CN113102765B - Copper nano-sphere particles and preparation method and application thereof - Google Patents
Copper nano-sphere particles and preparation method and application thereof Download PDFInfo
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- CN113102765B CN113102765B CN202110369153.3A CN202110369153A CN113102765B CN 113102765 B CN113102765 B CN 113102765B CN 202110369153 A CN202110369153 A CN 202110369153A CN 113102765 B CN113102765 B CN 113102765B
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000010949 copper Substances 0.000 title claims abstract description 129
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 128
- 239000002077 nanosphere Substances 0.000 title claims abstract description 78
- 239000002245 particle Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 43
- 239000002184 metal Substances 0.000 claims abstract description 43
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 239000012266 salt solution Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 238000004729 solvothermal method Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000002981 blocking agent Substances 0.000 claims abstract description 5
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 45
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 14
- 150000003839 salts Chemical class 0.000 claims description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 7
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229920000463 Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) Polymers 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
- ZKXWKVVCCTZOLD-UHFFFAOYSA-N copper;4-hydroxypent-3-en-2-one Chemical compound [Cu].CC(O)=CC(C)=O.CC(O)=CC(C)=O ZKXWKVVCCTZOLD-UHFFFAOYSA-N 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000010981 drying operation Methods 0.000 claims description 2
- 231100000252 nontoxic Toxicity 0.000 abstract description 5
- 230000003000 nontoxic effect Effects 0.000 abstract description 5
- 150000001298 alcohols Chemical class 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 16
- 238000007789 sealing Methods 0.000 description 9
- 150000001879 copper Chemical class 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000005749 Copper compound Substances 0.000 description 4
- 150000001880 copper compounds Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007769 metal material Substances 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000000635 electron micrograph Methods 0.000 description 3
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- SVOAENZIOKPANY-CVBJKYQLSA-L copper;(z)-octadec-9-enoate Chemical compound [Cu+2].CCCCCCCC\C=C/CCCCCCCC([O-])=O.CCCCCCCC\C=C/CCCCCCCC([O-])=O SVOAENZIOKPANY-CVBJKYQLSA-L 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B01J35/40—
-
- B01J35/50—
-
- B01J35/612—
-
- 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
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides copper nanosphere particles, 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 one time to obtain a first mixed solution; (2) And (3) carrying out secondary mixing on the first mixed solution and the reducing agent in the step (1) to obtain a second mixed solution, and then carrying out solvothermal reaction on the second mixed solution to obtain the copper nanosphere particles. The method adopts nontoxic alcohols as solvents, is safe, environment-friendly and economic, is easy to operate and control, is an environment-friendly preparation method with simple operation, and simultaneously the prepared copper nanosphere particles have higher specific surface area and more active sites.
Description
Technical Field
The invention belongs to the technical field of nano materials, and relates to copper nanosphere particles, a preparation method and application thereof.
Background
Catalysis is a pillar technology of current medical and health, food production and engine fuel, and is a basic stone of the modern chemical industry. In catalytic reactions, the choice of catalyst is particularly critical. With the continued development of nanotechnology, researchers have found that nano-metal particles exhibit higher catalytic performance due to their larger specific surface area and higher active sites. At present, the common nano metal catalyst is noble metal materials such as Au, pt and the like, but the cost consumption is higher because the catalyst is lost in the catalytic process and the like.
In order to solve the problem, researchers propose to prepare the metal nano material by taking Cu as a raw material, and the material can obviously reduce the cost and has wider application prospect. So far, the main methods for preparing the metal nanospheres at home and abroad are high-temperature heating, an electrolytic method and a reduction method. However, the heating method has complex process, the product is easy to oxidize in the air and even explode, and the electrolytic method is difficult to master and is not suitable for mass production.
CN102941350a discloses a method for synthesizing nanometer copper powder. Specifically, a copper compound is subjected to thermal decomposition reaction in an organic solvent at high temperature to prepare the nanometer copper powder. The specific method comprises the following steps: 1) Weighing copper compound and dissolving in an organic solvent to prepare 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 reaction temperature heated to is 240-350 ℃; the reaction time is 10-80 minutes; 3) And (3) cooling the solution obtained after the reaction in the step (2), adding a cleaning agent for washing and centrifuging, pouring out the upper liquid, and putting into a baking oven for baking to obtain the nanometer copper powder. However, the heating method provided in this document is complicated in process, the product is easily oxidized in the air, even explosion occurs, and the safety cannot be ensured.
