CN104475753A - Method for preparing nano Cu3.8 Ni alloy loaded on graphene by liquid phase reduction method - Google Patents
Method for preparing nano Cu3.8 Ni alloy loaded on graphene by liquid phase reduction method Download PDFInfo
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Abstract
The invention relates to a method for preparing nano Cu3.8 Ni alloy loaded on graphene, in particular to a method for preparing the nano Cu3.8 Ni alloy loaded on the graphene by a liquid phase reduction method. The method takes the graphene as a surface active agent, and solves the problem that the existing surface active agent is difficult to treat. The method comprises the steps of firstly, preparing graphene oxide, and then mixing CuSO4 5H2O solution, NiSO4 6H2O solution, NaOH solution and hydrazine hydrate solution with the graphene oxide for treatment. Related report of preparing the nano Cu3.8 Ni alloy loaded on the graphene by a reduction method is not reported yet; the method is simple and fast, and any surface modifying agent does not need to be added. After the reduction method is adopted, nano alloy particles loaded on the graphene are well dispersed and are uniform in size and smaller in particle size. The hydrazine hydrate is taken as a reducing agent, and a great deal of N2 is generated in the reaction process, so that the oxide is effectively prevented from being generated in the reduction process under the protection of the N2.
Description
Technical field
The present invention relates to the graphene-supported nanometer Cu of preparation
3.8the method of Ni alloy.
Background technology
Graphene is with sp by carbon atom
2the monoatomic layer of the close heap honeycomb structure of six sides that hybrid form is formed is the two-dimensional atomic crystal that the mankind find the earliest.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 unique two-dimensional nanostructure, large specific area, excellent electric conductivity and good chemical stability, make Graphene have good application prospect in fields such as transistor, solar cell, sensor, ultracapacitor, Flied emission and catalyst carriers, also become the carrier that a graphene-supported composite of preparation is ideal simultaneously.
Metallic nickel is a kind of magnetic metal material, is widely used in magnetic material, plated material field; Copper powder has electric conductivity, thermal conductivity and ductility, nanometer Cu
3.8ni alloy possesses all advantages of Nanometer Copper and nano nickel, is a kind of novel nano alloy.Receive much concern because it shows excellent character in electricity, magnetic and catalysis etc., there is important researching value.Therefore, graphene-supported nanometer Cu is prepared
3.8ni alloy, the combination of both realizations performance is the important research direction of a combined innovation and practicality.Graphene and electroconductive magnetic alloy combine by the present invention, prepare graphene-supported nanometer Cu
3.8ni alloy.The present invention's graphene oxide that adopted oxidation-reduction method to prepare, then reduce through reducing agent after Graphene is mixed with copper ion and nickel ion and obtain graphene-supported nanometer Cu
3.8ni alloy, the method is simple, quick, need not add any coating material, makes that graphenic surface alloy particle is evenly distributed, stable chemical performance, is a kind of more satisfactory preparation method.
Summary of the invention
The object of the invention is to adopt Graphene to serve as surfactant, in order to the unmanageable problem of the surfactant solving existing existence, and provide the method that liquid phase reduction prepares graphene-supported nanometer Cu3.8Ni alloy.
Liquid phase reduction of the present invention prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and the concentrated sulfuric acid being mixed in the ratio that mass volume ratio is 1g:40 ~ 60mL, stir 30min in the ice-water bath of 0 ~ 4 DEG C after, obtain mixed liquid; Mixed liquid is continued to remain in ice-water bath, add sodium nitrate in mixed liquid after, then adds potassium permanganate, after then stirring 2h, go to normal temperature and continue to stir 1h, obtain mixed solution; Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, mixed solution is diluted to 10% of original solution concentration with distilled water, and add hydrogen peroxide to mixed solution variable color, add again mixed solution 1 after dilution the watery 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 pellicle dialysis process until the pH value of lower floor's thick liquid is for neutral, 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 Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution, 0.4mol/L NiSO
46H
2o 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/LCuSO
45H
2o solution and 0.4mol/LNiSO
46H
2after O solution mixes, 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, obtain 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, through washing, filter, centrifugal, collect after solid formation puts into the dry 24h of vacuum drying chamber, obtain black powder, be graphene-supported nanometer Cu
3.8ni alloy; Wherein, CuSO
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:1 ~ 3; CuSO
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1 ~ 1.3; The mixed liquor of 0.5mol/LNaOH solution, 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, does not need to add any coating material.
