CN105328205A - Simple manufacturing method for ultra-small-size copper and nickel nano composite with stable graphene - Google Patents
Simple manufacturing method for ultra-small-size copper and nickel nano composite with stable graphene Download PDFInfo
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- CN105328205A CN105328205A CN201510709251.1A CN201510709251A CN105328205A CN 105328205 A CN105328205 A CN 105328205A CN 201510709251 A CN201510709251 A CN 201510709251A CN 105328205 A CN105328205 A CN 105328205A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
- B22F2009/245—Reduction reaction in an Ionic Liquid [IL]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
Abstract
The invention discloses a simple manufacturing method for an ultra-small-size copper and nickel nano composite with stable graphene. The simple manufacturing method includes the following steps: weighing oxidized graphene, nickel salt and copper salt solutions, alkali liquor is added after even mixing is carried out, quick heating is carried out for an reaction, centrifugal separation is carried out after the reaction is completed, and a product is washed and collected to obtain the ultra-small-size copper and nickel nano composite with stable graphene. The simple manufacturing method is simple in process, poisonous and explosive hydrazine hydrate does not need to be used as a reducing agent during the reaction, the preparation condition is common, the grain diameter of the product is quiet small, the morphology is stable, and the purity is high; and in addition, product processing is convenient and concise, and the simple manufacturing method is suitable for medium scale industrial production.
Description
Technical field
The invention belongs to field of material technology, particularly relate to the simple method for preparing of the stable super-small copper nickel nano-complex of a kind of Graphene.
Background technology
Nanoscale science and technology be late 1980s produce one just in the new technology of fast development.So-called nanometer technology refers to unit---the nanoparticle with some molecules or atomic building, the science and technology of manufactured materials or microdevice.Nanoparticle refers to the metal of size between 1 ~ 100nm or the fine particle of semiconductor.The special construction level that nanoparticle has, impart its much special character and function, nano particle has large specific area, surface atom number, surface energy and surface tension, decline with particle diameter sharply increases, skin effect, small-size effect, quantum size effect, macro quanta tunnel effect and Dielectric confinement effect etc. cause the thermal and magnetic of nano particle, light, sensitivity characteristic and surface stability etc. to be different from conventional particle, and this just makes it be with a wide range of applications.
Inorganic metal nano particle is evenly spread to graphene nanometer sheet surface and make graphene-based inorganic metal nano composite material, the dual-use function character of tool Graphene and inorganic metal nano particle can not only be accounted for, and the cooperative effect of some novelties may be produced.Itself have the performance of many excellences due to inorganic metal nano particle and apply widely, the compound of they and Graphene can be improved the performance of material further, greatly widen the range of application of inorganic metal nano particle and Graphene.Because the size of nano material and pattern directly affect the physics and chemistry character of material, so important trend is the research of engineering of tightening control in nanometer material preparation science and technical research, comprise the control of particle size, pattern, surface state and micro-structural.Again because nano metal has a wide range of applications in every field, so explore the control synthetic method of simple, effective Graphene metal nanometer composite material, the investigation and application for graphene inorganic nano metal composite has important theory and realistic meaning.
At present, the research of graphene-supported metal nano particle composite material mainly contains hydrothermal synthesis method and solvent-thermal process method.Metal nanoparticle is grapheme modified, and this not only can overcome Van der Waals force huge between graphene layer, prevents the reunion of graphene film, and the peculiar property of single-layer graphene is retained.Meanwhile, its many Performance Ratio metal of the composite obtained itself is more superior, has important using value in fields such as catalysis, ceramic chemical industry and batteries.
Summary of the invention
The object of this invention is to provide the simple method for preparing of the stable super-small copper nickel nano-complex of a kind of Graphene.
To achieve these goals, technical scheme of the present invention is as follows:
A simple method for preparing for the super-small copper nickel nano-complex that Graphene is stable, concrete steps are as follows:
Measure graphene oxide, nickel salt, mantoquita join in solvent, add alkali lye after mixing, carry out heating and carry out in oil bath pan, described reaction temperature is 180 DEG C, and the reaction time is 15min; Carry out centrifugation, washing after having reacted, collect product, obtain the super-small copper nickel nano-complex that Graphene is stable; Wherein: the proportion of graphene oxide quality and nickel salt and mantoquita gross mass is 1:0.001 ~ 1:0.004.
In the present invention, the mass concentration scope of the ethylene glycol solution of described graphene oxide is 0.07g/mL ~ 7g/mL;
Described nickel salt is NiCl
26H
2o, mantoquita is CuCl
26H
2o, the amount of substance scope of nickel salt and mantoquita is 1mmol ~ 0.001mmol.