CN111705338A discloses a method for preparing nanometer copper powder, which comprises the following steps: the electrolyte used for preparing the nanometer copper powder is a mixed solution of copper sulfate, sodium citrate and sodium phosphate, the working electrode is a waste recovered copper material, the platinum net is a counter electrode, the electrolyte is deoxidized firstly, then constant current is applied to the working electrode by a constant current power supply, after enough copper powder is deposited on the platinum net, the platinum net is taken down, the platinum net is sealed in absolute ethyl alcohol for ultrasonic cleaning, and then the red nanometer copper powder with the average grain diameter of 30-85 nm is obtained after suction filtration and drying. The electrolytic method provided by the document prepares nano copper, and is difficult to realize large-scale production.
The reduction method is the most commonly used method in the industry at present, however, the reduction agent may have toxicity, longer reaction time and other problems.
Therefore, how to find a simple, efficient, safe and nontoxic method for preparing copper nanosphere particles with high specific surface area and more active sites is a technical problem to be solved.
Disclosure of Invention
The invention aims to provide copper nanosphere particles, and a preparation method and application thereof. The method adopts nontoxic alcohols as solvents, is safe, environment-friendly and economic, is easy to operate and control, is an environment-friendly preparation method with simple operation, and simultaneously the prepared copper nanosphere particles have higher specific surface area and more active sites.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing copper nanosphere particles, the method comprising the steps of:
(1) Mixing a copper metal salt solution and a blocking agent for one time to obtain a first mixed solution;
(2) And (3) carrying out secondary mixing on the first mixed solution and the reducing agent in the step (1) to obtain a second mixed solution, and then carrying out solvothermal reaction on the second mixed solution to obtain the copper nanosphere particles.
According to the preparation method provided by the invention, the copper metal salt solution and the end capping agent are mixed, the shape of the nanocrystalline is designed and controlled by utilizing the end capping agent, the nanotopography is controlled by adjusting the reaction condition, and then the reducing agent is added to reduce the copper metal salt into the metal copper, so that the copper nanosphere particles 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 copper metal salt to capping agent in the copper metal salt solution in 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, etc., preferably 10:1 to 4:1.
In the invention, the molar ratio of the copper salt to the end capping agent cannot be too large or too small, the size of the metal sphere reaches the micron level due to the too large or too small, and the particles of the copper nanosphere particles are more uniform when the ratio is 10:1-4:1.
Preferably, the molar concentration of the copper metal salt solution in step (1) is 2 to 10mmol/l, for example 2mmol/l, 3mmol/l, 4mmol/l, 5mmol/l, 6mmol/l, 7mmol/l, 8mmol/l, 9mmol/l or 10mmol/l, etc.
Preferably, the copper metal salt in the copper metal salt solution of 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 in step (1) comprises any one or a combination of at least two of methanol, ethanol, ethylene glycol or glycerol.
In the invention, the used solvent is nontoxic and safe, and is environment-friendly and economical.
Preferably, the capping 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).
Preferably, the method of mixing of step (1) comprises ultrasound and/or stirring.
Preferably, the time of the one mixing in the step (1) is 10 to 30min, for example, 10min, 15min, 20min, 25min or 30min, etc.
Preferably, 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 in the range of 5:1 to 50:1, such as 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1 or 50:1, etc., preferably in the range of 15:1 to 50:1.
In the invention, too large a molar ratio of the reducing agent to the copper salt can cause accumulation of metal balls, and too small a molar ratio can cause incomplete reduction of the copper salt to metallic copper.
Preferably, the reducing agent of step (2) comprises any one or a combination of at least two of oxalic acid, sodium citrate or acrylic acid.
Preferably, the method of mixing of step (2) comprises ultrasound and/or stirring.
Preferably, the time of the secondary mixing in step (2) is 10 to 30min, for example 10min, 15min, 20min, 25min or 30min, etc.
