CN106670499A - Environment-friendly preparing method of nanometer copper with ascorbic acid and Arabic gum serving as reducing agent and protective agent - Google Patents
Environment-friendly preparing method of nanometer copper with ascorbic acid and Arabic gum serving as reducing agent and protective agent Download PDFInfo
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- CN106670499A CN106670499A CN201611156626.7A CN201611156626A CN106670499A CN 106670499 A CN106670499 A CN 106670499A CN 201611156626 A CN201611156626 A CN 201611156626A CN 106670499 A CN106670499 A CN 106670499A
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- arabic gum
- copper
- ascorbic acid
- nanometer copper
- nanometer
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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
Abstract
The invention relates to a preparing method of nanometer copper particles, in particular to an environment-friendly preparing method of nanometer copper with ascorbic acid and Arabic gum serving as a reducing agent and a protective agent. The method specifically comprises the steps that the Arabic gum and copper sulfate pentahydrate are prepared into an Arabic gum solution and a copper sulfate solution and mixed uniformly to obtain an Arabic gum-copper sulfate mixed solution; under the stirring effect, an ascorbic acid solution is dropped into the Arabic gum-copper sulfate mixed solution to react to obtain wine red nanometer copper sol; and finally black nanometer copper particles are obtained through the centrifuging, washing and vacuum drying manners. The particle size of the nanometer copper particles ranges from 100 nm to 200 nm, the average particle size is 160 nm, and in the ultraviolet-visible light spectrum, the characteristic absorption peak is located on the portion of 582.5 nm. The preparing method has the beneficial effects that preparation is efficient and fast, other auxiliary means is not needed, resource utilization is efficient, waste is reduced, the technology is simple, the cost is low, the method is environmentally friendly, and the application prospect is wide.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer copper particle, and in particular to a kind of to be made with ascorbic acid and arabic gum
For reducing agent and the Pallution-free preparation method of protectant Nanometer Copper.
Background technology
As a kind of emerging functional material, the physics and chemical property of the uniqueness that nano metal particles have so as to can
To be applied to optical material, catalyst material, anti-biotic material, biosensor material, coating, battery electrode material, antistatic
Material, low temperature superconducting material, also have a wide range of applications in fields such as information Store, photonic propulsion, induction apparatuss, imagings [Zhu Shidong,
Xu Ziqiang, Bai Zhenquan etc. domestic and international progress II of nano material --- applications to nanostructures and preparation method [J]. heat
Treatment technology and equipment, 2010,31 (4): 1-8].High-specific surface area and height that Nanometer Copper has nano material total because of which
Surface activity, can be used as catalyst, reduce chemical reaction temperature, improve reaction rate；According to the spy that its particle diameter is little, electric conductivity is high
Point, the electrocondution slurry that can be prepared by Nanometer Copper as the conductive particle in 3D printing conductive ink not only conductivity compared with
Height, and the usage amount of copper powder can be reduced；The good antibacterial characteristics that Nanometer Copper has make which be expected to become good antibacterial material
Material；In addition, Nanometer Copper applies also for pharmaceuticals industry and cosmetic industry etc..Therefore, the preparation of nanometer copper particle and application is ground
Study carefully with very big real value.And the application of Nanometer Copper depends greatly on size, pattern and the structure of particle.Its
In, it is significant to preparing the research of nanometer copper particle technology of pattern and size tunable.
The preparation method of Nanometer Copper has three kinds of vapor phase method, liquid phase method and solid phase method etc..Wherein, liquid phase method is current laboratory
With the industrial widely used method for preparing Nanometer Copper.Its process is mainly made into molten from one or more water solublity mantoquita
After liquid, from suitable precipitant or the operation such as be hydrolyzed, reduce, metal nanoparticle is crystallized or is precipitated out, finally
Drying and dewatering obtains product.During these, it usually needs enter in heating, under the conditions of adding protective gas or long-time reaction etc.