In the present invention, described solvent is ethylene glycol; The concentration of described alkali lye is 2mol/L ~ 0.002mol/L.
In the present invention, described washing is by deionized water and ethanol washed product respectively.
In the present invention, the preparation concrete steps of described graphene oxide are: in natural flake graphite and sodium nitrate, add the concentrated sulfuric acid, be uniformly mixed in ice-water bath, add potassium permanganate while stirring, control temperature continues stirring reaction, and then heat up stirring, after adding deionized water in batches, add hydrogen peroxide again, continue stirring reaction, after suction filtration, washing, centrifugation, drying obtains graphene oxide while hot.
In the present invention, the mass ratio of described natural flake graphite and sodium nitrate is 1:1 ~ 3:1; The mass ratio of described natural flake graphite and the concentrated sulfuric acid is 1:40 ~ 1:50; The mass ratio of described natural flake graphite and potassium permanganate is 1:2 ~ 1:5; The mass ratio of described natural flake graphite and hydrogen peroxide is 1:5 ~ 1:10.
In the present invention, described control temperature is <10 DEG C, continues stirring 1 ~ 3h;
The described temperature stirred that heats up is 35 DEG C, and mixing time is 2 ~ 3h;
The mass ratio of described natural flake graphite and deionized water is 1:10 ~ 1:50.
In the present invention, described in add hydrogen peroxide after continue stirring reaction 1 ~ 3h.
In the present invention, described washing carries out centrifuge washing by the salt solution of 100mL5% and the deionized water of 50 DEG C successively, is 7 to filtrate pH value.
In the present invention, described drying is dry 10h in 60 DEG C of vacuum drying chambers.
Owing to adopting such scheme, the present invention has following beneficial effect:
1, present invention achieves the presoma utilizing the graphite of common nickel salt and mantoquita and cheapness for reaction, synthesize the stable super-small copper nickel nano-complex of Graphene first by a stage reduction method.
2, method reducing agent of the present invention adopts nontoxic ethylene glycol, environmentally friendly, can not produce the accessory substances such as toxic and harmful.And conventional method generally adopts hydrazine hydrate as reducing agent, easily decompose and produce toxic and harmful, and the gas meeting augmenting response system pressure produced, greatly increase explosion danger, reduce safety coefficient.
3, technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product process is convenient succinct, is suitable for medium-scale industrial production.
4, the present invention adopts simple inorganic salts as reactant, has very strong versatility.
5, method of the present invention has mild condition, homogeneous heating, efficient energy-saving, is easy to the features such as control.
6, the product that prepared by the present invention has good p-nitrophenol degraded catalytic performance, as high performance catalyst, can have comparatively vast potential for future development and application space.
Accompanying drawing explanation
Fig. 1 is the TEM photo of the product obtained under the multiple of 10nm in embodiment 1.
Fig. 2 is the HRTEM photo of the product obtained under the multiple of 2nm in embodiment 1.
Fig. 3 is the electronic diffraction collection of illustrative plates of embodiment 1 products therefrom.
Fig. 4 is the XRD collection of illustrative plates of embodiment 1 products therefrom.
Fig. 5 is the XPS collection of illustrative plates of embodiment 1 products therefrom.
Fig. 6 is the TEM photo of the product obtained under the multiple of 400nm in embodiment 2.
Detailed description of the invention
Below in conjunction with accompanying drawing illustrated embodiment, the present invention is further detailed explanation.
Embodiment 1
1) Hummers method synthesis graphene oxide
The first step, takes 1g natural flake graphite and 0.5g sodium nitrate (mass ratio is 2:1), is added in 250mL tri-neck round-bottomed flask, more slowly add the 20-30ml concentrated sulfuric acid.Course of reaction mechanical agitation in ice-water bath of system.
Second step, slowly adds 2-5g potassium permanganate in whipping process, adds speed, reaction temperature is controlled within 10 DEG C by regulation and control.After adding, then continue low temperature stirring 1h.
3rd step, above-mentioned ice-water bath is changed into oil bath heating, temperature controls at 35 DEG C, and continues stirring 2 ~ 3h.
4th step, slowly adds 50mL deionized water several times, for dilution.
5th step, after stirring 0.5h, add the deionized water of 75mL50 DEG C, and add 30% hydrogen peroxide of 5 ~ 10mL, now product can become glassy yellow rapidly, continues to stir 1h.
6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing, to filtrate pH value close to 7 by the salt solution of 100mL5% and the deionized water of 50 DEG C successively.
7th step, centrifugal product under 3000rpm, collect upper strata centrifugate, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is graphene oxide.
