CN104475753B - Liquid phase reduction prepares graphene-supported nanometer of Cu3.8The method of Ni alloy - Google Patents
Liquid phase reduction prepares graphene-supported nanometer of Cu3.8The method of Ni alloy Download PDFInfo
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Abstract
Liquid phase reduction prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it relates to preparing graphene-supported nanometer of Cu3.8The method of Ni alloy.The present invention adopts Graphene to serve as surfactant, solves the intractable problem of surfactant of existing existence.The inventive method is: first prepare graphene oxide, then by CuSO4·5H2O solution, NiSO4·6H2After O solution, NaOH solution and hydrazine hydrate solution and graphene oxide mixed processing, namely complete.Not yet useful reducing process prepares graphene-supported nanometer of Cu at present3.8The relevant report of Ni alloy, the method for the present invention is simple, quick, it is not necessary to add any coating material.Utilizing the Nanoalloy particle that reducing process makes load on Graphene, good dispersion, size uniform, particle diameter is less.Hydrazine hydrate is that reducing agent generates a large amount of N in course of reaction2, at N2Protection lower can be prevented effectively from reduction process the generation of oxide.
Description
Technical field
The present invention relates to and prepare graphene-supported nanometer of Cu3.8The method of Ni alloy.
Background technology
Graphene is with sp by carbon atom2The monoatomic layer of the six close heap honeycomb structures of side that hybrid form is constituted, is the two-dimensional atomic crystal that find the earliest of the mankind.Graphene can be regarded as the basic building block of many carbon allotropes.The thickness of Graphene only has 0.335nm, is the thinnest in current known materials in the world.Graphene is owing to having the two-dimensional nanostructure of uniqueness, big specific surface area, excellent electric conductivity and good chemical stability, make Graphene have good application prospect in fields such as transistor, solaode, sensor, ultracapacitor, Flied emission and catalyst carriers, also become one simultaneously and prepare the carrier that graphene-supported composite is ideal.
Metallic nickel is a kind of magnetic metal material, is widely used in magnetic material, plated material field；Copper powder has electric conductivity, heat conductivity and ductility, nanometer Cu3.8Ni alloy possesses all advantages of Nanometer Copper and nano nickel, is a kind of novel nano alloy.Receive much concern because it shows the character of excellence in electricity, magnetic and catalysis etc., there is important researching value.Therefore, graphene-supported nanometer of Cu is prepared3.8Ni alloy, it is achieved the combination of both performances is the important research direction of a combined innovation and practicality.Graphene and electroconductive magnetic alloy are combined by the present invention, prepare graphene-supported nanometer of Cu3.8Ni alloy.The present invention adopts oxidation-reduction method to be prepared for graphene oxide, then obtains graphene-supported nanometer of Cu through reducing agent reduction after being mixed with copper ion and nickel ion by Graphene3.8Ni alloy, the method is simple, quick, need not add any coating material, makes graphenic surface alloy particle be evenly distributed, stable chemical performance, is a kind of more satisfactory preparation method.
Summary of the invention
It is an object of the invention to adopt Graphene to serve as surfactant, the intractable problem of surfactant in order to solve existing existence, and provide the method that liquid phase reduction prepares graphene-supported nanometer of Cu3.8Ni alloy.