OK, it is impossible to meet efficient, resource-effective requirement.In recent years, being increasingly incremented by environmental protection consciousness with people, advocates ring
Guarantor becomes one of developing goal of following all trades and professions.For chemical industry, materials industry, should more fulfil what is should use up in terms of environmental protection
Obligation, therefore, raising efficiency, reduction pollution, reduction energy resource consumption become theme.At present, although for nanometer copper particle
Environment-friendly preparation method thereof has considerable research, and used in experiment now and production, more reducing agent has ascorbic acid and Fructus Vitis viniferae
Sugar, protective agent then have numerous selections.Emphasis of its research is then presoma, reducing agent, protectant with when experiment condition pair
The impact of the particle diameter of product, particle diameter distribution, surface topography and performance etc., but excessively it is not related to output speed, if need
Carry out heating, being passed through under the anti-oxidation of protective gas or other subsidiary conditions, so as to extensive life cannot be advantageously applied to
In product, while also result in the waste of human and material resources.
The present invention with copper sulphate pentahydrate as copper source, with ascorbic acid as reducing agent, arabic gum is protective agent, room temperature,
In the environment of protective gas need not being passed through, particle diameter has been prepared in the nanometer copper particle that 100~200 nm, mean diameter are 160 nm
Son, can meet green, efficiently, the design requirement that economizes on resources.
The content of the invention
It is an object of the invention to overcome the shortcomings of that prior art is present, propose one kind and made with ascorbic acid and arabic gum
For reducing agent and the Pallution-free preparation method of protectant Nanometer Copper.
With ascorbic acid as reducing agent, arabic gum is prepared one kind proposed by the present invention for protectant Nanometer Copper greenization
Method, is arabic gum and copper sulphate pentahydrate to be distinguished wiring solution-forming and is mixed first, obtains arabic gum-copper sulfate mixing molten
Liquid；Under stirring ascorbic acid solution is added drop-wise in arabic gum-copper sulfate mixed solution and is reacted, obtain claret-red
Color colloidal sol；Again by modes such as centrifugation, washing and vacuum drying, black nano copper particle, i.e. final product are obtained.By high score
Distinguish that transmission electron microscope determines its size between 100~200 nm, and detect at 582.5 nm in UV-Vis spectra
Absworption peak, it was confirmed that the presence of Nanometer Copper colloidal sol, and the composition of Nanometer Copper is determined using X-ray diffraction.
It is proposed by the present invention a kind of using ascorbic acid and arabic gum as reducing agent and the green of protectant Nanometer Copper
Change preparation method, comprise the following steps that：
（1）Weigh 0.1~1 g arabic gums to be added in 15~150 mL deionized waters, dissolve which under magnetic stirring, match somebody with somebody
Into gumwater；
（2）Weigh 0.05~0.5 g copper sulfate pentahydrates to be added in 5~50 mL deionized waters, make which molten under magnetic stirring
Solution, is made into copper-bath；
（3）By step（2）The copper-bath for obtaining is poured into containing step（1）In the flask of the gumwater for obtaining,
40~60 DEG C are warming up to, 10~60 min of magnetic agitation makes the two mix homogeneously, obtains arabic gum-copper sulfate mixed solution；
（4）0.1~1 g ascorbic acid is measured, and adds 10~100 mL deionized waters mass concentration to be configured to for 0.01~0.5
The ascorbic acid solution of g/mL；
（5）Under magnetic stirring, by step（4）The ascorbic acid solution for obtaining is added drop-wise to step（3）Arabic gum-the sulfur for obtaining
In sour copper mixed solution, 40~60 DEG C are warming up to, 1~2 h is reacted under continuing magnetic force stirring, the Nanometer Copper in claret is obtained
Colloidal sol；
（6）By step（5）Obtained Nanometer Copper colloidal sol high speed centrifuge is centrifuged 15 under 5000~10000 r/min rotating speeds~
30 min, precipitate organic solvent washing 3~5 times are centrifuged 3~8 min under 2000~3000 r/min rotating speeds, and vacuum is done
6~24 h are dried in dry case, the nanometer copper particle of black is obtained.
In the present invention, step（6）Described in organic solvent using in methanol, ethanol or acetone any one.
In the present invention, the Nanometer Copper size of gained between 100~200 nm, and in UV-Vis spectra
Absworption peak is detected at 582.5 nm.