2) synthesis of the super-small copper nickel nano-complex that Graphene is stable
The first step, measures 20mMCuCl
2, NiCl
2ethylene glycol mixed solution 0.5mL and 0.5gmL
-1the ethylene glycol solution 1.4mL of graphene oxide mix in glass reactor, magnetic agitation ten minutes.
Second step, the ethylene glycol solution 0.2mL and the extra ethylene glycol 6mL that measure 0.2mol/L NaOH join in previous solu, continue magnetic agitation 10 minutes.
3rd step, be quickly transferred in the oil bath pan being heated to 180 DEG C by glass reactor, under magnetic agitation, previous solu instant heating is kept 15min to 180 DEG C.
4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification, collect required product.Be dissolved in by freshly prepared product in 5ml ethanol, sealing is stored in sample cell.
After the composite obtained is characterized by XPS, prove containing Ni, Cu, C, O element in composite, and prove that Ni and Cu is simple substance and non-oxidized substance by XRD.
Fig. 1 is the TEM photo of the product obtained under the multiple of 10nm in embodiment 1; Fig. 2 is the HRTEM photo of the product obtained under the multiple of 2nm in embodiment 1; Fig. 3 is the electronic diffraction collection of illustrative plates of embodiment 1 products therefrom; Fig. 4 is the XRD collection of illustrative plates of embodiment 1 products therefrom, illustrates that the Ni element in compound exists with the form of the Ni of zero-valent state instead of oxide.Fig. 5 is the XPS collection of illustrative plates of embodiment 1 products therefrom.There is the element peak of Ni, Cu in XPS collection of illustrative plates, indicate the existence of these two kinds of elements.
Embodiment 2
1) Hummers method synthesis graphene oxide
The first step, takes 1g natural flake graphite and 0.3333g sodium nitrate, is added in 250mL tri-neck round-bottomed flask, more slowly adds the 20-30ml concentrated sulfuric acid.Course of reaction mechanical agitation in ice-water bath of system.
Second step, slowly adds 2-5g potassium permanganate in whipping process, adds speed, reaction temperature is controlled within 10 DEG C by regulation and control.After adding, then continue low temperature stirring 1h.
3rd step, above-mentioned ice-water bath is changed into oil bath heating, temperature controls at 35 DEG C, and continues stirring 2 ~ 3h.
4th step, slowly adds 50mL deionized water several times, for dilution.
5th step, after stirring 0.5h, add the deionized water of 75mL50 DEG C, and add 30% hydrogen peroxide of 5 ~ 10mL, now product can become glassy yellow rapidly, continues to stir 1h.
6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing, to filtrate pH value close to 7 by the salt solution of 100mL5% and the deionized water of 50 DEG C successively.
7th step, centrifugal product under 3000rpm, collect upper strata centrifugate, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is graphene oxide.
2) synthesis of the super-small copper nickel nano-complex that Graphene is stable
The first step, takes CuCl
2, NiCl
2ethylene glycol salt-mixture 0.1mmol be dissolved in 14mL0.5gmL
-1the ethylene glycol solution of graphene oxide mix in glass reactor, magnetic agitation ten minutes.
Second step, the ethylene glycol solution 1mL and the extra ethylene glycol 7mL that measure 0.2M NaOH join in previous solu, continue magnetic agitation 10 minutes.
3rd step, transfers to glass reactor in oil bath pan, is slowly heated to 180 DEG C, slowly drips 400uL hydrazine hydrate and keep 15min under magnetic agitation.
4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification, collect required product.Be dissolved in by freshly prepared product in 5ml ethanol, sealing is stored in sample cell.
Fig. 6 is the TEM figure of products therefrom in embodiment 2, shows that the size of monel nano particle is larger when using hydrazine hydrate as reducing agent.
Embodiment 3
1) Hummers method synthesis graphene oxide
The first step, takes 1g natural flake graphite and 0.3333g sodium nitrate, is added in 250mL tri-neck round-bottomed flask, more slowly adds the 20-30ml concentrated sulfuric acid.Course of reaction mechanical agitation in ice-water bath of system.
Second step, slowly adds 2-5g potassium permanganate in whipping process, adds speed, reaction temperature is controlled within 10 DEG C by regulation and control.After adding, then continue low temperature stirring 1h.
3rd step, above-mentioned ice-water bath is changed into oil bath heating, temperature controls at 35 DEG C, and continues stirring 2 ~ 3h.
4th step, slowly adds 50mL deionized water several times, for dilution.
