CN109822108A - A kind of nano copper particle preparation method of the surface with bayonet fittings - Google Patents
A kind of nano copper particle preparation method of the surface with bayonet fittings Download PDFInfo
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- CN109822108A CN109822108A CN201910257371.0A CN201910257371A CN109822108A CN 109822108 A CN109822108 A CN 109822108A CN 201910257371 A CN201910257371 A CN 201910257371A CN 109822108 A CN109822108 A CN 109822108A
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Abstract
Copper sulphate is reduced to nano copper particle of the surface with bayonet fittings using liquid phase reduction by a kind of nano copper particle preparation method of the surface with bayonet fittings.The performance of nanocatalyst depends greatly on the microstructures such as the size of nanoparticle size, growth morphology, improve the specific surface area of nano particle, increase its Active sites, bigger with the contact area of catalysant matter, the effect of catalytic action shows more significant.Nano copper particle surface prepared by the present invention has bayonet fittings, uneven, significantly increases the specific surface area of itself.Copper grain diameter prepared by the present invention is about 500nm, due to the introducing of surfactant in preparation process, so that it has preferable dispersibility.
Description
Technical field
The invention belongs to metal nano material preparation technical field, Nanometer Copper of specifically a kind of surface with bayonet fittings
The preparation method of grain.
Background technique
Nano metal material lubrication, ceramic toughening, absorbing material, catalysis, in terms of show excellent performance,
It has potential application, is the important directions of material, chemical research all the time.Wherein, nano copper particle and its nanometer
Composite metal powder obtains a degree of application with unique performance, at catalyst, combustion-supporting aspect.Prepared in recent years in relation to it,
The research of performance and application is at home and abroad widely paid close attention to.
For nano copper particle, preparation method has ball physical method (physical vaporous deposition, ball-milling method, ray spoke at present
Penetrate method etc.) and chemical method (chemical vapour deposition technique, chemical precipitation method, microemulsion method, sol-gel method, hydro-thermal method, electrolysis method,
Liquid phase reduction etc.).Patent CN101890507A discloses a kind of preparation method of Nanometer Copper, wherein using atoleine as molten
Agent and reducing agent, while surfactant is added and is heat-treated in atmosphere of inert gases.The method increase copper particles
Dispersibility, but experimentation is complicated, post-processing is difficult, is unfavorable for industrial production.Patent CN104550993A discloses one kind
The preparation method of dispersed nano copper particle prepares presoma basic copper carbonate with coprecipitation, after 500 DEG C of roastings
Directly and oxidation-reduction reaction occurs for ethyl alcohol, and this method also needs experience hot environment, and technique is more complex.Patent
CN107745133A discloses a kind of method for preparing Nanometer Copper by water-alcohol thermal method, and this method does not need to add toxic reduction
Agent, environmentally protective, but need to use water heating kettle hydro-thermal 6h~12h under the conditions of 160 DEG C~200 DEG C, reaction temperature is higher and the time
It is longer, it is longer for industrial production campaign, increase production cost.And liquid phase reduction is that metal salt is direct by reducing agent
It is reduced into nano particle, cost is relatively low for this method, is suitable for industrial production.And for well control nano copper particle stability,
Surfactant, aminated compounds or other surfaces dressing agent can be added during the preparation process with full in dispersibility, size and pattern
Foot production needs.For poplar etc. using copper sulphate as raw material, oleic acid is surfactant, and glucose and ascorbic acid are reducing agent, liquid phase
Reduction is prepared for the copper particle (J Mater Sci, the 18th phase in 2007) that partial size 30nm has oxidation resistance.Gu great Ming etc. is used
Sodium hypophosphite under certain condition by copper sulphate be reduced to partial size about 50nm nano copper particle (Harbin Institute of Technology's journal,
8th phase in 2003).Liu Zhijie etc. using formaldehyde as reducing agent be prepared for 200~400nm nano copper particle (chemistry be notified to, 1996
Year o. 11th).
To sum up, there are many kinds of the preparation methods of nano copper particle, liquid phase reduction is the emphasis of research.In nano material
Under the premise of composition determines, the performance of nano material depends greatly on the size of nanoparticle, growth shape
The microstructures such as looks.The nano copper particle that existing method is prepared at present is mostly spherical shape, and surface is smooth, and surface does not have complexity substantially
Appearance structure.And increase the specific surface area of nano material, the position of nano material is improved, is conducive to improve its catalysis work
With.Therefore, how simply and effectively the structure and size of nano material and pattern etc. to be controlled in the solution, prepares ratio
The biggish nano copper particle of surface area is one of the emphasis of research.
