CN103887080A - Nanocomposite material of nitrogen doped with graphene/copper ferrite and preparation method thereof - Google Patents
Nanocomposite material of nitrogen doped with graphene/copper ferrite and preparation method thereof Download PDFInfo
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- CN103887080A CN103887080A CN201410079443.4A CN201410079443A CN103887080A CN 103887080 A CN103887080 A CN 103887080A CN 201410079443 A CN201410079443 A CN 201410079443A CN 103887080 A CN103887080 A CN 103887080A
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Abstract
The invention discloses a nanocomposite material of nitrogen doped with graphene/copper ferrite and a preparation method thereof. The method comprises the steps that graphite oxides are put in a mixed solvent for conducting ultrasonic dispersion for a period of time, a mixed solution of dissolved ferric nitrate and copper nitrate is poured into an evenly-dispersed graphene oxide solution, then urea is added in the mixed solution, after the urea is stirred and dissolved, the obtained mixed solution is moved into a hydrothermal kettle for conducting a solvothermal reaction, and after the reaction is over and products are centrifugally washed and dried, the nanocomposite material of the nitrogen doped with the graphene/copper ferrite is obtained. According to the nanocomposite material of the nitrogen doped with the graphene/copper ferrite and the preparation method thereof, the nitrogen doped with the graphene is obtained while the graphite oxides are reduced, copper ferrite nano particles are grown on the surface of the nitrogen doped with the graphene, the nanocomposite material of the nitrogen doped with the graphene/copper ferrite is prepared, and the prepared nanocomposite material has a good application prospect on the aspect of energy storage elements and electrocatalysis.
Description
Technical field
The invention belongs to Nano-composite materials field, specifically relate to a kind of nitrogen-doped graphene/coppe ferrite nano composite material and preparation.
Background technology
An Deliegaimu and two scientists of Constantine Nuo Woxiaoluofu from Univ Manchester UK in 2004 find and have prepared Graphene, but preparation method is at that time by simple mechanical stripping method.And the performance of Graphene has caused attention widely, so need a large amount of Graphenes, simple mechanical stripping cannot meet the demand of Graphene.At present, the preparation method of Graphene has a variety of, but the Graphene of preparing exists corresponding defect, has destroyed the structure of its perfect hexatomic ring, and its performance is reduced, and has limited its extensive use.In order to reduce defect, to the preparation of Graphene, modify doping or the compound focus that becomes research.
The people such as Klaus M ü llen adulterated on the surface of Graphene by hydro thermal method nitrogen, boron (Three-Dimensional Nitrogen and Boron Co-doped Graphene for High-Performance All-Solid-State Supercapacitors.Advanced Materials2012,24 (37): 5130-5135.) simultaneously; Chinese patent (CN103274393A, CN102760866A, CN103359708A, CN103359711A and CN102167310A etc.) has been introduced nitrogenous source by different chemical methodes, prepared nitrogen-doped graphene, wherein a lot of preparation methods are faced with that production cost is high, reaction equipment needed thereby complexity, severe reaction conditions, the problem such as yield poorly; Although the nitrogen-doped graphene obtaining, compared with Graphene, has improved its electric conductivity, as set it as the electrode material of ultracapacitor, its chemical property (as than electric capacity) cannot meet the requirement of practical application far away.Coppe ferrite is due to environmentally safe, and electrode material (Facile Fabrication of Hierarchically Porous CuFe more stable and that be widely used
2o
4nanospheres with Enhanced Capacitance Property.ACS Applied Materials & Interfaces, 2013.5 (13): 6030-6037.).But coppe ferrite exists corresponding defect because of the structure of self.
For its performance is improved, nitrogen-doped graphene and coppe ferrite are carried out compound, current, nitrogen-doped graphene/coppe ferrite have not been reported.
Summary of the invention
For the defect problem that will solve, the object of this invention is to provide a kind of simple synthetic nitrogen doped graphene/coppe ferrite nano composite material and preparation method thereof, the composite material that obtains can pass through cooperative effect, make up defect separately, make Performance optimization, and this preparation method's synthesis technique is simple, and lower cost, is suitable for large-scale industrial production.