5th step, after stirring 0.5h, add the deionized water of 75mL50 DEG C, and add 30% hydrogen peroxide of 5 ~ 10mL, now product can become glassy yellow rapidly, continues to stir 1h.
6th step, by this bright yellow solution suction filtration while hot, and carries out centrifuge washing, to filtrate pH value close to 7 by the salt solution of 100mL5% and the deionized water of 50 DEG C successively.
7th step, centrifugal product under 3000rpm, collect upper strata centrifugate, in 60 DEG C of vacuum drying chambers, dry 10h, products therefrom is graphene oxide.
2) synthesis of the super-small copper nickel nano-complex that Graphene is stable
The first step, takes CuCl
2, NiCl
2ethylene glycol salt-mixture 0.1mmol be dissolved in 14mL0.5gmL
-1the ethylene glycol solution of graphene oxide mix in glass reactor, magnetic agitation ten minutes.
Second step, the ethylene glycol solution 1mL and the extra ethylene glycol 7mL that measure 0.2M NaOH join in previous solu, continue magnetic agitation 10 minutes.
3rd step, transfers to glass reactor in oil bath pan, be slowly heated to 180 DEG C, under magnetic agitation, previous solu instant heating is kept 15min to 180 DEG C.
4th step, centrifugation black precipitate goes out precipitation with the rotating speed centrifugation of 3000rpm, with deionized water and ethanol washing, discards centrifugate; Until centrifugate achromaticity and clarification, collect required product.Be dissolved in by freshly prepared product in 5ml ethanol, sealing is stored in sample cell.
Experiment effect is with embodiment 1.
The above-mentioned description to embodiment can understand and apply the invention for ease of those skilled in the art.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (10)
1. a simple method for preparing for the super-small copper nickel nano-complex that Graphene is stable, is characterized in that concrete steps are as follows:
Measure graphene oxide, nickel salt, mantoquita join in solvent, add alkali lye after mixing, carry out adding thermal response in oil bath pan, described reaction temperature is 180 DEG C, and the reaction time is 15min; Carry out centrifugation, washing after having reacted, collect product, obtain the super-small copper nickel nano-complex that Graphene is stable; Wherein: graphene oxide quality and nickel salt and mantoquita total mass ratio are 1:0.001 ~ 1:0.004.
2. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 1 is stable, is characterized in that: the mass concentration scope of the ethylene glycol solution of described graphene oxide is 0.07g/mL ~ 7g/mL;
Described nickel salt is NiCl
26H
2o, mantoquita is CuCl
26H
2o, the amount of substance scope of nickel salt and mantoquita is 1mmol ~ 0.001mmol.
3. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 1 is stable, is characterized in that: described solvent is ethylene glycol; The concentration of described alkali lye is 2mol/L ~ 0.002mol/L.
4. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 1 is stable, is characterized in that: described washing is by deionized water and ethanol washed product respectively.
5. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 1 is stable, it is characterized in that the preparation concrete steps of described graphene oxide are: in natural flake graphite and sodium nitrate, add the concentrated sulfuric acid, be uniformly mixed in ice-water bath, add potassium permanganate while stirring, control temperature continues stirring reaction, then heat up stirring, after adding deionized water in batches, add hydrogen peroxide again, continue stirring reaction, after suction filtration, washing, centrifugation, drying obtains graphene oxide while hot.
6. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 5 is stable, is characterized in that the mass ratio of described natural flake graphite and sodium nitrate is 1:1 ~ 3:1; The mass ratio of described natural flake graphite and the concentrated sulfuric acid is 1:40 ~ 1:50; The mass ratio of described natural flake graphite and potassium permanganate is 1:2 ~ 1:5; The mass ratio of described natural flake graphite and hydrogen peroxide is 1:5 ~ 1:10.
7. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 5 is stable, is characterized in that: described control temperature is <10 DEG C, continues stirring 1 ~ 3h;
The described temperature stirred that heats up is 35 DEG C, and mixing time is 2 ~ 3h;
The mass ratio of described natural flake graphite and deionized water is 1:10 ~ 1:50.
8. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 5 is stable, continues stirring reaction 1 ~ 3h described in it is characterized in that after adding hydrogen peroxide.
9. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 5 is stable, is characterized in that: described washing carries out centrifuge washing by the salt solution of 100mL5% and the deionized water of 50 DEG C successively, is 7 to filtrate pH value.
10. the simple method for preparing of the super-small copper nickel nano-complex that Graphene according to claim 5 is stable, it is characterized in that: described drying is dry 10h in 60 DEG C of vacuum drying chambers.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
-
2015
- 2015-10-28 CN CN201510709251.1A patent/CN105328205A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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