The liquid phase reduction of the present invention prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and concentrated sulphuric acid being mixed in the ratio that mass volume ratio is 1g:40～60mL, after stirring 30min in the ice-water bath of 0～4 DEG C, obtain mixed liquid；Mixed liquid is continually maintained in ice-water bath, after adding sodium nitrate in mixed liquid, adds potassium permanganate, then after stirring 2h, go to room temperature and continue stirring 1h, obtain mixed solution；Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, with distilled water, mixed solution is diluted to the 10% of original solution concentration, and add hydrogen peroxide to mixed solution variable color, add mixed solution after dilution 1 the dilute hydrochloric acid of 50 times of volumes, then after mixed solution being cooled to room temperature, centrifugal, collect lower floor's thick liquid, lower floor's thick liquid is put into dialysis in semipermeable membrane process until the pH value of lower floor's thick liquid is neutrality, obtain graphene oxide；Wherein, the mass volume ratio of sodium nitrate and mixed liquid is 1g:30～40mL, and the mass volume ratio of potassium permanganate and mixed liquid is 1g:5～10mL；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution, 0.4mol/LNiSO4·6H2O solution, 0.5mol/LNaOH solution and hydrazine hydrate solution；
Secondly, graphene oxide ultrasonic dissolution step one prepared becomes the colloidal sol of 0.01g/mL；Then by 0.4mol/LCuSO4·5H2O solution and 0.4mol/LNiSO4·6H2After O solution mix homogeneously, join ultrasonic 1h in graphene oxide colloidal sol, then the solution after ultrasonic is added under stirring the mixed liquor of 0.5mol/LNaOH solution and hydrazine hydrate solution, obtains mixed solution；Finally mixed solution is placed in the water-bath of 93 DEG C, under 200r/min mixing speed, stirring reaction 40min, after having reacted, after being statically placed in room temperature environment cooling 1h, scrubbed, filter, centrifugal, collect solid formation and put in vacuum drying oven after dry 24h, obtain black powder, be graphene-supported nanometer of Cu3.8Ni alloy；Wherein, CuSO4·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:1～3；CuSO4·5H2O solution and NiSO4·6H2The volume ratio of O solution is 1:1～1.3；0.5mol/LNaOH solution, the mixed liquor of hydrazine hydrate solution and the volume ratio of graphene oxide colloidal sol are 1:1～2:1.
The present invention comprises following beneficial effect:
1, the method is simple, quick, it is not necessary to add any coating material.
2, utilizing the Nanoalloy particle that reducing process makes load on Graphene, good dispersion, size uniform, particle diameter is less.
3, hydrazine hydrate is that reducing agent generates a large amount of N in course of reaction2, at N2Protection lower can be prevented effectively from reduction process the generation of oxide.
4, being connected with chemical bond between Graphene and the Nanoalloy particle after utilizing the method that graphene oxide reduces can make reduction, its chemical property is also more stable.
5, have no not yet and prepare graphene-supported nanometer of Cu by reducing process3.8The relevant report of Ni alloy.
Owing to Graphene is able to the two dimensional crystal of stable existence; its structural integrity is single, surface inertness; and the active force of solvent is far smaller than the intermolecular force between graphene sheet layer and lamella, it is easy in the solution to assemble and difficult dispersion, is unfavorable for large-scale production, and nanometer Cu3.8The existence of Ni particle can effectively increase the distance between graphene sheet layer, thus the Van der Waals force being greatly reduced between Graphene, simultaneously nanometer Cu3.8The character of Graphene itself will not be had impact by Ni particle, reunites on the other hand being effectively prevented from Graphene, and nanoparticle had not only been modified Graphene and simultaneously but also remained the excellent properties of Graphene itself, and nanometer Cu3.8The character of Ni particle itself affects to some extent without because of Graphene, remains so therebetween respective inherent character simultaneously and mutually promotes again, which produces cooperative effect.
Accompanying drawing explanation
Fig. 1 is graphene oxide, Graphene, graphene-supported nanometer of Cu3.8Ni alloy, nanometer Cu3.8The XRD spectra of Ni alloy；Wherein, a is the XRD spectra of Graphene, and b is the XRD spectra of graphene oxide, and c is graphene-supported nanometer of Cu3.8The XRD spectra of Ni alloy, d is a nanometer Cu3.8The XRD spectra of Ni alloy；
Fig. 2 is the graphene-supported nanometer of Cu that embodiment one prepares3.8The SEM figure of Ni alloy.
