CN113102765A - Copper nano-sphere particle and preparation method and application thereof - Google Patents

Copper nano-sphere particle and preparation method and application thereof Download PDF

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CN113102765A
CN113102765A CN202110369153.3A CN202110369153A CN113102765A CN 113102765 A CN113102765 A CN 113102765A CN 202110369153 A CN202110369153 A CN 202110369153A CN 113102765 A CN113102765 A CN 113102765A
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copper
metal salt
mixed solution
copper metal
salt solution
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CN113102765B (en
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胡超权
宋洋
李琳
马猛
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Nanjing Zhongkegetekang Technology Co ltd
Zhongke Nanjing Green Manufacturing Industry Innovation Research Institute
Institute of Process Engineering of CAS
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Nanjing Zhongkegetekang Technology Co ltd
Nanjing Green Manufacturing Industry Innovation Research Institute of Process Engineering of CAS
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Abstract

The invention provides a copper nano-sphere particle and a preparation method and application thereof. The preparation method comprises the following steps: (1) mixing a copper metal salt solution and a blocking agent for the first time to obtain a first mixed solution; (2) and (2) mixing the first mixed solution in the step (1) with a reducing agent for the second time to obtain a second mixed solution, and then carrying out a solvothermal reaction on the second mixed solution to obtain the copper nanosphere particles. The preparation method disclosed by the invention adopts nontoxic alcohols as solvents, is safe, environment-friendly and economical, is simple to operate and easy to control, is an environment-friendly and simple-to-operate preparation method, and the prepared copper nanosphere particles have a high specific surface area and more active sites.

Description

Copper nano-sphere particle and preparation method and application thereof
Technical Field
The invention belongs to the technical field of nano materials, and relates to a copper nanosphere particle as well as a preparation method and application thereof.
Background
Catalysis is the technology of the support of medicine, health, food production and engine fuel at present, and is the cornerstone of modern chemical industry. In the catalytic reaction, the selection of the catalyst is particularly critical. With the continuous development of nanotechnology, researchers find that nano metal particles exhibit higher catalytic performance due to larger specific surface area and higher active sites. At present, the common nano metal catalyst is a noble metal material such as Au, Pt and the like, but the cost consumption is high due to the problems of catalyst loss and the like in the catalysis process.
In order to solve the problem, researchers propose that Cu is used as a raw material to prepare a metal nano material, and the material can obviously reduce the cost and has a wide application prospect. So far, the main methods for preparing metal nanospheres at home and abroad are high-temperature heating, electrolytic method and reduction method. However, the heating method has complex process, the product is easy to oxidize in the air and even explode, and the electrolysis method is difficult to master and is not suitable for large-scale production.
CN102941350A discloses a method for synthesizing nano copper powder. Specifically, the copper compound is subjected to thermal decomposition reaction in an organic solvent at a high temperature to prepare the nano copper powder. The specific method comprises the following steps: 1) weighing a copper compound, and dissolving the copper compound in an organic solvent to prepare a copper solution; the copper compound is copper sulfate, copper nitrate, copper acetate, copper chloride, copper acetylacetonate or copper oleate; the mass ratio of the copper compound to the organic solvent is 1: (2-60); the organic solvent is one or more of octadecene, hexadecene, oleylamine or oleic acid; 2) stirring, heating and reacting the copper solution prepared in the step 1) in an inert gas environment; wherein the heating reaction temperature is 240-350 ℃; the reaction time is 10-80 minutes; 3) cooling the solution obtained after the reaction in the step 2), adding a cleaning agent for washing and centrifuging, pouring out the upper layer liquid, and putting the upper layer liquid into an oven for drying to obtain the nano copper powder. However, the heating method provided by the document has a complex process, the product is easily oxidized in the air and even explodes, and the safety cannot be guaranteed.
CN111705338A discloses a method for preparing nano-copper powder, which comprises the following steps: the method comprises the steps of preparing the red purple nano-copper powder, wherein an electrolyte used for preparing the nano-copper powder is a mixed solution of copper sulfate, sodium citrate and sodium phosphate, a working electrode is a waste and recovered copper material, a platinum net is a counter electrode, deoxidizing the electrolyte, applying constant current to the working electrode by using a constant current power supply, taking down the platinum net after enough copper powder is deposited on the platinum net, sealing the platinum net in absolute ethyl alcohol for ultrasonic cleaning, and then carrying out suction filtration and drying to obtain the red purple nano-copper powder with the average particle size of 30-85 nm. The electrolytic method provided by the document is used for preparing the nano copper, and large-scale production is difficult to realize.