Summary of the invention
To improve the catalytic action of nano copper particle, increasing the specific surface area of nano copper particle, and then increase catalytic action
Point, the nano copper particle preparation method the invention proposes a kind of surface with bayonet fittings.
Detailed process of the invention is:
Step 1, the preparation of copper sulfate solution and cetyl trimethylammonium bromide ethanol solution；
When preparing copper sulfate solution, anhydrous cupric sulfate is weighed.100mL distillation is added in weighed anhydrous cupric sulfate
Water, dissolution obtain the copper sulfate solution that concentration is 0.1~0.25g/mL.
When preparing cetyl trimethylammonium bromide ethanol solution, cetyl trimethylammonium bromide is weighed.Weighed
100mL ethyl alcohol is added in cetyl trimethylammonium bromide, the cetyl that concentration is 0.02~0.05g/mL is obtained after dissolution
Trimethylammonium bromide ethanol solution.
Step 2, the preparation of nano copper particle of the surface with bayonet fittings.
Obtained copper sulfate solution is put into 70 DEG C of stirred in water bath, while the cetyl trimethyl bromination that will be obtained
Ammonium ethanol solution is added in the copper sulfate solution, obtains mixed liquor.Lasting stirring, and be added into the mixed liquor dense
Degree is 6mol/L sodium hydroxide solution, until the pH that the mixed liquor of sodium hydroxide solution is added is 9~11.Successively have to the addition
10~25mL hydrazine hydrate and 5~15mL ethyl alcohol are added in the mixed liquor of sodium hydroxide solution, and makes the hydrazine hydrate: ethyl alcohol=
1.67~2.0:1.Continue 0.5~2.5h of stirring；Copper sulfate solution, sodium hydroxide, hydrazine hydrate are reacted with ethyl alcohol generation, are formed
Granular solids.
10min is stood, the precipitation of solid material is made.Obtained solids is washed three times repeatedly；Consolidate to by washing
Body object is washed twice with ethyl alcohol, and room temperature is dried, and obtains nano copper particle of the surface with bayonet fittings.
The output capacity of the nano copper particle is 81.5~95.7%, and the percentage is mass percent；The nanometer
The specific surface area of copper particle is 42~51m2/g。
The calculation method of the output capacity of the nano copper particle is: (surface wait for the quality of the nano copper particle of bayonet fittings/
The content of copper in copper sulfate solution) × 100%.
The present invention uses liquid phase reduction, and copper sulphate is reduced to nano copper particle of the surface with bayonet fittings.
The performance of nanocatalyst depends greatly on the microcosmic knot such as the size of nanoparticle size, growth morphology
Structure improves the specific surface area of nano particle, increases its Active sites, bigger with the contact area of catalysant matter, urges
The effect of change effect shows more significant.The appearance structure of commercially available nano copper particle is shown in Fig. 1, and surface is more smooth, wherein partial size
It is about 11m for the commercially available copper specific grain surface product of 500nm2/g.On the one hand, the partial size of copper particle is smaller, and specific surface area is bigger, reason
It is higher by catalytic efficiency.But partial size too small simultaneously can increase the surface of nano copper particle, and activity increases, and then leads to copper
Particle is easy to reunite, is unfavorable for evenly dispersed during post-production.Therefore need taken into account when preparing nano copper particle partial size,
Balance between specific surface area and dispersibility is reducing copper grain diameter, improves its point while increasing copper specific grain surface product
Dissipate property.Nano copper particle surface prepared by the present invention has bayonet fittings, uneven, significantly increases the specific surface of itself
Product.Copper grain diameter prepared by the present invention is about 500nm, due to the introducing of surfactant in preparation process, so that it has
Preferable dispersibility.
In previous work, influence of the surfactant types to the partial size and pattern of product nano copper particle is had studied.
