CN110355379A - A kind of difference draw ratio NANO CRYSTAL COPPER WIRE and its synthetic method - Google Patents
A kind of difference draw ratio NANO CRYSTAL COPPER WIRE and its synthetic method Download PDFInfo
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- CN110355379A CN110355379A CN201910702435.3A CN201910702435A CN110355379A CN 110355379 A CN110355379 A CN 110355379A CN 201910702435 A CN201910702435 A CN 201910702435A CN 110355379 A CN110355379 A CN 110355379A
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- crystal copper
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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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Abstract
The invention belongs to the technical field of nano material, a kind of different draw ratio NANO CRYSTAL COPPER WIREs and its synthetic method are referred specifically to；The present invention is first according to a certain ratio by CuSO4·5H2O solution and NaOH solution are added into round-bottomed flask, are stirred;A certain amount of directed agents methylamine is added into above-mentioned solution；Round-bottomed flask is put into 30oC water-bath, is stirred to react mixing after a certain period of time, then be warming up to reaction temperature；The hydrazine hydrate solution centainly matched is added dropwise to dropwise in above-mentioned solution by certain flow rate, stopping reaction being added dropwise, reaction product preservation is in ethanol solution by mixed solution after being filtered, washed.The NANO CRYSTAL COPPER WIRE that the draw ratio of this method preparation is 8-30:1.
Description
Technical field
The invention belongs to the technical field of nano material, a kind of different draw ratio NANO CRYSTAL COPPER WIREs and its synthesis side are referred specifically to
Method.
Background technique
Nano material refers to that at least one dimension in three-dimensional space is in the material of nanoscale (1 ~ 100 nm) size.Relatively
In the variation in macroscopic material, size also along with the change of property.Therefore, nano material has the physics of many specificity
Chemical property, such as: mechanics, optics, electricity and heat performance are completely different in block materials and former molecular microcosmic material
Performance.Be situated between in the nanometer system seen, people have been observed that several new effects, including skin effect, small-size effect,
Quantum size effect and macro quanta tunnel effect.Nano material size is smaller, and specific surface area is larger, material surface electronics
The otherness of distribution and the otherness of internal-external keep its prospect in terms of catalytic applications long-range.Therefore, to preparing Nanometer Copper
The research of line is more and more.Although having been achieved for certain achievement in the study on the synthesis of NANO CRYSTAL COPPER WIRE, still there are many
" bottleneck " hinders the development in the field.For example, the microstructure of NANO CRYSTAL COPPER WIRE can not be accurately controlled；Influence NANO CRYSTAL COPPER WIRE size
Key factor controllably constructed etc. lacks the theoretical research of directiveness.Therefore, the serial controllable structure of research NANO CRYSTAL COPPER WIRE size
Build with its catalytic performance structure-activity relationship, have great importance.
Since nano material is with a wide range of applications, the preparation method of nano material is domestic and international experts and scholars' research
Hot spot.Existing market requires production cost low the preparation of nano material, simple process, produces environmentally protective.
Summary of the invention
It is an object of the invention to overcome one of the technical problems existing in the prior art, and propose a kind of different draw ratios
NANO CRYSTAL COPPER WIRE and its synthetic method.
Present invention firstly provides a kind of different draw ratio NANO CRYSTAL COPPER WIREs, the draw ratio of the NANO CRYSTAL COPPER WIRE is 8-30:1.
The present invention also provides a kind of synthetic methods of different draw ratio Nanometer Coppers, include the following steps:
According to a certain ratio by CuSO4·5H2O solution and NaOH solution are added in reaction vessels, are stirred；
Wherein, the CuSO4·5H2The concentration of O solution and NaOH solution ratio is 1:20-1:40；The CuSO4·5H2O solution
Volume ratio with NaOH solution is 1:0.5-1:2.
In the mixed solution that a certain amount of directed agents are added；
Wherein, the CuSO4·5H2The molar ratio of O and directed agents are as follows: 1:60-1:80；The directed agents are methylamine.This
Directed agents in invention mainly induce the direction of growth of NANO CRYSTAL COPPER WIRE, control the size (draw ratio) of NANO CRYSTAL COPPER WIRE.Size is different
It will affect the catalytic activity of NANO CRYSTAL COPPER WIRE, the i.e. structure-activity relationship of size and catalytic activity accordingly.
Reflection vessel are put into water-bath, are stirred reaction after a certain period of time, then be warming up to reaction temperature；
Wherein, it is described by reflection vessel be put into water-bath when, bath temperature be 30 DEG C；The time that is stirred is 0.5-8
Hour；Reaction temperature is 60-80 DEG C.
Hydrazine hydrate solution is added dropwise to dropwise in above-mentioned reaction solution, stopping reaction being added dropwise, after being filtered, washed,
Reaction product preservation is in ethanol solution.