The composition principle of nanometer copper particle of the present invention is as follows：
CuSO4·5H2O→Cu2++SO4 2-+5H2O
Cu2++ C6H8O6 → Cu+3H2+6CO+2H+（Arabic gum is protective agent）
In the present invention, the chemical formula of ascorbic acid is：C6H8O6；The chemical formula of copper sulphate pentahydrate is：CuSO4·5H2O；It is Arabic
Glue is a kind of carbohydrate polymer, is the mixture being polymerized by many kinds of substance, few including arabogalactan
Sugar, polysaccharide and protein sugar etc..
The beneficial effects of the present invention is：1. the present invention is a kind of green by protectant nanometer copper particle of arabic gum
Change preparation method, can relatively rapid prepare nanometer copper particle of the particle diameter in 100~200 nm；2. in the preparation process, nothing
Need to except stirring in addition to other supplementary meanss, be such as passed through protective gas antioxidation, heating etc., efficiently make use of resource, reduce people
The waste of power material resources；3. synthesis technique of the present invention is simple, with low cost, and excludes without harmful gass, and application prospect is extensive.
Description of the drawings
Fig. 1 is the transmission electron microscope picture of the Nanometer Copper as reducing agent and obtained in protective agent with ascorbic acid and arabic gum.
Fig. 2 is that the ultraviolet-visible light of the Nanometer Copper as reducing agent and obtained in protective agent with ascorbic acid and arabic gum is inhaled
Receive collection of illustrative plates.
The X ray diffracting spectrum of Fig. 3 Nanometer Coppers as reducing agent and obtained in protective agent with ascorbic acid and arabic gum.
Specific embodiment
Such scheme is described further below in conjunction with specific embodiment.It should be understood that these embodiments are for illustrating
The present invention and be not limited to limit the scope of the present invention.The implementation condition adopted in embodiment can be done according to the condition of concrete producer
Further adjust, not marked implementation condition is usually the condition in normal experiment.
The present invention is described in detail with reference to embodiment, it will be appreciated that citing described herein is only to explain this
Invention, is not intended to limit the present invention.
Embodiment 1
0.3 g arabic gums are weighed, is added in 250 mL there-necked flasks, added 15 mL deionized waters, make under magnetic stirring
Its dissolving, is made into gumwater；
Weigh 0.05 g copper sulphate pentahydrate to be added in 50 mL beakers, add 5 mL deionized waters, make which molten under magnetic stirring
Solution, forms copper-bath；
The copper-bath for preparing is poured in the there-necked flask containing gumwater, 50 DEG C is warming up to, magnetic agitation 10
Min makes the two mix homogeneously, obtains arabic gum-copper sulfate mixed solution；
0.3 g ascorbic acid is weighed, is added in 50 mL beakers, and add 10 mL deionized waters mass concentration to be made into for 0.15
The ascorbic acid solution of g/mL；
Under magnetic agitation effect, ascorbic acid solution is dropped in arabic gum-copper sulfate mixed solution, 50 are warming up to
DEG C, magnetic agitation reacts 1 h, obtains the Nanometer Copper colloidal sol of claret；
Obtained Nanometer Copper colloidal sol high speed centrifuge is centrifuged into 15 min, precipitate dehydrated alcohol under 10000 r/min
Washing 3 times, is centrifuged 5 min under 3000 r/min, 12 h is dried in vacuum drying oven, obtain the nanometer copper particle of black.
Fig. 1 is the transmission electron microscope picture of the Nanometer Copper as reducing agent and obtained in protective agent with ascorbic acid and arabic gum,
Fig. 2 is the UV-Visible absorption collection of illustrative plates of the Nanometer Copper as reducing agent and obtained in protective agent with ascorbic acid and arabic gum, figure
3 with ascorbic acid and arabic gum the Nanometer Copper as reducing agent and obtained in protective agent X ray diffracting spectrum.The present embodiment is obtained
Nanometer Copper size be 100~200 nm, mean diameter be 160 nm, the characteristic absorption in UV-Vis spectra
Peak is 582.5 nm.
Embodiment 2：It is same as Example 1, but step（1）In the consumption of arabic gum be changed into 0.5 g, deionized water
It is changed into 150 mL.
Embodiment 3：It is same as Example 1, but step（2）In the consumption of copper sulphate pentahydrate be changed into 0.1 g, deionization
Water is changed into 20 mL.