Detailed description of the invention
Detailed description of the invention one: the liquid phase reduction of present embodiment prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and concentrated sulphuric acid being mixed in the ratio that mass volume ratio is 1g:40～60mL, after stirring 30min in the ice-water bath of 0～4 DEG C, obtain mixed liquid；Mixed liquid is continually maintained in ice-water bath, after adding sodium nitrate in mixed liquid, adds potassium permanganate, then after stirring 2h, go to room temperature and continue stirring 1h, obtain mixed solution；Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, with distilled water, mixed solution is diluted to the 10% of original solution concentration, and add hydrogen peroxide to mixed solution variable color, add mixed solution after dilution 1 the dilute hydrochloric acid of 50 times of volumes, then after mixed solution being cooled to room temperature, centrifugal, collect lower floor's thick liquid, lower floor's thick liquid is put into dialysis in semipermeable membrane process until the pH value of lower floor's thick liquid is neutrality, obtain graphene oxide；Wherein, the mass volume ratio of sodium nitrate and mixed liquid is 1g:30～40mL, and the mass volume ratio of potassium permanganate and mixed liquid is 1g:5～10mL；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution, 0.4mol/LNiSO4·6H2O solution, 0.5mol/LNaOH solution and hydrazine hydrate solution；
Secondly, graphene oxide ultrasonic dissolution step one prepared becomes the colloidal sol of 0.01g/mL；Then by 0.4mol/LCuSO4·5H2O solution and 0.4mol/LNiSO4·6H2After O solution mix homogeneously, join ultrasonic 1h in graphene oxide colloidal sol, then the solution after ultrasonic is added under stirring the mixed liquor of 0.5mol/LNaOH solution and hydrazine hydrate solution, obtains mixed solution；Finally mixed solution is placed in the water-bath of 93 DEG C, under 200r/min mixing speed, stirring reaction 40min, after having reacted, after being statically placed in room temperature environment cooling 1h, scrubbed, filter, centrifugal, collect solid formation and put in vacuum drying oven after dry 24h, obtain black powder, be graphene-supported nanometer of Cu3.8Ni alloy；Wherein, CuSO4·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:1～3；CuSO4·5H2O solution and NiSO4·6H2The volume ratio of O solution is 1:1～1.3；0.5mol/LNaOH solution, the mixed liquor of hydrazine hydrate solution and the volume ratio of graphene oxide colloidal sol are 1:1～2:1.
Detailed description of the invention two: present embodiment and detailed description of the invention one the difference is that: in step one, sodium nitrate is 1g:32～38mL with the mass volume ratio of mixed liquid.Other is identical with detailed description of the invention one.
Detailed description of the invention three: present embodiment and detailed description of the invention one the difference is that: in step one, sodium nitrate is 1g:34～36mL with the mass volume ratio of mixed liquid.Other is identical with detailed description of the invention one.
Detailed description of the invention four: present embodiment and detailed description of the invention one the difference is that: in step one, sodium nitrate is 1g:35mL with the mass volume ratio of mixed liquid.Other is identical with detailed description of the invention one.
Detailed description of the invention five: present embodiment and detailed description of the invention one the difference is that: in step one, potassium permanganate is 1g:7～9mL with the mass volume ratio of mixed liquid.Other is identical with detailed description of the invention one.
Detailed description of the invention six: present embodiment and detailed description of the invention one the difference is that: in step one, potassium permanganate is 1g:8mL with the mass volume ratio of mixed liquid.Other is identical with detailed description of the invention one.
Detailed description of the invention seven: present embodiment and detailed description of the invention one the difference is that: in step one, graphite powder and concentrated sulphuric acid are 1g:45～55mL by mass volume ratio.Other is identical with detailed description of the invention one.
Detailed description of the invention eight: present embodiment and detailed description of the invention one the difference is that: in step one, graphite powder and concentrated sulphuric acid are 1g:48～52mL by mass volume ratio.Other is identical with detailed description of the invention one.
Detailed description of the invention nine: present embodiment and detailed description of the invention one the difference is that: in step one, graphite powder and concentrated sulphuric acid are 1g:50mL by mass volume ratio.Other is identical with detailed description of the invention one.
Detailed description of the invention ten: present embodiment and detailed description of the invention one are the difference is that CuSO in step 24·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:1.5～2.5.Other is identical with detailed description of the invention one.
Detailed description of the invention 11: present embodiment and detailed description of the invention one are the difference is that CuSO in step 24·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:1.8～2.2.Other is identical with detailed description of the invention one.
Detailed description of the invention 12: present embodiment and detailed description of the invention one are the difference is that CuSO in step 24·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:2.Other is identical with detailed description of the invention one.
Detailed description of the invention 13: present embodiment and detailed description of the invention one are the difference is that CuSO in step 24·5H2O solution and NiSO4·6H2The volume ratio of O solution is 1:1.1～1.3.Other is identical with detailed description of the invention one.
Detailed description of the invention 14: present embodiment and detailed description of the invention one are the difference is that CuSO in step 24·5H2O solution and NiSO4·6H2The volume ratio of O solution is 1:1.1～1.2.Other is identical with detailed description of the invention one.