The reduction method is the most commonly used method in industry at present, but the reducing agent has the problems of possible toxicity, long reaction time and the like.
Therefore, how to find a simple, efficient, safe and nontoxic method for preparing copper nanoparticle with high specific surface area and more active sites is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a copper nano-sphere particle, a preparation method and application thereof. The preparation method disclosed by the invention adopts nontoxic alcohols as solvents, is safe, environment-friendly and economical, is simple to operate and easy to control, is an environment-friendly and simple-to-operate preparation method, and the prepared copper nanosphere particles have a high specific surface area and more active sites.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing copper nanoparticle, comprising the steps of:
(1) mixing a copper metal salt solution and a blocking agent for the first time to obtain a first mixed solution;
(2) and (2) mixing the first mixed solution in the step (1) with a reducing agent for the second time to obtain a second mixed solution, and then carrying out a solvothermal reaction on the second mixed solution to obtain the copper nanosphere particles.
By adopting the preparation method provided by the invention, the copper metal salt solution and the end capping reagent are mixed, the shape of the nanocrystalline is designed and controlled by utilizing the end capping reagent, the nano morphology is controlled by adjusting the reaction conditions, and then the reducing agent is added to reduce the copper metal salt into the metal copper, so that the copper nanoparticle with larger specific surface area and more active sites can be finally obtained. Meanwhile, the preparation method provided by the invention is simple to operate, easy to control, environment-friendly and suitable for large-scale production.
Preferably, the molar ratio of the copper metal salt to the capping agent in the copper metal salt solution in the step (1) is 10:1 to 1:1, for example, 10:1, 9:1, 8:1, 7:1, 6:1, 5:1, 4:1, 2:1 or 1:1, and the like, and is preferably 10:1 to 4: 1.
According to the invention, the molar ratio of the copper salt to the end-capping reagent cannot be too large or too small, the metal ball reaches the micron level when the molar ratio is too large or too small, and the particles of the copper nano-ball particles are more uniform when the molar ratio is 10: 1-4: 1.
Preferably, the molar concentration of the copper metal salt solution in step (1) is 2-10 mmol/l, such as 2mmol/l, 3mmol/l, 4mmol/l, 5mmol/l, 6mmol/l, 7mmol/l, 8mmol/l, 9mmol/l or 10 mmol/l.
Preferably, the copper metal salt in the copper metal salt solution in step (1) comprises any one of copper acetylacetonate, copper sulfate or copper chloride or a combination of at least two of the above.
Preferably, the solvent in the copper metal salt solution of step (1) comprises any one of methanol, ethanol, ethylene glycol or glycerol or a combination of at least two thereof.
In the invention, the used solvent is nontoxic, safe, environment-friendly and economical.
Preferably, the blocking agent comprises any one of polyvinylpyrrolidone, oleylamine or poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) or a combination of at least two thereof.
Preferably, the method of mixing in step (1) comprises sonication and/or stirring.
Preferably, the time for the first mixing in step (1) is 10-30 min, such as 10min, 15min, 20min, 25min or 30 min.
Preferably, the molar ratio of the reducing agent in the step (2) to the copper metal salt in the copper metal salt solution in the step (1) is 5:1 to 50:1, for example, 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1, and the like, and is preferably 15:1 to 50: 1.
In the present invention, too large a molar ratio of the reducing agent to the copper salt results in the accumulation of metal spheres, and too small a molar ratio results in the incomplete reduction of the copper salt to metallic copper.
Preferably, the reducing agent in step (2) comprises any one or a combination of at least two of oxalic acid, sodium citrate or acrylic acid.
Preferably, the mixing method of step (2) comprises ultrasound and/or stirring.
Preferably, the time for the secondary mixing in the step (2) is 10-30 min, such as 10min, 15min, 20min, 25min or 30 min.
Preferably, the temperature of the solvothermal reaction in step (2) is 100 to 220 ℃, such as 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, preferably 140 to 220 ℃.
In the present invention, too high a solvothermal reaction temperature leads to deactivation of the reaction, and too low a solvothermal reaction temperature leads to incomplete reaction.