2, utilize 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 reaction
2, at N
2protection under effectively can avoid the generation of oxide in reduction process.
4, the Graphene after the method utilizing graphene oxide to reduce can make reduction is connected with chemical bond with between Nanoalloy particle, and its chemical property is also more stable.
Even 5 have no and prepare graphene-supported nanometer Cu by reducing process
3.8the relevant report of Ni alloy.
Because Graphene is can 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, is easy in the solution assemble and difficult dispersion, is unfavorable for large-scale production, and nanometer Cu
3.8the existence of Ni particle effectively can increase the distance between graphene sheet layer, thus reduces the Van der Waals force between Graphene greatly, simultaneously nanometer Cu
3.8ni particle can not have impact to the character of Graphene itself, and effectively to avoid Graphene to reunite on the other hand, nano particle had not only modified Graphene simultaneously but also remain the excellent properties of Graphene itself, and nanometer Cu
3.8the character of Ni particle itself also can not affect because of Graphene to some extent, remains respective inherent characteristic so therebetween simultaneously and mutually promotes again, which produces cooperative effect.
Accompanying drawing explanation
Fig. 1 is graphene oxide, Graphene, graphene-supported nanometer Cu
3.8ni alloy, nanometer Cu
3.8the 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 Cu
3.8the XRD spectra of Ni alloy, d is nanometer Cu
3.8the XRD spectra of Ni alloy;
Fig. 2 is the graphene-supported nanometer Cu that embodiment one obtains
3.8the 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 Cu
3.8the method of Ni alloy, it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and the concentrated sulfuric acid being mixed in the ratio that mass volume ratio is 1g:40 ~ 60mL, stir 30min in the ice-water bath of 0 ~ 4 DEG C after, obtain mixed liquid; Mixed liquid is continued to remain in ice-water bath, add sodium nitrate in mixed liquid after, then adds potassium permanganate, after then stirring 2h, go to normal temperature and continue to stir 1h, obtain mixed solution; Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, mixed solution is diluted to 10% of original solution concentration with distilled water, and add hydrogen peroxide to mixed solution variable color, add again mixed solution 1 after dilution the watery 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 pellicle dialysis process until the pH value of lower floor's thick liquid is for neutral, 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 Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution, 0.4mol/L NiSO
46H
2o 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/LCuSO
45H
2o solution and 0.4mol/LNiSO
46H
2after O solution mixes, 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, obtain 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, through washing, filter, centrifugal, collect after solid formation puts into the dry 24h of vacuum drying chamber, obtain black powder, be graphene-supported nanometer Cu
3.8ni alloy; Wherein, CuSO
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:1 ~ 3; CuSO
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1 ~ 1.3; The mixed liquor of 0.5mol/LNaOH solution, 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 unlike: in step one, the mass volume ratio of sodium nitrate and mixed liquid is 1g:32 ~ 38mL.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 unlike: in step one, the mass volume ratio of sodium nitrate and mixed liquid is 1g:34 ~ 36mL.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 unlike: in step one, the mass volume ratio of sodium nitrate and mixed liquid is 1g:35mL.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 unlike: in step one, the mass volume ratio of potassium permanganate and mixed liquid is 1g:7 ~ 9mL.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 unlike: in step one, the mass volume ratio of potassium permanganate and mixed liquid is 1g:8mL.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 unlike: in step one, graphite powder and the concentrated sulfuric 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 unlike: in step one, graphite powder and the concentrated sulfuric 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 unlike: in step one, graphite powder and the concentrated sulfuric 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 unlike CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 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 unlike CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 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 unlike CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 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 unlike CuSO in step 2
45H
2o solution and NiSO
46H
2the 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 unlike CuSO in step 2
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1.1 ~ 1.2.Other is identical with detailed description of the invention one.