The technical solution that realizes the object of the invention is: a kind of nitrogen-doped graphene/coppe ferrite nano composite material, described composite material is made up of basis material nitrogen-doped graphene and coppe ferrite, wherein, the mass ratio of basis material nitrogen-doped graphene and coppe ferrite is 1:5～1:10; In described basis material nitrogen-doped graphene, the doping of nitrogen is 1～2%.
A kind of preparation method of nitrogen-doped graphene/coppe ferrite nano composite material comprises the steps:
The first step: by graphite oxide ultrasonic a period of time in mixed solvent, obtain finely dispersed graphene oxide solution;
Second step: a certain amount of ferric nitrate and copper nitrate are added in above-mentioned mixed solvent, and stir and cause it and dissolve completely;
The 3rd step: urea is joined to the 3rd step and obtain in mixed system, again stir, it is uniformly dispersed, wherein the mass ratio of urea and graphite oxide is 100:1～200:1;
The 4th step: the above-mentioned mixed solution mixing is transferred in water heating kettle, carries out hydro-thermal reaction at 120～200 DEG C;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
Mixed solvent described in step 1 is absolute ethyl alcohol and deionized water, and described absolute ethyl alcohol and the volume ratio of deionized water are 1:1～1:4, and ultrasonic jitter time is 3h.
The mol ratio of the ferric nitrate described in step 2 and copper nitrate is 2:1, and the mass ratio of coppe ferrite and graphite oxide is 5:1～10:1, and the dispersed with stirring time is 5～30min.
Mixing time described in step 3 is 30～60min.
The reaction time of the solvent thermal reaction described in step 4 is 12～20h.
Compared with prior art, tool of the present invention has the following advantages in the present invention: (1) synthesis technique of the present invention is simple, and production cost is low, is beneficial to large-scale production cheaply, and reaction reagent is nontoxic, and environmental pollution is little, (2) adopt urea to reduce to graphene oxide, in reduction, at the surface doping of Graphene nitrogen-atoms, the doping of nitrogen-atoms has changed Graphene surface chemical property, make up chemical method and prepared the blemish while that Graphene exists, the alkalescence that urea provides, coppe ferrite is formed on the surface of nitrogen-doped graphene, coppe ferrite nano particle can further stop Graphene accumulation between layers to be reunited simultaneously, so improving the chemical property of composite material is combined with each other nitrogen-doped graphene and coppe ferrite, give full play to both advantages, improve defect separately, thereby obtain the electrode material of chemical property excellence.
Brief description of the drawings
Accompanying drawing 1 is the TEM photo of the prepared nitrogen-doped graphene/coppe ferrite nano composite material of the embodiment of the present invention 1.
Accompanying drawing 2 is TEM photos of the prepared nitrogen-doped graphene/coppe ferrite nano composite material of the embodiment of the present invention 2.
Accompanying drawing 3 is XPS spectrum figure (a) and structural characterization Raman spectrograms (b) of the prepared nitrogen-doped graphene/coppe ferrite nano composite material of the embodiment of the present invention 2.
Accompanying drawing 4 is Electrochemical Characterization cyclic voltammetry figure of the prepared nitrogen-doped graphene/coppe ferrite nano composite material of the embodiment of the present invention 3.
Embodiment
Mainly in conjunction with specific embodiments the preparation method of nitrogen-doped graphene/coppe ferrite nano composite material is described in further detail below.
Embodiment 1: the preparation method of nitrogen-doped graphene/coppe ferrite nano composite material (graphite oxide and coppe ferrite mass ratio are 1:5) that nitrogen doping is 1%, specifically comprises the following steps:
The first step, the graphite oxide that is 100mg by content ultrasonic 3h in 100mL mixed solvent (1:1) obtains finely dispersed graphene oxide solution;
Second step, joins 1.6888g ferric nitrate and 0.5050g copper nitrate in above-mentioned mixed liquor dispersed with stirring 5min;
The 3rd step, joins 10g urea in obtained finely dispersed mixed liquor, and dispersed with stirring 30min again, and it is mixed;
The 4th step, is transferred to the above-mentioned mixed solution mixing in water heating kettle and carries out solvent thermal reaction, and reaction temperature is 120 DEG C, and the reaction time is 20h;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
As shown in Figure 1, coppe ferrite nano particle is distributed in the surface of nitrogen-doped graphene to its TEM photo.