Preferably, the solvothermal reaction time in the step (2) is 5-25 h, such as 5h, 6h, 8h, 10h, 12h, 14h, 15h, 16h, 18h, 20h, 22h, 24h or 25h, and the like, and preferably 6-12 h.
Preferably, after the solvothermal reaction in the step (2) is finished, the washing, centrifuging and drying operations are carried out sequentially.
Preferably, the rotation speed of the centrifugation is 2000-8000 rpm/min, such as 2000rpm/min, 3000rpm/min, 4000rpm/min, 5000rpm/min, 6000rpm/min, 7000rpm/min or 8000rpm/min, etc., preferably 2000-4000 rpm/min.
Preferably, the drying temperature is 40-80 ℃, such as 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, preferably 50-60 ℃.
Preferably, the drying time is 4-16 h, such as 4h, 5h, 6h, 8h, 10h, 12h, 14h, 15h or 16h, and preferably 6-12 h.
As a preferred technical scheme, the preparation method of the copper nano-sphere particles comprises the following steps:
(1) carrying out ultrasonic treatment on a copper metal salt solution with the molar concentration of 2-10 mmol/l and a capping agent for 10-30 min, wherein the molar ratio of the copper metal salt in the copper metal salt solution to the capping agent is 10: 1-4: 1, so as to obtain a first mixed solution;
(2) carrying out ultrasonic treatment on the mixed solution obtained in the step (1) and a reducing agent for 10-30 min, wherein the molar ratio of the reducing agent to the copper metal salt in the copper metal salt solution obtained in the step (1) is 15: 1-50: 1 to obtain a second mixed solution, carrying out solvothermal reaction on the second mixed solution at 140-220 ℃ for 6-12 h, washing, centrifuging at the rotating speed of 2000-4000 rpm/min, and finally drying at 50-60 ℃ for 6-12 h to obtain copper nanosphere particles;
wherein, the copper metal salt in the copper metal salt solution in the step (1) comprises any one or the combination of at least two of copper acetylacetonate, copper sulfate or copper chloride;
the solvent in the copper metal salt solution in the step (1) comprises any one or the combination of at least two of methanol, ethanol, glycol or glycerol; the blocking agent comprises any one or a combination of at least two of polyvinylpyrrolidone, oleylamine or poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol); the reducing agent in the step (2) comprises any one or the combination of at least two of oxalic acid, sodium citrate or acrylic acid.
In a second aspect, the present invention also provides a copper nanosphere particle prepared by the method for preparing the copper nanosphere particle of the first aspect.
Preferably, the diameter of the copper nanoparticle is 50 to 900nm, such as 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm, 900nm, or the like.
In a third aspect, the present invention also provides a use of the copper nanosphere particle of the second aspect for catalytic reaction.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method provided by the invention can obtain spherical copper metal particles, the copper nanosphere particles have higher specific surface area and more active sites, the diameter range is within 900nm, the molar ratio and the temperature are further adjusted, the diameter of the copper nanosphere particles is smaller and can reach 300nm, and the specific surface area is 4.7m2And/g and above, and the nontoxic alcohol is adopted as the solvent, so that the preparation method is safe, environment-friendly, economic, simple to operate and easy to control, and is an environment-friendly preparation method with simple operation.
Drawings
Figure 1 TEM electron micrograph of copper nanosphere particles provided in example 3.
Figure 2 TEM electron micrograph of copper nanosphere particles provided in example 4.
Figure 3 TEM electron micrograph of copper nanosphere particles provided in example 5.
Fig. 4 TEM electron micrograph of copper nanoplates provided in comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a copper nanoparticle.
The preparation method of the copper nano-sphere particles comprises the following steps:
(1) placing 0.12mmol copper chloride, 0.02mmol polyvinylpyrrolidone and 20ml ethylene glycol solution in a 50ml beaker for mixing, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a first mixed solution;
(2) adding 0.324g (3.6mmol) of oxalic acid into the first mixed solution in the step (1), sealing a beaker, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a second mixed solution
(3) Putting the second mixed solution into a stainless steel reaction kettle for sealing, and then putting the stainless steel reaction kettle into a high-temperature oven for carrying out solvothermal reaction for 12 hours at the temperature of 140 ℃;
(4) and (3) after the reaction in the step (3) is finished, washing the resultant with an ethylene glycol solution, centrifuging the resultant in a centrifuge at the rotating speed of 4000rpm/min for 10min after the washing is finished, pouring out a supernatant after the centrifugation, repeating the centrifuging operation for 3 times, and then drying the centrifuged solid matter at 40 ℃ for 4h to obtain the copper nanosphere particles.