Wherein surfactant used has dodecyl sodium sulfate (SDS), polyvinylpyrrolidone (PVP), cetyl trimethyl bromine
Change ammonium (CTAB).It the results are shown in Table 1.As can be seen that CTAB is more advantageous to the dispersion of nano copper particle, while in terms of Product characteristics
Out, only in the reaction that CTAB is added, the nano copper particle surface of preparation has bayonet fittings, sees Fig. 1.This may be due to
Contain amino in CTAB, coordination can be generated with copper ion, induce the growth of copper crystal, ultimately generate thorn-like bulge-structure.
It can be seen that particle size is uniform, and single copper particle surface has intensively from the stereoscan photograph of the nano copper particle of preparation
Thorn-like bulge-structure, the copper particle smooth compared to surface, it is clear that this structure greatly improves copper granule surface area, warp
The specific surface area that characterization obtains copper particle prepared by the present invention is greater than 40m2/ g, much larger than the specific surface area of commercially available copper particle.
The feature of nano copper particle is prepared under the conditions of 1 differential responses of table
| Serial number | Kinds of surfactants | Product characteristics |
| 1 | SDS | Poor dispersion, low output, copper particle surface are smooth |
| 2 | PVP | Poor dispersion, copper particle surface are smooth |
| 3 | CTAB | It is scattered, copper particle surface bayonet fittings |
Compared with prior art, nano copper particle surface prepared by the present invention has bayonet fittings, greatly improves this
The specific surface area of copper particle is conducive to the raising of auto-catalytic activity.
The present invention and the comparison of prior art main difference are shown in Table 2.
The comparison of 2 technology main difference of table
| Project | The prior art | The present invention |
| Copper particle surface state | It is smooth | Bayonet fittings |
| Specific surface area | 11m2/g (commercially available copper particle) | Greater than 40m2/g |
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of commercially available nano copper particle.
Fig. 2 is the scanning electron microscope (SEM) photograph of nano copper particle of the surface with bayonet fittings prepared in previous work.
Fig. 3 is flow chart of the invention.
Specific embodiment
The present invention is a kind of preparation method of nano copper particle of the surface with bayonet fittings, is retouched in detail by 7 embodiments
State the technical solution.
The detailed process of the preparation is:
Step 1, the preparation of copper sulfate solution and cetyl trimethylammonium bromide ethanol solution:
Weigh anhydrous cupric sulfate.100mL distilled water is added in weighed anhydrous cupric sulfate, it is 0.1 that dissolution, which obtains concentration,
The copper sulfate solution of~0.25g/mL.
Weigh cetyl trimethylammonium bromide.100mL ethyl alcohol is added in weighed cetyl trimethylammonium bromide,
The cetyl trimethylammonium bromide ethanol solution that concentration is 0.02~0.05g/mL is obtained after dissolution.
Step 2, the preparation of nano copper particle of the surface with bayonet fittings.
Obtained copper sulfate solution is put into 70 DEG C of stirred in water bath, while the cetyl trimethyl bromination that will be obtained
Ammonium ethanol solution is added in the copper sulfate solution, obtains mixed liquor.Lasting stirring, and be added into the mixed liquor dense
Degree is 6mol/L sodium hydroxide solution, until the pH that the mixed liquor of sodium hydroxide solution is added is 9~11.Successively have to the addition
10~25mL hydrazine hydrate and 5~15mL ethyl alcohol are added in the mixed liquor of sodium hydroxide solution, and makes the hydrazine hydrate: ethyl alcohol=
1.67~2.0:1.Continue 0.5~2.5h of stirring；Copper sulfate solution, sodium hydroxide, hydrazine hydrate are reacted with ethyl alcohol generation, are formed
Granular solids.
10min is stood, the precipitation of solid material is made.Obtained solids is washed three times repeatedly；Consolidate to by washing
Body object ethyl alcohol is washed twice, and room temperature is dried, and obtains nano copper particle of the surface with bayonet fittings.
The preparation process of each embodiment is identical in the present invention.The difference is that the technological parameter of each embodiment.It is each to implement
The component of example is shown in Table 3.
Each embodiment component of table 3 and conditional parameter table
The yield of nano copper particle prepared by each embodiment, specific surface area are tested, test result is shown in Table 4.
Each embodiment test result of table 4
Test proves that it is quality percentage that the nano copper particle with bayonet fittings, which prepares yield greater than 80% percentage,
Than；Specific surface area is greater than 40m2/g。
The calculation method of the output capacity of the nano copper particle is: (surface wait for the quality of the nano copper particle of bayonet fittings/
The content of copper in copper sulfate solution) × 100%.