Content of the 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 equally also can realize the object of inventing.
Beneficial effect of the present invention is verified by following examples:
Embodiment one
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, carry out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and the 75mL concentrated sulfuric acid are put into 500mL three-necked bottle, in the ice-water bath of 0 ~ 4 DEG C, stirs 30min; Above-mentioned solution is remained in ice-water bath, slowly adds 2.3g sodium nitrate simultaneously, more slowly add 15g potassium permanganate, stir 2h; Reactant liquor is continued at normal temperatures to stir 1h after stirring 2h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to dilute, and add hydrogen peroxide to golden yellow, add the watery hydrochloric acid of 10 ~ 20mL amount again, carry out centrifugal after cooling, finally solution is put into pellicle dialysis process until neutrality;
Step 2: graphene-supported nanometer Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution 5mL, 0.4mol/L NiSO
46H2O solution 6mL, 0.5mol/LNaOH solution 15mL, hydrazine hydrate solution 10mL;
The graphene oxide ultrasonic dissolution getting the preparation of 25mL step one becomes the colloidal sol of 0.01g/mL; Then, by CuSO
45H
2o and NiSO
46H
2add graphene oxide after O solution mixes and mix ultrasonic 1h, its mixed solution is joined in 250mL three-necked bottle and accelerate to stir, under agitation the NaOH prepared and hydrazine hydrate solution being added is equipped with in the three-necked bottle of mixed solution again, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, after having reacted by after static for product cooling 1h wash, filter, centrifugal, finally put into vacuum drying chamber and obtain black powder after 24 hours, be namely uniformly dispersed, the graphene-supported nanometer Cu of stable chemical performance
3.8ni alloy.
What the present embodiment obtained is uniformly dispersed, the graphene-supported nanometer Cu of stable chemical performance
3.8the SEM figure of Ni alloy as shown in Figure 2.
The graphene-supported nanometer Cu obtained by the present embodiment
3.8ni alloy and graphene oxide, Graphene and nanometer Cu
3.8ni alloy carries out the analysis of XRD trace analysis, result as shown in Figure 1, can be drawn by Fig. 1, curve a is the XRD spectra of graphene oxide, the narrow peak that an intensity is very high is there is in ° position, 2 θ=9.76, 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 Cu
3.8the curve of Ni alloy, three in curve sharp-pointed diffraction maximums be respectively 2 θ=43.6 °, 50.76 °, 74.44 °, corresponding Cu respectively
3.8(111), (200), (220) crystallographic plane diffraction peak of Ni alloy, do not have the carbide of copper and mickel or the peak of oxide to occur, show 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; In 2 θ=24 also there is the characteristic peak of Graphene in a ° place simultaneously, and the peak that peak height compares the Graphene in curve b is less.Curve d is nanometer Cu
3.8the diffraction maximum of Ni alloy, can see the diffraction maximums corresponding Cu respectively at 2 θ=43.6 °, 50.76 °, 74.44 ° places
3.8(111), (200), (220) crystal face diffraction of Ni lattice.Foregoing illustrates: hydrazine hydrate is the common redox graphene of reducing agent and Cu
3.8ni alloy, prepares composite concept feasible, and the alloy prepared by the method does not have impurity, does not add surfactant and can generate graphene-supported Cu after adding Graphene
3.8the concentration of Ni alloy is high, and composite is only containing Graphene and Cu
3.8the face-centered cube of Ni alloy, does not have the impurity such as oxide; In composite, Nanometer Copper and nano nickel particle can effectively reduce between graphene layer and pile up superposition agglomeration traits.