Embodiment 2: the preparation method of nitrogen-doped graphene/coppe ferrite nano composite material (graphite oxide and coppe ferrite mass ratio are 1:8) that nitrogen doping is 1.5%, specifically comprises the following steps:
The first step, the graphite oxide that is 100mg by content ultrasonic 3h in 100mL mixed solvent (1:2) obtains finely dispersed graphene oxide solution;
Second step, joins 2.7021g ferric nitrate and 0.8079g copper nitrate in above-mentioned mixed liquor dispersed with stirring 20min;
The 3rd step, joins 15g urea in obtained finely dispersed mixed liquor, and dispersed with stirring 40min again, and it is mixed;
The 4th step, is transferred to the above-mentioned mixed solution mixing in water heating kettle and carries out solvent thermal reaction, and reaction temperature is 180 DEG C, and the reaction time is 18h;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
As shown in Figure 2, coppe ferrite nano particle is distributed in the surface of nitrogen-doped graphene to its TEM photo as we can see from the figure, and load capacity is more than Fig. 1.As shown in Fig. 3 (a) XPS, in figure, contain and have carbon, oxygen, five kinds of elements of nitrogen and iron and copper, have illustrated the successful doping of nitrogen element, and the existence of coppe ferrite; Accompanying drawing 3(b) be the Raman spectrogram of nitrogen-doped graphene/coppe ferrite nano composite material, the Raman peaks from figure can determine that prepared composite material is nitrogen-doped graphene/coppe ferrite nano composite material.
Embodiment 3: the preparation method of nitrogen-doped graphene/coppe ferrite nano composite material (graphite oxide and coppe ferrite mass ratio are 1:10) that nitrogen doping is 2%, specifically comprises the following steps:
The first step, the graphite oxide that is 100mg by content ultrasonic 3h in 100mL mixed solvent (1:4) obtains finely dispersed graphene oxide solution;
Second step, joins 3.3777g ferric nitrate and 1.0099g copper nitrate in above-mentioned mixed liquor dispersed with stirring 30min;
The 3rd step, joins 20g urea in obtained finely dispersed mixed liquor, and dispersed with stirring 60min again, and it is mixed;
The 4th step, is transferred to the above-mentioned mixed solution mixing in water heating kettle and carries out solvent thermal reaction, and reaction temperature is 200 DEG C, and the reaction time is 12h;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
Accompanying drawing 4 is the Electrochemical Characterization figure of nitrogen-doped graphene/coppe ferrite binary electrode material.Electrochemical property test utilizes three-electrode system to carry out in 1M KOH, as we can see from the figure, when sweeping speed while changing from 1～100mV/s, the shape of its curve remains unchanged substantially, illustrate that nitrogen-doped graphene/coppe ferrite electrode material has excellent multiplying power property, cut this electrode material has higher ratio electric capacity compared with one-component, its than electric capacity up to 378F/g.
Claims (7)
1. nitrogen-doped graphene/coppe ferrite nano composite material, is characterized in that described composite material is made up of basis material nitrogen-doped graphene and coppe ferrite, and wherein, the mass ratio of basis material nitrogen-doped graphene and coppe ferrite is 1:5～1:10; In described basis material nitrogen-doped graphene, the doping of nitrogen is 1～2%.