Preferably, the temperature of the solvothermal reaction in step (2) is 100 to 220 ℃, for example 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, 210 ℃ or 220 ℃, etc., preferably 140 to 220 ℃.
In the present invention, too high a reaction temperature of solvothermal leads to deactivation of the reaction, and too low a reaction temperature leads to incomplete reaction.
Preferably, the solvothermal reaction in step (2) is carried out for a period of time ranging from 5 to 25 hours, for example from 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours, 16 hours, 18 hours, 20 hours, 22 hours, 24 hours or 25 hours, etc., preferably from 6 to 12 hours.
Preferably, after the solvothermal reaction in step (2) is finished, washing, centrifuging and drying operations are continued in sequence.
Preferably, the rotational speed of the centrifugation is 2000 to 8000rpm/min, for example 2000rpm/min, 3000rpm/min, 4000rpm/min, 5000rpm/min, 6000rpm/min, 7000rpm/min or 8000rpm/min, etc., preferably 2000 to 4000rpm/min.
Preferably, the drying temperature is 40 to 80 ℃, for example 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ or the like, preferably 50 to 60 ℃.
Preferably, the drying time is 4 to 16 hours, for example 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 15 hours or 16 hours, etc., preferably 6 to 12 hours.
As a preferred technical scheme, the preparation method of the copper nanosphere particles comprises the following steps:
(1) Ultrasonic treatment is carried out on a copper metal salt solution with the molar concentration of 2-10 mmol/l and a blocking agent for 10-30 min, wherein the molar ratio of the copper metal salt in the copper metal salt solution to the blocking 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, obtaining a second mixed solution, carrying out solvothermal reaction on the second mixed solution for 6-12 h at 140-220 ℃, washing, centrifuging at the rotating speed of 2000-4000 rpm/min, and finally drying at 50-60 ℃ for 6-12 h to obtain the copper nanosphere particles;
wherein the copper metal salt in the copper metal salt solution in the step (1) comprises any one or a combination of at least two of copper acetylacetonate, copper sulfate and copper chloride;
the solvent in the copper metal salt solution in the step (1) comprises any one or a combination of at least two of methanol, ethanol, glycol or glycerol; the end-capping 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 a 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 produced by the method of producing a copper nanosphere particle according to the first aspect.
Preferably, the diameter of the copper nanosphere particles is 50 to 900nm, such as 50nm, 100nm, 200nm, 300nm, 400nm, 500nm, 600nm, 700nm, 800nm or 900nm, etc.
In a third aspect, the present invention also provides a use of the copper nanosphere particles of the second aspect for catalyzing a 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, and the copper nanosphere particles have higher specific surface area and more active sitesThe diameter range is 900nm, and the molar ratio and the temperature are further adjusted, so that the diameter of the copper nanosphere particles is smaller and reaches 300nm, and the specific surface area is 4.7m 2 And/g and above, and adopting nontoxic alcohols as solvents, the preparation method is safe, environment-friendly, economical, simple to operate and easy to control, and is an environment-friendly and simple to operate preparation method.
Drawings
TEM electron microscope image of copper nanosphere particles provided in example 3 of FIG. 1.
Fig. 2 is a TEM electron micrograph of copper nanosphere particles as provided in example 4.
Fig. 3 TEM electron microscopy images of copper nanosphere particles provided in example 5.
Fig. 4 is a TEM electron micrograph of the copper nanoplatelets provided in comparative example 1.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a copper nanosphere particle.
The preparation method of the copper nanosphere particles comprises the following steps:
(1) Placing 0.12mmol of copper chloride, 0.02mmol of polyvinylpyrrolidone and 20ml of ethylene glycol solution into a 50ml beaker for mixing, and carrying out ultrasonic treatment for 30min until the copper chloride and the ethylene glycol solution are completely dissolved to obtain a first mixed solution;
(2) Adding 0.324g (3.6 mmol) oxalic acid into the first mixed solution in the step (1), and sealing the beaker for ultrasonic treatment for 30min until the oxalic acid is completely dissolved to obtain a second mixed solution
(3) Sealing the second mixed solution in a stainless steel reaction kettle, and then performing solvothermal reaction in a high-temperature oven at 140 ℃ for 12 hours;
(4) Washing the product after the reaction in the step (3) by using glycol solution, centrifuging in a centrifuge at a rotating speed of 4000rpm/min for 10min after the washing, pouring out supernatant after centrifuging, repeating the centrifugal separation operation for 3 times, and drying the centrifuged solid matters at 40 ℃ for 4 hours to obtain the copper nanosphere particles.