Embodiment 4：It is same as Example 1, but step（4）In the consumption of ascorbic acid be changed into 0.6 g.
Embodiment 5：It is same as Example 1, but step（6）In centrifugation rate and time be changed into 8000 r/min respectively
With 10 min.
Embodiment 6：It is same as Example 1, but step（6）In precipitate be changed into first with absolute ethanol washing 2 times, then
With washing with acetone 2 times.
Above-described embodiment technology design only to illustrate the invention and feature, its object is to allow person skilled in the art
It is to will appreciate that present disclosure and implement according to this, can not be limited the scope of the invention with this.It is all according to the present invention
Equivalent transformation or modification that spirit is done, should all be included within the scope of the present invention.
Claims (3)
1. a kind of using ascorbic acid and arabic gum as reducing agent and the Pallution-free preparation method of protectant Nanometer Copper, which is special
Levy is to comprise the following steps that：
（1）Weigh 0.1~1 g arabic gums to be added in 15~150 mL deionized waters, dissolve which under magnetic stirring, match somebody with somebody
Into gumwater；
（2）Weigh 0.05~0.5 g copper sulfate pentahydrates to be added in 5~50 mL deionized waters, make which molten under magnetic stirring
Solution, is made into copper-bath；
（3）By step（2）The copper-bath for obtaining is poured into containing step（1）In the flask of the gumwater for obtaining,
40~60 DEG C are warming up to, 10~60 min of magnetic agitation makes the two mix homogeneously, obtains arabic gum-copper sulfate mixed solution；
（4）0.1~1 g ascorbic acid is measured, and adds 10~100 mL deionized waters mass concentration to be configured to for 0.01~0.5
The ascorbic acid solution of g/mL；
（5）Under magnetic stirring, by step（4）The ascorbic acid solution for obtaining is added drop-wise to step（3）Arabic gum-the sulfur for obtaining
In sour copper mixed solution, 40~60 DEG C are warming up to, 1~2 h is reacted under continuing magnetic force stirring, the Nanometer Copper in claret is obtained
Colloidal sol；
（6）By step（5）Obtained Nanometer Copper colloidal sol high speed centrifuge is centrifuged 15 under 5000~10000 r/min rotating speeds~
30 min, precipitate organic solvent washing 3~5 times are centrifuged 3~8 min under 2000~3000 r/min rotating speeds, and vacuum is done
6~24 h are dried in dry case, the nanometer copper particle of black is obtained.
2. according to claim 1 a kind of using ascorbic acid and arabic gum as reducing agent and protectant Nanometer Copper
Pallution-free preparation method, it is characterised in that step（6）Described in organic solvent using in methanol, ethanol or acetone any one.
3. according to claim 1 a kind of using ascorbic acid and arabic gum as reducing agent and protectant Nanometer Copper
Pallution-free preparation method, it is characterised in that the Nanometer Copper size of gained between 100~200 nm, and in ultraviolet-visible light
Absworption peak is detected at 582.5 nm in spectrum.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109807348A (en) * | 2019-03-01 | 2019-05-28 | 淮海工学院 | A kind of simple environment-friendly preparation method thereof of micro-nano silver |
| CN110102774A (en) * | 2019-05-14 | 2019-08-09 | 桂林理工大学 | A kind of environment-friendly preparation method thereof of the copper nano-particle based on citrus pectin and its application |
| CN111421143A (en) * | 2020-04-01 | 2020-07-17 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109807348A (en) * | 2019-03-01 | 2019-05-28 | 淮海工学院 | A kind of simple environment-friendly preparation method thereof of micro-nano silver |
| CN110102774A (en) * | 2019-05-14 | 2019-08-09 | 桂林理工大学 | A kind of environment-friendly preparation method thereof of the copper nano-particle based on citrus pectin and its application |
| CN110102774B (en) * | 2019-05-14 | 2022-05-31 | 桂林理工大学 | Green preparation method and application of copper nanoparticles based on citrus pectin |
| CN111421143A (en) * | 2020-04-01 | 2020-07-17 | 中国人民解放军陆军军医大学第一附属医院 | Preparation method of nano-copper particles for treating inflammatory diseases |
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