Present invention is not limited only to the content of the respective embodiments described above, and the combination of one of them or several detailed description of the invention can also realize the purpose of invention equally.
Beneficial effects of the present invention is verified by following example:
Embodiment one
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, carries out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and 75mL concentrated sulphuric acid are put in 500mL three-necked bottle, the ice-water bath of 0～4 DEG C stirs 30min；Above-mentioned solution is maintained in ice-water bath, is slowly added 2.3g sodium nitrate, be slow added into 15g potassium permanganate, stir 2h；After stirring 2h, reactant liquor is continued at normal temperatures stirring 1h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to be diluted, and add hydrogen peroxide to golden yellow, add the dilute hydrochloric acid of 10～20mL amount, it is centrifuged after cooling, finally solution is put in semipermeable membrane dialysis and processes until neutral；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution 5mL, 0.4mol/LNiSO46H2O solution 6mL, 0.5mol/LNaOH solution 15mL, hydrazine hydrate solution 10mL；
The graphene oxide ultrasonic dissolution taking the preparation of 25mL step one becomes the colloidal sol of 0.01g/mL；Then, by CuSO4·5H2O and NiSO4·6H2Add graphene oxide after O solution mix homogeneously and mix ultrasonic 1h, it is mixed solution and joins acceleration stirring in 250mL three-necked bottle, under agitation again the sodium hydroxide prepared and hydrazine hydrate solution are equipped with in the three-necked bottle of mixed solution, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, to wash after product non-shock chilling 1h, filter, be centrifuged after having reacted, obtain black powder after being finally putting in vacuum drying oven 24 hours, be namely uniformly dispersed, graphene-supported nanometer of Cu of stable chemical performance3.8Ni alloy.
What the present embodiment prepared be uniformly dispersed, graphene-supported nanometer of Cu of stable chemical performance3.8The SEM of Ni alloy schemes as shown in Figure 2.
The graphene-supported nanometer of Cu that the present embodiment is prepared3.8Ni alloy and graphene oxide, Graphene and nanometer Cu3.8Ni alloy carries out XRD figure spectrum comparative analysis, result is as shown in Figure 1, can be drawn by Fig. 1, curve a is the XRD spectra of graphene oxide, in 2 positions, θ=9.76 °, the narrow peak that one intensity is significantly high occurs, curve b is the XRD spectra of Graphene, and the broad peak about 2 θ=24 ° is the characteristic peak of Graphene prepared by redox graphene.Curve c is graphene-supported nanometer of Cu3.8The curve of Ni alloy, three sharp-pointed diffraction maximums respectively 2 θ=43.6 ° in curve, 50.76 °, 74.44 °, corresponding Cu respectively3.8(111), (200) of Ni alloy, (220) crystallographic plane diffraction peak, it does not have the carbide of copper and mickel or the peak of oxide occur, it was shown that nickel ion and copper ion adsorb and be reduced to nickel particles and copper ion on Graphene.Diffraction maximum be can't see in the position of 2 θ=10 °, illustrate that graphene oxide is reduced；Also occur in that the characteristic peak of Graphene at 2 θ=24 ° places simultaneously, and peak height to compare the peak of Graphene in curve b less.Curve d is a nanometer Cu3.8The diffraction maximum of Ni alloy, it can be seen that 2 θ=43.6 °, 50.76 °, the 74.44 ° diffraction maximum located corresponding Cu respectively3.8(111), (200) of Ni lattice, (220) crystal face diffraction.Foregoing illustrates: hydrazine hydrate is the common redox graphene of reducing agent and Cu3.8Ni alloy, prepares composite concept feasible, and the alloy prepared by the method does not have impurity, can generate graphene-supported Cu without surfactant after adding Graphene3.8The concentration of Ni alloy is high, and composite is containing only having Graphene and Cu3.8The face-centered cube of Ni alloy, it does not have the impurity such as oxide；In composite, Nanometer Copper and nano nickel particle can effectively reduce accumulation superposition agglomeration traits between graphene layer.