Example 2
The present embodiment provides a copper nanoparticle.
The preparation method of the copper nano-sphere particles comprises the following steps:
(1) placing 0.12mmol copper chloride, 0.012mmol oleylamine and 20ml ethanol solution in a 50ml beaker for mixing, and stirring for 30min until complete dissolution to obtain a first mixed solution;
(2) adding 0.54g (6mmol) of oxalic acid into the first mixed solution in the step (1), sealing a beaker, and stirring for 30min until complete dissolution to obtain a second mixed solution;
(3) putting the second mixed solution into a stainless steel reaction kettle for sealing, and then putting the stainless steel reaction kettle into a high-temperature oven for carrying out solvothermal reaction for 6 hours at 220 ℃;
(4) and (3) after the reaction in the step (3) is finished, washing the product by using an ethylene glycol solution, centrifuging the product in a centrifuge at the rotating speed of 3000rpm/min for 10min after the washing is finished, pouring out a supernatant after the centrifugation, repeating the centrifugation for 3 times, and then drying the centrifuged solid matter at 60 ℃ for 6h to obtain the copper nanosphere particles.
Example 3
The present embodiment provides a copper nanoparticle.
The preparation method of the copper nano-sphere particles comprises the following steps:
(1) placing 0.12mmol of copper chloride, 0.03mmol of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 20ml of glycerol solution into a 50ml beaker for mixing, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a first mixed solution;
(2) adding 0.162g (1.8mmol) of oxalic acid into the first mixed solution in the step (1), sealing a beaker, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a second mixed solution;
(3) putting the second mixed solution into a stainless steel reaction kettle for sealing, and then putting the stainless steel reaction kettle into a high-temperature oven for carrying out solvothermal reaction for 10 hours at the temperature of 170 ℃;
(4) and (3) after the reaction in the step (3) is finished, washing the resultant with a glycerol solution, centrifuging the resultant in a centrifuge at the rotating speed of 4000rpm/min for 10min after the washing is finished, pouring out a supernatant after the centrifugation, repeating the centrifugation for 3 times, and drying the centrifuged solid matter at 40 ℃ for 4h to obtain the copper nanosphere particles.
As can be seen from fig. 1, copper nanoparticle particles having a high degree of dispersion and a diameter ranging around 100nm were formed in example 3.
Example 4
The present embodiment provides a copper nanoparticle.
The preparation method of the copper nano-sphere particles comprises the following steps:
(1) putting 0.12mmol of copper sulfate, 0.12mmol of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 20ml of glycol solution into a 50ml beaker for mixing, and carrying out ultrasonic treatment for 10min until complete dissolution to obtain a first mixed solution;
(2) adding 0.054g (0.6mmol) of oxalic acid into the first mixed solution in the step (1), sealing a beaker, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a second mixed solution;
(3) putting the second mixed solution into a stainless steel reaction kettle for sealing, and then putting the stainless steel reaction kettle into a high-temperature oven for carrying out solvothermal reaction for 25 hours at the temperature of 100 ℃;
(4) and (3) after the reaction in the step (3) is finished, washing the resultant with an ethylene glycol solution, centrifuging the resultant in a centrifuge at the rotating speed of 4000rpm/min for 10min after the washing is finished, pouring out a supernatant after the centrifugation, repeating the centrifuging operation for 3 times, and then drying the centrifuged solid matter at 80 ℃ for 4h to obtain the copper nanosphere particles.
As can be seen from fig. 2, copper particles having a diameter of about 500nm were formed in example 4.
Example 5
The present embodiment provides a copper nanoparticle.
