentration is the FeCl of 15-30%
3the aqueous solution, when magnetic agitation, by FeCl
3the aqueous solution is added dropwise in the water of boiling, FeCl
3the mass ratio of the aqueous solution and water is 1:1-5, boils 1-5 minute again after dropwising, and obtains the Fe (OH) of surface with positive charge
3colloidal sol;
(2) be distributed in water by graphene oxide under ultrasound condition, the mass volume ratio of graphene oxide and water is 1:10-20, obtains the graphene oxide colloidal sol of surface with negative charge;
(3) by graphene oxide colloidal sol and Fe (OH)
3colloidal sol mixes, graphene oxide colloidal sol and Fe (OH)
3the mass ratio of colloidal sol is 1:1-1:50, occurs that brownish black precipitates under magnetic agitation, is separated, outwells supernatant liquid, obtain Fe (OH)
3with the mixture of graphene oxide, by mixture 300-800 DEG C, reduce under nitrogen atmosphere, obtain Fe
3o
4/ graphene nanocomposite material.
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| CN110615431B (en) * | 2019-10-25 | 2021-08-10 | 青岛科技大学 | Preparation method of two-dimensional nano magnetons with stable solution dispersibility |
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