Embodiment 2
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, carries out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and 75mL concentrated sulphuric acid are put in 500mL three-necked bottle, the ice-water bath of 0～4 DEG C stirs 30min；Above-mentioned solution is maintained in ice-water bath, is slowly added 2.3g sodium nitrate, be slow added into 15g potassium permanganate, stir 2h；After stirring 2h, reactant liquor is continued at normal temperatures stirring 1h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to be diluted, and add hydrogen peroxide to golden yellow, add the dilute hydrochloric acid of 10～20mL amount, it is centrifuged after cooling, finally solution is put in semipermeable membrane dialysis and processes until neutral；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution 8mL, 0.4mol/LNiSO4·6H2O solution 10mL, 0.5mol/LNaOH solution 20mL, hydrazine hydrate solution 15mL；
The graphene oxide ultrasonic dissolution taking the preparation of 30mL step one becomes the colloidal sol of 0.01g/mL；Then, by CuSO4·5H2O and NiSO4·6H2Add graphene oxide after O solution mix homogeneously and mix ultrasonic 1h, it is mixed solution and joins acceleration stirring in 250mL three-necked bottle, under agitation again the sodium hydroxide prepared and hydrazine hydrate solution are equipped with in the three-necked bottle of mixed solution, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, to wash after product non-shock chilling 1h, filter, be centrifuged after having reacted, obtain black powder after being finally putting in vacuum drying oven 24 hours, be namely uniformly dispersed, graphene-supported nanometer of Cu of stable chemical performance3.8Ni alloy.
The method of the present embodiment is simple, quick, it is not necessary to adding any coating material, the present embodiment utilizes the Nanoalloy particle that reducing process makes load on Graphene, good dispersion, and size uniform, particle diameter is less.The hydrazine hydrate of the present embodiment is that reducing agent generates a large amount of N in course of reaction2, at N2Protection lower can be prevented effectively from reduction process the generation of oxide.The present embodiment utilize the method that graphene oxide reduces can make reduction after Graphene and Nanoalloy particle between be connected with chemical bond, its chemical property is also more stable.
Embodiment 3
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, carries out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and 75mL concentrated sulphuric acid are put in 500mL three-necked bottle, the ice-water bath of 0～4 DEG C stirs 30min；Above-mentioned solution is maintained in ice-water bath, is slowly added 2.3g sodium nitrate, be slow added into 15g potassium permanganate, stir 2h；After stirring 2h, reactant liquor is continued at normal temperatures stirring 1h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to be diluted, and add hydrogen peroxide to golden yellow, add the dilute hydrochloric acid of 10～20mL amount, it is centrifuged after cooling, finally solution is put in semipermeable membrane dialysis and processes until neutral；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution 10mL, 0.4mol/LNiSO4·6H2O solution 12mL, 0.5mol/LNaOH solution 20mL, hydrazine hydrate solution 15mL；
The graphene oxide ultrasonic dissolution taking the preparation of 20mL step one becomes the colloidal sol of 0.01g/mL；Then, by CuSO4·5H2O and NiSO4·6H2Add graphene oxide after O solution mix homogeneously and mix ultrasonic 1h, it is mixed solution and joins acceleration stirring in 250mL three-necked bottle, under agitation again the sodium hydroxide prepared and hydrazine hydrate solution are equipped with in the three-necked bottle of mixed solution, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, to wash after product non-shock chilling 1h, filter, be centrifuged after having reacted, obtain black powder after being finally putting in vacuum drying oven 24 hours, be namely uniformly dispersed, graphene-supported nanometer of Cu of stable chemical performance3.8Ni alloy.
The method of the present embodiment is simple, quick, it is not necessary to adding any coating material, the present embodiment utilizes the Nanoalloy particle that reducing process makes load on Graphene, good dispersion, and size uniform, particle diameter is less.The hydrazine hydrate of the present embodiment is that reducing agent generates a large amount of N in course of reaction2, at N2Protection lower can be prevented effectively from reduction process the generation of oxide.The present embodiment utilize the method that graphene oxide reduces can make reduction after Graphene and Nanoalloy particle between be connected with chemical bond, its chemical property is also more stable.