The preparation method of the copper nano-sphere particles comprises the following steps:
(1) placing 0.12mmol of copper acetylacetonate, 0.012mmol of oleylamine and 20ml of glycol solution into a 50ml beaker for mixing, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a first mixed solution;
(2) adding 0.6g of sodium citrate into the first mixed solution in the step (1), sealing a beaker, and carrying out ultrasonic treatment for 30min until the sodium citrate is completely dissolved to obtain a second mixed solution;
(3) putting the second mixed solution into a stainless steel reaction kettle for sealing, and then putting the stainless steel reaction kettle into a high-temperature oven for carrying out solvothermal reaction for 14 hours at the reaction temperature of 200 ℃;
(4) and taking out the reaction kettle after the reaction is finished, pouring the solution in the kettle into a beaker after the reaction kettle is cooled, pouring ethylene glycol into the beaker to wash the product, performing 4000rpm/min centrifugation for 20min after washing, pouring out the supernatant after centrifugation, and repeating the centrifugation for 3 times. After the completion, the solid material was loaded into a test tube and placed in a vacuum drying oven. And drying for 4h at 40 ℃ to obtain the copper nanosphere particles.
As can be seen from FIG. 3, copper nanoparticles having a diameter of about 50 to 200nm were formed in example 5.
Example 6
The difference between this example and example 1 is that the molar amount of polyvinylpyrrolidone in step (1) of this example is 0.01 mmol/L.
The remaining preparation methods and parameters were in accordance with example 1.
Example 7
The difference between this example and example 1 is that the molar amount of polyvinylpyrrolidone in step (1) of this example is 0.18 mmol/L.
The remaining preparation methods and parameters were in accordance with example 1.
Example 8
The present example is different from example 1 in that the mass of oxalic acid in step (2) of the present example is 0.594g (6.6 mmol).
The remaining preparation methods and parameters were in accordance with example 1.
Example 9
The difference between this example and example 1 is that the mass of oxalic acid in step (2) of this example is 0.032g (0.36 mmol).
The remaining preparation methods and parameters were in accordance with example 1.
Example 10
This example differs from example 1 in that the solvothermal reaction temperature in step (3) of this example was 80 ℃.
The remaining preparation methods and parameters were in accordance with example 1.
Comparative example 1
The comparative example obtained a nanosheet copper metal material.
The difference between the preparation method of the copper metal material and the embodiment 1 is that the operation of the step (1) and the step (2) is combined into one step, and the specific method is as follows:
placing 0.12mmol of copper chloride, 0.324g (3.6mmol) of oxalic acid, 0.02mmol of polyvinylpyrrolidone and 20ml of ethylene glycol solution in a 50ml beaker for mixing, and carrying out ultrasonic treatment for 30min until complete dissolution to obtain a mixed solution;
on the basis of this, the remaining preparation processes and parameters were in accordance with example 1.
As can be seen from fig. 4, the copper metal material obtained in comparative example 1, which is in the form of nanosheets, did not obtain copper nanosphere particles.
Table 1 shows the diameters of the copper nanosphere particles provided in examples 1-10 and the specific surface areas of the products of examples 1-10 (copper nanosphere particles were not obtained in comparative example 1).
TABLE 1
Figure BDA0003008614070000111
Figure BDA0003008614070000121
From the data of example 1 and examples 6 and 7, it can be seen that when the molar ratio of the copper salt to the capping agent is too large or too small, the diameter of the resulting copper nanoparticle increases.
From the data results of example 1 and examples 8 and 9, it can be seen that when the molar ratio of the reducing agent to the copper salt is too large, the diameter of the obtained copper nanoparticle is significantly increased; when the molar ratio of the reducing agent to the copper salt is too small, the specific surface area of the resulting copper nanoball may be significantly reduced.
From the data results of examples 1 and 10, it is understood that when the solvothermal reaction temperature is too low, the specific surface area of the copper nanoparticle is greatly reduced.
As can be seen from the data results of example 1 and comparative example 1, when the copper salt solution, the reducing agent, and the capping agent were simultaneously mixed, spherical copper nanoparticles could not be obtained.
In summary, when the copper salt solution is mixed with the capping agent first, the structure is adjusted, and then the reducing agent is added, the copper nanosphere particles can be obtained, the diameter range is within 900nm, the molar ratio and the temperature are further adjusted, the diameter of the copper nanosphere particles can be smaller and can reach within 300nm, and the specific surface area is 4.7m2(ii) a/g and above.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. A preparation method of copper nano-sphere particles is characterized by comprising the following steps:
(1) mixing a copper metal salt solution and a blocking agent for the first time to obtain a first mixed solution;
(2) and (2) mixing the first mixed solution in the step (1) with a reducing agent for the second time to obtain a second mixed solution, and then carrying out a solvothermal reaction on the second mixed solution to obtain the copper nanosphere particles.