Claims (3)
1. a kind of nano copper particle preparation method of surface with bayonet fittings, which is characterized in that detailed process is:
Step 1, the preparation of copper sulfate solution and cetyl trimethylammonium bromide ethanol solution；
Step 2, the preparation of nano copper particle of the surface with bayonet fittings；
Obtained copper sulfate solution is put into 70 DEG C of stirred in water bath, while the cetyl trimethylammonium bromide second that will be obtained
Alcoholic solution is added in the copper sulfate solution, obtains mixed liquor；Lasting stirring, and concentration is added into the mixed liquor and is
6mol/L sodium hydroxide solution, until the pH that the mixed liquor of sodium hydroxide solution is added is 9~11；Successively there is hydrogen-oxygen to the addition
Change and 10~25mL hydrazine hydrate and 5~15mL ethyl alcohol are added in the mixed liquor of sodium solution, and makes the hydrazine hydrate: ethyl alcohol=1.67~
2.0:1；Continue 0.5~2.5h of stirring；Copper sulfate solution, sodium hydroxide, hydrazine hydrate are reacted with ethyl alcohol generation, form graininess
Solids；
10min is stood, the precipitation of solid material is made；Obtained solids is washed three times repeatedly；To the solids by washing
It is washed twice with ethyl alcohol, room temperature is dried, and nano copper particle of the surface with bayonet fittings is obtained.
2. nano copper particle preparation method of the surface as described in claim 1 with bayonet fittings, it is characterised in that:
When preparing copper sulfate solution, anhydrous cupric sulfate is weighed；100mL distilled water is added in weighed anhydrous cupric sulfate, it is molten
Solution obtains the copper sulfate solution that concentration is 0.1~0.25g/mL；
When preparing cetyl trimethylammonium bromide ethanol solution, cetyl trimethylammonium bromide is weighed；Weighed 16
100mL ethyl alcohol is added in alkyl trimethyl ammonium bromide, the cetyl front three that concentration is 0.02~0.05g/mL is obtained after dissolution
Base ammonium bromide ethanol solution.
3. nano copper particle preparation method of the surface as described in claim 1 with bayonet fittings, it is characterised in that: the Nanometer Copper
The yield of particle is 81.5~95.7%, and the percentage is mass percent；The specific surface area of the nano copper particle is 42
~51m2/g。
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147417A (en) * | 2001-11-02 | 2003-05-21 | Japan Science & Technology Corp | Nano-size metal particles and method for manufacturing the same |
| CN101104205A (en) * | 2006-07-10 | 2008-01-16 | 三星电机株式会社 | Method for manufacturing copper nano granule and copper nano granule produced thereby |
| CN102381725A (en) * | 2010-08-31 | 2012-03-21 | 合肥学院 | Preparation method of hollow pumpkin-shaped CuO nano-material |
| CN103555049A (en) * | 2013-10-24 | 2014-02-05 | 北京印刷学院 | Preparation method of nano-copper conductive ink capable of realizing mass production |
| CN106513696A (en) * | 2015-09-09 | 2017-03-22 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
-
2019
- 2019-04-01 CN CN201910257371.0A patent/CN109822108A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003147417A (en) * | 2001-11-02 | 2003-05-21 | Japan Science & Technology Corp | Nano-size metal particles and method for manufacturing the same |
| CN101104205A (en) * | 2006-07-10 | 2008-01-16 | 三星电机株式会社 | Method for manufacturing copper nano granule and copper nano granule produced thereby |
| CN102381725A (en) * | 2010-08-31 | 2012-03-21 | 合肥学院 | Preparation method of hollow pumpkin-shaped CuO nano-material |
| CN103555049A (en) * | 2013-10-24 | 2014-02-05 | 北京印刷学院 | Preparation method of nano-copper conductive ink capable of realizing mass production |
| CN106513696A (en) * | 2015-09-09 | 2017-03-22 | 广州千顺工业材料有限公司 | Micro-nano copper powder and preparation method thereof |
| CN107498068A (en) * | 2017-09-22 | 2017-12-22 | 大连理工大学 | A kind of preparation method of flower-like nanometer copper |
Non-Patent Citations (1)
| Title |
|---|
| 刘花蓉: ""单质铜颗粒的制备及其光催化性能研究"", 《广州化工》 * |
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