Claims (5)
1. liquid phase reduction prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it is characterised in that it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and concentrated sulphuric acid being mixed in the ratio that mass volume ratio is 1g:40～60mL, after stirring 30min in the ice-water bath of 0～4 DEG C, obtain mixed liquid；Mixed liquid is continually maintained in ice-water bath, after adding sodium nitrate in mixed liquid, adds potassium permanganate, then after stirring 2h, go to room temperature and continue stirring 1h, obtain mixed solution；Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, with distilled water, mixed solution is diluted to the 10% of original solution concentration, and add hydrogen peroxide to mixed solution variable color, add mixed solution after dilution 1 the dilute hydrochloric acid of 50 times of volumes, then after mixed solution being cooled to room temperature, centrifugal, collect lower floor's thick liquid, lower floor's thick liquid is put into dialysis in semipermeable membrane process until the pH value of lower floor's thick liquid is neutrality, obtain graphene oxide；Wherein, the mass volume ratio of sodium nitrate and mixed liquid is 1g:30～40mL, and the mass volume ratio of potassium permanganate and mixed liquid is 1g:5～10mL；
Step 2: graphene-supported nanometer of Cu3.8The preparation of Ni alloy
First, preparation 0.4mol/LCuSO4·5H2O solution, 0.4mol/LNiSO4·6H2O solution, 0.5mol/LNaOH solution and hydrazine hydrate solution；
Secondly, graphene oxide ultrasonic dissolution step one prepared becomes the colloidal sol of 0.01g/mL；Then by 0.4mol/LCuSO4·5H2O solution and 0.4mol/LNiSO4·6H2After O solution mix homogeneously, join ultrasonic 1h in graphene oxide colloidal sol, then the solution after ultrasonic is added under stirring the mixed liquor of 0.5mol/LNaOH solution and hydrazine hydrate solution, obtains mixed solution；Finally mixed solution is placed in the water-bath of 93 DEG C, under 200r/min mixing speed, stirring reaction 40min, after having reacted, after being statically placed in room temperature environment cooling 1h, scrubbed, filter, centrifugal, collect solid formation and put in vacuum drying oven after dry 24h, obtain black powder, be graphene-supported nanometer of Cu3.8Ni alloy；Wherein, CuSO4·5H2O solution and NiSO4·6H2The volume ratio of the mixed solution of O solution and graphene oxide colloidal sol is 1:1～1.5；CuSO4·5H2O solution and NiSO4·6H2The volume ratio of O solution is 1:1.1～1.2；0.5mol/LNaOH solution, the mixed liquor of hydrazine hydrate solution and the volume ratio of graphene oxide colloidal sol are 1:1～2:1.
2. liquid phase reduction according to claim 1 prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it is characterised in that in step one, sodium nitrate is 1g:32～38mL with the mass volume ratio of mixed liquid.
3. liquid phase reduction according to claim 1 prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it is characterised in that in step one, potassium permanganate is 1g:7～9mL with the mass volume ratio of mixed liquid.
4. liquid phase reduction according to claim 1 prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it is characterised in that in step one, potassium permanganate is 1g:8mL with the mass volume ratio of mixed liquid.
5. liquid phase reduction according to claim 1 prepares graphene-supported nanometer of Cu3.8The method of Ni alloy, it is characterised in that in step one, graphite powder and concentrated sulphuric acid are 1g:45～55mL by mass volume ratio.
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| CN103736993A (en) * | 2014-01-03 | 2014-04-23 | 上海交通大学 | Preparation method of graphene/copper composite material |
| CN104028272A (en) * | 2014-06-26 | 2014-09-10 | 聊城大学 | Graphene-supported copper-nickel composite nanometer photocatalyst, and preparation method and application thereof |
| CN104028269A (en) * | 2014-06-20 | 2014-09-10 | 南京工业大学 | Graphene loaded metal nano composite material, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102218540A (en) * | 2010-04-14 | 2011-10-19 | 韩国科学技术院 | Graphene/metal nanocomposite powder and method of manufacturing the same |
| CN103157809A (en) * | 2013-02-05 | 2013-06-19 | 西南科技大学 | Preparation method of graphene/metal nanoparticle composite material with sandwich structure |
| CN103540786A (en) * | 2013-10-31 | 2014-01-29 | 青岛科技大学 | Preparation method of graphene/copper-nickel nano composite material |
| CN103736993A (en) * | 2014-01-03 | 2014-04-23 | 上海交通大学 | Preparation method of graphene/copper composite material |
| CN104028269A (en) * | 2014-06-20 | 2014-09-10 | 南京工业大学 | Graphene loaded metal nano composite material, and preparation method and application thereof |
| CN104028272A (en) * | 2014-06-26 | 2014-09-10 | 聊城大学 | Graphene-supported copper-nickel composite nanometer photocatalyst, and preparation method and application thereof |
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