Example 2
The present embodiment provides a copper nanosphere particle.
The preparation method of the copper nanosphere particles comprises the following steps:
(1) Placing 0.12mmol of copper chloride, 0.012mmol of oleylamine and 20ml of ethanol solution in a 50ml beaker, mixing, stirring for 30min until complete dissolution, and obtaining a first mixed solution;
(2) Adding 0.54g (6 mmol) of oxalic acid into the first mixed solution in the step (1), and stirring in a sealed beaker for 30min until the oxalic acid is completely dissolved to obtain a second mixed solution;
(3) Sealing the second mixed solution in a stainless steel reaction kettle, and then performing solvothermal reaction in a high-temperature oven at 220 ℃ for 6 hours;
(4) Washing the product after the reaction in the step (3) by using glycol solution, centrifuging in a centrifuge at a rotating speed of 3000rpm/min for 10min after the washing, pouring out supernatant after centrifuging, repeating the centrifugal separation operation for 3 times, and drying the centrifuged solid matters at 60 ℃ for 6h to obtain the copper nanosphere particles.
Example 3
The present embodiment provides a copper nanosphere particle.
The preparation method of the copper nanosphere particles comprises the following steps:
(1) Mixing 0.12mmol of copper chloride, 0.03mmol of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 20ml of glycerol solution in a 50ml beaker, and performing ultrasonic treatment for 30min until the solution is completely dissolved to obtain a first mixed solution;
(2) Adding 0.162g (1.8 mmol) of oxalic acid into the first mixed solution in the step (1), and sealing the beaker for ultrasonic treatment for 30min until the oxalic acid is completely dissolved to obtain a second mixed solution;
(3) Sealing the second mixed solution in a stainless steel reaction kettle, and then performing solvothermal reaction in a high-temperature oven at 170 ℃ for 10 hours;
(4) Washing the product after the reaction in the step (3) by using glycerol solution, centrifuging in a centrifuge at a rotating speed of 4000rpm/min for 10min after the washing, pouring out supernatant after the centrifugation, repeating the centrifugation operation for 3 times, and drying the centrifuged solid matters at 40 ℃ for 4 hours to obtain the copper nanosphere particles.
As can be seen from FIG. 1, copper nanosphere particles with a high dispersity and a diameter in the range of about 100nm were formed in example 3.
Example 4
The present embodiment provides a copper nanosphere particle.
The preparation method of the copper nanosphere particles comprises the following steps:
(1) Mixing 0.12mmol of copper sulfate, 0.12mmol of poly (ethylene glycol) -block-poly (propylene glycol) -block-poly (ethylene glycol) and 20ml of ethylene glycol solution in a 50ml beaker, and carrying out ultrasonic treatment for 10min until complete dissolution to obtain a first mixed solution;
(2) Adding 0.054g (0.6 mmol) of oxalic acid into the first mixed solution in the step (1), and sealing the beaker for ultrasonic treatment for 30min until the oxalic acid is completely dissolved to obtain a second mixed solution;
(3) Sealing the second mixed solution in a stainless steel reaction kettle, and then performing solvothermal reaction in a high-temperature oven at 100 ℃ for 25 hours;
(4) Washing the product after the reaction in the step (3) by using glycol solution, centrifuging in a centrifuge at a rotating speed of 4000rpm/min for 10min after the washing, pouring out supernatant after centrifuging, repeating the centrifugal separation operation for 3 times, and drying the centrifuged solid matters at 80 ℃ for 4 hours 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 nanosphere particle.