Wherein, the CuSO4·5H2The molar ratio of O and hydrazine hydrate is 1:15-1:35；The dropwise addition of the hydrazine hydrate solution
Speed are as follows: 10-30 mL/h.
Wherein, the centrifuge washing rate is 9000 revs/min.
Copper ion reduction is prepared into the small copper crystalline substance of partial size using being wet-chemical reduction method, first with reducing agent by the present invention
Grain, then carries out fusion growth under the action of methylamine directed agents, ultimately forms the NANO CRYSTAL COPPER WIRE of polycrystalline structure.
The invention has the benefit that
(1) this method carries out in aqueous solution, is not necessarily to organic solvent.
(2) this method experimental implementation is easy simple, and cost of material is low, and yield is high.
(3) NANO CRYSTAL COPPER WIRE that the draw ratio of this method preparation is 8:1-30:1, NANO CRYSTAL COPPER WIRE size is different, physics, chemistry
Property can be different, have dimensional effect, meet actual demand.
Detailed description of the invention:
Fig. 1 is that the SEM of 1 gained NANO CRYSTAL COPPER WIRE of embodiment schemes.
Fig. 2 is that the SEM of 2 gained NANO CRYSTAL COPPER WIRE of embodiment schemes.
Fig. 3 is that the SEM of 3 gained NANO CRYSTAL COPPER WIRE of embodiment schemes.
Specific embodiment
The following is an embodiment of the present invention, better understood when the present invention, but embodiments of the present invention are not limited thereto, together
When its shown data do not represent the limitation to feature of present invention range.
Embodiment 1:
(1) copper sulphate (CuSO of 1.87 g is weighed4•5H2O it) is dissolved in deionized water with the sodium hydroxide of 6 g (NaOH), respectively
It is configured to 0.15 moL L-1With 3 moL L-1Aqueous solution；
(2) copper sulphate and sodium hydroxide solution are separately added into 10 mL copper-baths, 5 mL hydrogen according to the volume ratio of 1:0.5
Sodium hydroxide solution is stirred into 100 mL round-bottomed flasks with 10 revs/min of speed, adds 17 mL methylamines according to the ratio
(concentration 25%-30%) solution is in wherein；
(4) round-bottomed flask is put into 30 DEG C of water-bath, after being stirred to react 0.5 hour, is warming up to 60 DEG C；
(5) the 0.45mol/L hydrazine hydrate solution of 50 mL is added dropwise in above-mentioned solution with 10 mL/ hours flow velocity, is dripped
Finish, stops reaction；
(6) reaction product is washed 10 times in the case where centrifugation rate is 9000 revs/min of rates with dehydrated alcohol, reaction product is protected
There are in dehydrated alcohol.
Product nano copper wire property is shown in attached drawing 1, table 1.
Fig. 1 is the SEM figure of the NANO CRYSTAL COPPER WIRE prepared under 1 experiment condition of embodiment.It is found from figure, in the embodiment condition
Under, the Nanometer Copper of preparation is made of NANO CRYSTAL COPPER WIRE and nano copper particle, and wherein NANO CRYSTAL COPPER WIRE and nano copper particle quantity ratio are 2:
1, wherein the draw ratio of NANO CRYSTAL COPPER WIRE is 30:1, and the average grain diameter of nano copper particle is 220 nm.
Embodiment 2:
(1) copper sulphate (CuSO of 1.87 g is weighed4•5H2O it) is dissolved in deionized water with the sodium hydroxide of 9 g (NaOH), respectively
It is configured to 0.15 moL L-1With 4.5 moL L-1Solution；
(2) copper sulphate and sodium hydroxide solution are separately added into 10 mL copper-baths, 10 mL hydrogen according to the volume ratio of 1:1
Sodium hydroxide solution is stirred into 100 mL round-bottomed flasks with 15 revs/min of speed, adds 19 mL methylamines according to the ratio
(concentration 25%-30%) solution is in wherein；
(4) round-bottomed flask is put into 30 DEG C of water-bath, after being stirred to react 2 hours, is warming up to 70 DEG C；
(5) the 0.75mol/L hydrazine hydrate solution of 50 mL is added dropwise in above-mentioned solution with 15 mL/ hours flow velocity, is dripped
Finish, stops reaction；
(6) reaction product is washed 10 times in the case where centrifugation rate is 9000 revs/min of rates with dehydrated alcohol, reaction product is protected
There are in dehydrated alcohol.
Product nano copper wire property is shown in attached drawing 2, table 1.
Fig. 2 is the SEM figure of the NANO CRYSTAL COPPER WIRE prepared under 2 experiment condition of embodiment.Comparative example 1, in the embodiment item
Under part, the pattern of the Nanometer Copper of preparation is mainly threadiness, and only a small amount of spheric granules shows that concentration proportioning has weight to granule-morphology
It influences, wherein the draw ratio of NANO CRYSTAL COPPER WIRE is 25:1, and the average grain diameter of nano copper particle is 170 nm.