2. The preparation method of the copper nanoparticle particles according to claim 1, wherein the molar ratio of the copper metal salt to the capping agent in the copper metal salt solution in the step (1) is 10: 1-1: 1, preferably 10: 1-4: 1;
preferably, the molar concentration of the copper metal salt solution in the step (1) is 2-10 mmol/l;
preferably, the copper metal salt in the copper metal salt solution in step (1) comprises any one or a combination of at least two of copper acetylacetonate, copper sulfate or copper chloride;
preferably, the solvent in the copper metal salt solution of step (1) comprises any one of methanol, ethanol, ethylene glycol or glycerol or a combination of at least two of the same;
preferably, the blocking agent comprises any one of polyvinylpyrrolidone, oleylamine or poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) or a combination of at least two thereof.
3. The method for preparing copper nanoparticle particles according to claim 1 or 2, wherein the primary mixing method of step (1) comprises ultrasonic and/or stirring;
preferably, the time of the primary mixing in the step (1) is 10-30 min.
4. The method for preparing copper nanoparticle particles according to any one of claims 1 to 3, wherein the molar ratio of the reducing agent in step (2) to the copper metal salt in the copper metal salt solution in step (1) is 5:1 to 50:1, preferably 15:1 to 50: 1;
preferably, the reducing agent in step (2) comprises any one or a combination of at least two of oxalic acid, sodium citrate or acrylic acid.
5. The method for preparing copper nanoparticle particles according to any one of claims 1 to 4, wherein the secondary mixing in step (2) comprises sonication and/or stirring;
preferably, the time for the secondary mixing in the step (2) is 10-30 min;
preferably, the temperature of the solvothermal reaction in the step (2) is 100-220 ℃, and preferably 140-220 ℃;
preferably, the solvothermal reaction time in the step (2) is 5-25 h, and preferably 6-12 h.
6. The method for preparing copper nano-sphere particles according to any one of claims 1 to 5, wherein after the solvothermal reaction in the step (2) is finished, the washing, centrifuging and drying operations are sequentially carried out;
preferably, the rotating speed of the centrifugation is 2000-8000 rpm/min, preferably 2000-4000 rpm/min;
preferably, the drying temperature is 40-80 ℃, and preferably 50-60 ℃;
preferably, the drying time is 4-16 h, preferably 6-12 h.
7. The method for preparing copper nanoparticle particles according to any one of claims 1 to 6, comprising the steps of:
(1) carrying out ultrasonic treatment on a copper metal salt solution with the molar concentration of 2-10 mmol/l and a capping agent for 10-30 min, wherein the molar ratio of the copper metal salt in the copper metal salt solution to the capping agent is 10: 1-4: 1, so as to obtain a first mixed solution;
(2) carrying out ultrasonic treatment on the mixed solution obtained in the step (1) and a reducing agent for 10-30 min, wherein the molar ratio of the reducing agent to the copper metal salt in the copper metal salt solution obtained in the step (1) is 15: 1-50: 1 to obtain a second mixed solution, carrying out solvothermal reaction on the second mixed solution at 140-220 ℃ for 6-12 h, washing, centrifuging at the rotating speed of 2000-4000 rpm/min, and finally drying at 50-60 ℃ for 6-12 h to obtain copper nanosphere particles;
wherein, the copper metal salt in the copper metal salt solution in the step (1) comprises any one or the combination of at least two of copper acetylacetonate, copper sulfate or copper chloride;
the solvent in the copper metal salt solution in the step (1) comprises any one or the combination of at least two of methanol, ethanol, glycol or glycerol; the blocking agent comprises any one or a combination of at least two of polyvinylpyrrolidone, oleylamine or poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol); the reducing agent in the step (2) comprises any one or the combination of at least two of oxalic acid, sodium citrate or acrylic acid.
8. A copper nanoball particle prepared by the method for preparing the copper nanoball particle of any one of claims 1 to 7.
9. The copper nanoparticle according to claim 8, wherein the diameter of the copper nanoparticle is 50 to 900 nm.
10. Use of copper nanosphere particles according to claim 8 or 9 for catalytic reactions.
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