2. nitrogen-doped graphene/coppe ferrite nano composite material according to claim 1, is characterized in that described composite material prepared through the following steps:
The first step: by graphite oxide ultrasonic dispersion in mixed solvent, obtain finely dispersed graphene oxide solution;
Second step: ferric nitrate and copper nitrate are added in above-mentioned mixed solvent, and stir and cause it and dissolve completely;
The 3rd step: urea is joined to the 3rd step and obtain in mixed system, again stir, it is uniformly dispersed, wherein the mass ratio of urea and graphite oxide is 100:1～200:1;
The 4th step: the above-mentioned mixed solution mixing is transferred in water heating kettle, carries out hydro-thermal reaction at 120～200 DEG C;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
3. a preparation for nitrogen-doped graphene/coppe ferrite nano composite material, is characterized in that comprising the steps:
The first step: by graphite oxide ultrasonic dispersion in mixed solvent, obtain finely dispersed graphene oxide solution;
Second step: ferric nitrate and copper nitrate are added in above-mentioned mixed solvent, and stir and cause it and dissolve completely;
The 3rd step: urea is joined to the 3rd step and obtain in mixed system, again stir, it is uniformly dispersed, wherein the mass ratio of urea and graphite oxide is 100:1～200:1;
The 4th step: the above-mentioned mixed solution mixing is transferred in water heating kettle, carries out hydro-thermal reaction at 120～200 DEG C;
The 5th step: product is carried out to centrifugation, and obtain nitrogen-doped graphene/coppe ferrite nano composite material after repeatedly washing, being dried.
4. the preparation of nitrogen-doped graphene/coppe ferrite nano composite material according to claim 3, it is characterized in that the mixed solvent described in the first step is absolute ethyl alcohol and deionized water, described absolute ethyl alcohol and the volume ratio of deionized water are 1:1～1:4, and ultrasonic jitter time is 3h.
5. the preparation of nitrogen-doped graphene/coppe ferrite nano composite material according to claim 3, the mol ratio that it is characterized in that the ferric nitrate described in second step and copper nitrate is 2:1, the mass ratio of coppe ferrite and graphite oxide is 5:1～10:1, and the dispersed with stirring time is 5～30min.
6. the preparation of nitrogen-doped graphene/coppe ferrite nano composite material according to claim 3, is characterized in that the mixing time described in the 3rd step is 30～60min.
7. the preparation of nitrogen-doped graphene/coppe ferrite nano composite material according to claim 3, the reaction time that it is characterized in that the solvent thermal reaction described in the 4th step is 12～20h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
| CN104638244A (en) * | 2015-02-12 | 2015-05-20 | 陕西理工学院 | Process for preparing electrode material of sodium-ion battery by use of ammonium jarosite and chalcanthite |
| CN108330506A (en) * | 2018-01-16 | 2018-07-27 | 嘉兴学院 | Nanometer copper alloy/N doping class graphene composite catalyst and preparation method thereof |
| CN108607594A (en) * | 2018-05-08 | 2018-10-02 | 河北北方学院 | A kind of coppe ferrite/carbon nano-fiber/nitrogen-doped graphene composite electro catalytic material |
| CN115282994A (en) * | 2022-07-04 | 2022-11-04 | 西北大学 | Preparation method and application of high-energy composite material based on copper ferrite, aluminum and graphite carbon nitride |
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| IT201800010540A1 (en) * | 2018-11-23 | 2020-05-23 | Torino Politecnico | Reduced and doped graphene oxide, and its production method |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104058461A (en) * | 2014-07-04 | 2014-09-24 | 武汉理工大学 | Low-temperature preparation method for CuFeO2 crystal material of delafossite structure |
| CN104058461B (en) * | 2014-07-04 | 2016-07-06 | 武汉理工大学 | A kind of delafossite structure CuFeO2The low temperature preparation method of crystalline material |
| CN104638244A (en) * | 2015-02-12 | 2015-05-20 | 陕西理工学院 | Process for preparing electrode material of sodium-ion battery by use of ammonium jarosite and chalcanthite |
| CN108330506A (en) * | 2018-01-16 | 2018-07-27 | 嘉兴学院 | Nanometer copper alloy/N doping class graphene composite catalyst and preparation method thereof |
| CN108330506B (en) * | 2018-01-16 | 2019-06-21 | 嘉兴学院 | Nanometer copper alloy/N doping class graphene composite catalyst and preparation method thereof |
| CN108607594A (en) * | 2018-05-08 | 2018-10-02 | 河北北方学院 | A kind of coppe ferrite/carbon nano-fiber/nitrogen-doped graphene composite electro catalytic material |
| CN115282994A (en) * | 2022-07-04 | 2022-11-04 | 西北大学 | Preparation method and application of high-energy composite material based on copper ferrite, aluminum and graphite carbon nitride |
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