Embodiment 2
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, carry out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and the 75mL concentrated sulfuric acid are put into 500mL three-necked bottle, in the ice-water bath of 0 ~ 4 DEG C, stirs 30min; Above-mentioned solution is remained in ice-water bath, slowly adds 2.3g sodium nitrate simultaneously, more slowly add 15g potassium permanganate, stir 2h; Reactant liquor is continued at normal temperatures to stir 1h after stirring 2h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to dilute, and add hydrogen peroxide to golden yellow, add the watery hydrochloric acid of 10 ~ 20mL amount again, carry out centrifugal after cooling, finally solution is put into pellicle dialysis process until neutrality;
Step 2: graphene-supported nanometer Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution 8mL, 0.4mol/L NiSO
46H
2o solution 10mL, 0.5mol/LNaOH solution 20mL, hydrazine hydrate solution 15mL;
The graphene oxide ultrasonic dissolution getting the preparation of 30mL step one becomes the colloidal sol of 0.01g/mL; Then, by CuSO
45H
2o and NiSO
46H
2add graphene oxide after O solution mixes and mix ultrasonic 1h, its mixed solution is joined in 250mL three-necked bottle and accelerate to stir, under agitation the NaOH prepared and hydrazine hydrate solution being added is equipped with in the three-necked bottle of mixed solution again, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, after having reacted by after static for product cooling 1h wash, filter, centrifugal, finally put into vacuum drying chamber and obtain black powder after 24 hours, be namely uniformly dispersed, the graphene-supported nanometer Cu of stable chemical performance
3.8ni alloy.
The method of the present embodiment is simple, quick, and do not need to add any coating material, the Nanoalloy particle that the present embodiment utilizes reducing process to make load on Graphene, good dispersion, 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 reaction
2, at N
2protection under effectively can avoid the generation of oxide in reduction process.Graphene after the method that the present embodiment utilizes graphene oxide to reduce can make reduction is connected with chemical bond with between Nanoalloy particle, and its chemical property is also more stable.
Embodiment 3
The liquid phase reduction of the present embodiment prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, carry out according to following steps:
Step one: the preparation of graphene oxide
1.8g graphite powder and the 75mL concentrated sulfuric acid are put into 500mL three-necked bottle, in the ice-water bath of 0 ~ 4 DEG C, stirs 30min; Above-mentioned solution is remained in ice-water bath, slowly adds 2.3g sodium nitrate simultaneously, more slowly add 15g potassium permanganate, stir 2h; Reactant liquor is continued at normal temperatures to stir 1h after stirring 2h, then mixed liquor is placed in 35 DEG C of water-baths and reacts 10h, add distilled water after 10h to dilute, and add hydrogen peroxide to golden yellow, add the watery hydrochloric acid of 10 ~ 20mL amount again, carry out centrifugal after cooling, finally solution is put into pellicle dialysis process until neutrality;
Step 2: graphene-supported nanometer Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution 10mL, 0.4mol/LNiSO
46H
2o solution 12mL, 0.5mol/LNaOH solution 20mL, hydrazine hydrate solution 15mL;
The graphene oxide ultrasonic dissolution getting the preparation of 20mL step one becomes the colloidal sol of 0.01g/mL; Then, by CuSO
45H
2o and NiSO
46H
2add graphene oxide after O solution mixes and mix ultrasonic 1h, its mixed solution is joined in 250mL three-necked bottle and accelerate to stir, under agitation the NaOH prepared and hydrazine hydrate solution being added is equipped with in the three-necked bottle of mixed solution again, finally mixed solution is placed in the water-bath of 93 DEG C, 200r/min stirring reaction 40min, after having reacted by after static for product cooling 1h wash, filter, centrifugal, finally put into vacuum drying chamber and obtain black powder after 24 hours, be namely uniformly dispersed, the graphene-supported nanometer Cu of stable chemical performance
3.8ni alloy.
The method of the present embodiment is simple, quick, and do not need to add any coating material, the Nanoalloy particle that the present embodiment utilizes reducing process to make load on Graphene, good dispersion, 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 reaction
2, at N
2protection under effectively can avoid the generation of oxide in reduction process.Graphene after the method that the present embodiment utilizes graphene oxide to reduce can make reduction is connected with chemical bond with between Nanoalloy particle, and its chemical property is also more stable.