The preparation method of the copper nanosphere particles comprises the following steps:
(1) Placing 0.12mmol of copper acetylacetonate, 0.012mmol of oleylamine and 20ml of ethylene glycol solution into a 50ml beaker for mixing, and performing 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), and sealing a beaker for ultrasonic treatment for 30min until the sodium citrate is completely dissolved to obtain a second mixed solution;
(3) Sealing the second mixed solution in a stainless steel reaction kettle, and then placing the stainless steel reaction kettle in a high-temperature oven to carry out solvothermal reaction for 14h at the reaction temperature of 200 ℃;
(4) Taking out the reaction kettle after the reaction is finished, pouring the solution in the reaction kettle into a beaker after the reaction kettle is cooled, pouring glycol into the beaker to wash the product, performing centrifugal operation at 4000rpm/min for 20min after washing, pouring out the supernatant after centrifugation, and repeating the centrifugal separation operation for 3 times. After the completion, the solid material was put into a test tube and placed into a vacuum drying oven. And drying for 4 hours at the temperature of 40 ℃ to obtain the copper nanosphere particles after the drying is finished.
As can be seen from FIG. 3, copper nanoparticles having diameters 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 was 0.01mmol/L.
The remaining preparation methods and parameters were consistent 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 was 0.18mmol/L.
The remaining preparation methods and parameters were consistent with example 1.
Example 8
The difference between this example and example 1 is that the mass of oxalic acid in step (2) of this example was 0.594g (6.6 mmol).
The remaining preparation methods and parameters were consistent 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 was 0.032g (0.36 mmol).
The remaining preparation methods and parameters were consistent with example 1.
Example 10
The difference between this example and example 1 is that the solvothermal reaction temperature in step (3) of this example is 80 ℃.
The remaining preparation methods and parameters were consistent with example 1.
Comparative example 1
The comparative example yielded a nanosheet-shaped copper metal material.
The preparation method of the copper metal material is different from the embodiment 1 in that the operation of the step (1) and the operation of the step (2) are combined into one step, and the specific method is as follows:
mixing 0.12mmol of copper chloride, 0.324g (3.6 mmol) of oxalic acid, 0.02mmol of polyvinylpyrrolidone and 20ml of ethylene glycol solution in a 50ml beaker, and carrying out ultrasonic treatment for 30min until the mixed solution is completely dissolved to obtain a mixed solution;
on this basis, the remaining preparation methods and parameters remain the same as in example 1.
As can be seen from fig. 4, the nano-platelet-shaped copper metal material obtained in comparative example 1 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
From the data of examples 1 and 6 and 7, it is understood that when the molar ratio of copper salt to capping agent is too large or too small, the diameter of the resulting copper nanosphere particles increases.
From the data of examples 1 and 8 and 9, it is understood that when the molar ratio of the reducing agent to the copper salt is too large, the diameter of the obtained copper nanosphere particles is significantly increased; when the molar ratio of the reducing agent to the copper salt is too small, the specific surface area of the obtained copper nanospheres is remarkably reduced.
From the data of example 1 and example 10, it is understood that when the solvothermal reaction temperature is too low, the specific surface area of the copper nanosphere particles is greatly reduced.
From the data of example 1 and comparative example 1, it is understood that spherical copper nanoparticles cannot be obtained when the copper salt solution, the reducing agent and the capping agent are simultaneously mixed.
In summary, when the copper salt solution is mixed with the end capping agent to perform structure control, and then the reducing agent is added, the copper nanosphere particles can be obtained, the diameter range is 900nm, and the molar ratio and the temperature are further adjusted, so that the diameter of the copper nanosphere particles is smaller and reaches 300nm, and the specific surface area is 4.7m 2 And/g and above.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (24)
1. A method for preparing copper nanosphere particles, comprising the steps of:
(1) Mixing a copper metal salt solution and a blocking agent for one time to obtain a first mixed solution;
(2) Secondary mixing is carried out on the first mixed solution and the reducing agent in the step (1) to obtain a second mixed solution, and then solvothermal reaction is carried out on the second mixed solution to obtain the copper nanosphere particles; the reducing agent in the step (2) comprises any one or a combination of at least two of oxalic acid, sodium citrate or acrylic acid; the molar ratio of the copper metal salt in the copper metal salt solution in the step (1) to the end capping agent is 10:1-1:1; the molar concentration of the copper metal salt solution in the step (1) is 2-10 mmol/l; 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 5:1-50:1.
2. The method for preparing copper nanosphere particles according to claim 1, wherein the molar ratio of copper metal salt to capping agent in the copper metal salt solution is 10:1-4:1.