Embodiment 3:
(1) copper sulphate (CuSO of 1.87 g is weighed4•5H2O it) is dissolved in deionized water with the sodium hydroxide of 12 g (NaOH), point
It is not configured to 0.15 moL L-1With 6 moL L-1Solution；
(2) copper sulphate and sodium hydroxide solution are separately added into 10 mL copper-baths, 20mL hydrogen-oxygen according to the volume ratio of 1:2
Change sodium solution into 100 mL round-bottomed flasks, is stirred with 20 revs/min of speed, adds 22 mL methylamines according to the ratio
(concentration 25%-30%) solution is in wherein；
(4) round-bottomed flask is put into 30 DEG C of water-bath, after being stirred to react 8 hours, is warming up to 80 DEG C；
(5) the 1.05mol/L hydrazine hydrate solution of 50 mL is added dropwise in above-mentioned solution with 30 mL/ hours flow velocity, is dripped
Finish, stops reaction；
(6) reaction product is washed 10 times in the case where centrifugation rate is 9000 revs/min of rates with dehydrated alcohol, reaction product is protected
There are in dehydrated alcohol.
Product nano copper wire property is shown in attached drawing 3, table 1.
Fig. 3 is the SEM figure of the NANO CRYSTAL COPPER WIRE prepared under 3 experiment condition of embodiment.Comparative example 1,2, in the embodiment
Under the conditions of, linear Nanometer Copper is made of spheric granules, and wherein the draw ratio of NANO CRYSTAL COPPER WIRE is 8:1, the average grain of nano copper particle
Diameter is 150 nm.
Meanwhile by table 1 it can also be seen that the concentration of methylamine has a major impact the size of nano copper particle, pattern, first
Concentration must control within limits amine in the solution, otherwise can not prepare expected copper wire.
Embodiment 4:
The NANO CRYSTAL COPPER WIRE prepared when 0.28g reacts 2h using methylamine as directed agents is weighed respectively and ball shaped nano copper particle is distinguished
It is added in paint (conventional commercial, color are unlimited), is mixed and uniformly paves, after naturally dry 6h, surveyed with four probe of RTS-8 type
Trying its sheet resistance that instrument is surveyed is respectively 1463.2 K Ω/ and 1980.2 K Ω/, the results showed that is improved in the presence of NANO CRYSTAL COPPER WIRE
The electric conductivity of copper.Meanwhile dispersing the NANO CRYSTAL COPPER WIRE of the different draw ratios of preparation in paint, analysis is found after tested,
With the increase of draw ratio of NANO CRYSTAL COPPER WIRE, its electric conductivity is also improved therewith.When selection 30% (refers here to addition
NANO CRYSTAL COPPER WIRE NANO CRYSTAL COPPER WIRE and paint mixed solution quality accounting) draw ratio be 30:1 NANO CRYSTAL COPPER WIRE carry out test point
When analysis, sheet resistance is only 350K Ω/.
The size of the nanometer copper sample prepared under 1. different condition of table
Claims (9)
1. a kind of NANO CRYSTAL COPPER WIRE of difference draw ratio, which is characterized in that the draw ratio of the NANO CRYSTAL COPPER WIRE is 8-30:1.
2. a kind of synthetic method of difference draw ratio NANO CRYSTAL COPPER WIRE, which comprises the steps of:
According to a certain ratio by CuSO4·5H2O solution and NaOH solution are added in reaction vessels, are stirred；
In the mixed solution that a certain amount of directed agents methylamine is added；
Reflection vessel are put into water-bath, are stirred reaction after a certain period of time, then be warming up to reaction temperature；
Hydrazine hydrate solution is added dropwise to dropwise in above-mentioned reaction solution, stopping reaction being added dropwise, it, will be anti-after being filtered, washed
Product preservation is answered to be in ethanol solution.
3. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that the CuSO4·5H2O
The concentration of solution and NaOH solution ratio is 1:20-1:40.
4. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that the CuSO4·5H2O
The volume ratio of solution and NaOH solution is 1:0.5-1:2.
5. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that the CuSO4·
5H2The molar ratio of O and directed agents are as follows: 1:60-1:80.
6. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that described by reactor
When ware is put into water-bath, bath temperature is 30 DEG C.
7. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that described is stirred
Time is 0.5-8 hour；Reaction temperature is 60-80 DEG C.
8. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, which is characterized in that the CuSO4·
5H2The molar ratio of O and hydrazine hydrate is 1:15-1:35.
9. a kind of preparation method for preparing NANO CRYSTAL COPPER WIRE according to claim 1, it is characterised in that the hydrazine hydrate solution
Rate of addition are as follows: 10-30 mL/h.
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Application publication date: 20191022 |