Claims (10)
1. liquid phase reduction prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that it carries out according to following steps:
Step one: the preparation of graphene oxide
After graphite powder and the concentrated sulfuric acid being mixed in the ratio that mass volume ratio is 1g:40 ~ 60mL, stir 30min in the ice-water bath of 0 ~ 4 DEG C after, obtain mixed liquid; Mixed liquid is continued to remain in ice-water bath, add sodium nitrate in mixed liquid after, then adds potassium permanganate, after then stirring 2h, go to normal temperature and continue to stir 1h, obtain mixed solution; Then mixed solution is placed in 35 DEG C of water-baths and reacts 10h, mixed solution is diluted to 10% of original solution concentration with distilled water, and add hydrogen peroxide to mixed solution variable color, add again mixed solution 1 after dilution the watery 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 pellicle dialysis process until the pH value of lower floor's thick liquid is for neutral, 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 Cu
3.8the preparation of Ni alloy
First, 0.4mol/L CuSO is prepared
45H
2o solution, 0.4mol/LNiSO
46H
2o 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/L CuSO
45H
2o solution and 0.4mol/LNiSO
46H
2after O solution mixes, 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, obtain 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, through washing, filter, centrifugal, collect after solid formation puts into the dry 24h of vacuum drying chamber, obtain black powder, be graphene-supported nanometer Cu
3.8ni alloy; Wherein, CuSO
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:1 ~ 3; CuSO
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1 ~ 1.3; The mixed liquor of 0.5mol/LNaOH solution, 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 Cu
3.8the method of Ni alloy, is characterized in that the mass volume ratio of sodium nitrate and mixed liquid in step one is 1g:32 ~ 38mL.
3. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that the mass volume ratio of potassium permanganate and mixed liquid in step one is 1g:7 ~ 9mL.
4. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that the mass volume ratio of potassium permanganate and mixed liquid in step one is 1g:8mL.
5. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that in step one, graphite powder and the concentrated sulfuric acid are 1g:45 ~ 55mL by mass volume ratio.
6. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:1.5 ~ 2.5.
7. liquid phase reduction according to claim 6 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:1.8 ~ 2.2.
8. liquid phase reduction according to claim 7 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that CuSO in step 2
45H
2o solution and NiSO
46H
2the mixed solution of O solution and the volume ratio of graphene oxide colloidal sol are 1:2.
9. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that CuSO in step 2
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1.1 ~ 1.3.
10. liquid phase reduction according to claim 1 prepares graphene-supported nanometer Cu
3.8the method of Ni alloy, is characterized in that CuSO in step 2
45H
2o solution and NiSO
46H
2the volume ratio of O solution is 1:1.1 ~ 1.2.
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| CN106591822A (en) * | 2016-11-28 | 2017-04-26 | 广东工业大学 | Preparation method and application of graphene strengthened copper base composite coating |
| CN108080652A (en) * | 2017-12-21 | 2018-05-29 | 黑龙江大学 | A kind of method that liquid phase reduction prepares nano-copper-nickel alloy cladding polystyrene core-shell structure composite material |
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| CN108080652A (en) * | 2017-12-21 | 2018-05-29 | 黑龙江大学 | A kind of method that liquid phase reduction prepares nano-copper-nickel alloy cladding polystyrene core-shell structure composite material |
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| CN110624552A (en) * | 2019-10-24 | 2019-12-31 | 南京苏展智能科技有限公司 | Preparation method of graphene nano metal composite material |
| CN110922742A (en) * | 2019-10-31 | 2020-03-27 | 深圳市超导新材料有限公司 | Novel transparent conductive film and preparation method thereof |
| CN110814358A (en) * | 2019-11-15 | 2020-02-21 | 桂林电子科技大学 | Preparation method and application of Ag-Cu nano alloy with blood sugar detection characteristic |
| CN110814358B (en) * | 2019-11-15 | 2022-08-30 | 桂林电子科技大学 | Preparation method and application of Ag-Cu nano alloy with blood sugar detection characteristic |
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