3. The method for producing copper nanosphere particles according to claim 1, wherein the copper metal salt in the copper metal salt solution of step (1) comprises any one or a combination of at least two of copper acetylacetonate, copper sulfate, and copper chloride.
4. The method for producing copper nanosphere particles according to claim 1, wherein the solvent in the copper metal salt solution of step (1) comprises any one or a combination of at least two of methanol, ethanol, ethylene glycol or glycerol.
5. The method of preparing copper nanosphere particles according to claim 1, wherein the capping 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).
6. The method of preparing copper nanosphere particles according to claim 1, wherein the one-time mixing method of step (1) comprises ultrasound and/or stirring.
7. The method for preparing copper nanosphere particles according to claim 1, wherein the time of the one-time mixing in the step (1) is 10 to 30 minutes.
8. The method for preparing copper nanosphere particles according to claim 1, 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 15:1 to 50:1.
9. The method of preparing copper nanosphere particles according to claim 1, wherein the secondary mixing method of step (2) comprises ultrasound and/or stirring.
10. The method for preparing copper nanosphere particles according to claim 1, wherein the secondary mixing time in step (2) is 10 to 30 minutes.
11. The method for preparing copper nanosphere particles according to claim 1, wherein the solvothermal reaction in step (2) is at a temperature of 100-220 ℃.
12. The method for preparing copper nanosphere particles according to claim 11, wherein the solvothermal reaction in step (2) is carried out at a temperature of 140-220 ℃.
13. The method for preparing copper nanosphere particles according to claim 1, wherein the solvothermal reaction in step (2) is carried out for a period of 5 to 25 hours.
14. The method for preparing copper nanosphere particles according to claim 13, wherein the solvothermal reaction time of step (2) is 6-12 hours.
15. The method for preparing copper nanosphere particles according to claim 1, wherein the washing, centrifuging and drying operations are continued in sequence after the solvothermal reaction of step (2) is completed.
16. The method for preparing copper nanosphere particles according to claim 15, wherein the rotational speed of the centrifugation is 2000-8000 rpm/min.
17. The method of producing copper nanosphere particles as recited in claim 16, wherein the rotational speed of centrifugation is 2000 to 4000rpm/min.
18. The method of producing copper nanosphere particles according to claim 15, wherein the drying temperature is 40-80 ℃.
19. The method of producing copper nanosphere particles according to claim 18, wherein the drying temperature is 50 to 60 ℃.
20. The method of producing copper nanosphere particles as recited in claim 15, wherein the drying time is from 4 to 16 hours.
21. The method of producing copper nanosphere particles as recited in claim 20, wherein the drying time is from 6 to 12 hours.
22. The method for preparing copper nanosphere particles according to claim 1, characterized in that the preparation method comprises the following steps:
(1) Ultrasonic treatment is carried out on the copper metal salt solution and the end capping agent for 10-30 min, wherein a first mixed solution is obtained;
(2) Carrying out ultrasonic treatment on the mixed solution obtained in the step (1) and a reducing agent for 10-30 min, wherein a second mixed solution is obtained, carrying out solvothermal reaction on the second mixed solution for 6-12 h at 140-220 ℃, washing, centrifuging at a rotating speed of 2000-4000 rpm/min, and finally drying at 50-60 ℃ for 6-12 h to obtain the copper nanosphere particles;
wherein the copper metal salt in the copper metal salt solution in the step (1) comprises any one or a combination of at least two of copper acetylacetonate, copper sulfate and copper chloride;
the solvent in the copper metal salt solution in the step (1) comprises any one or a combination of at least two of methanol, ethanol, glycol or glycerol; the end-capping 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 a combination of at least two of oxalic acid, sodium citrate or acrylic acid.
23. The method for preparing copper nanosphere particles according to claim 1, wherein the specific surface area of the copper nanosphere particles is not less than 4.7m 2 /g。
24. The method for preparing copper nanosphere particles according to claim 1, wherein the diameter of the copper nanosphere particles is 50-900 nm.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407344A (en) * | 2011-11-13 | 2012-04-11 | 西安科技大学 | Industrial production method of copper nanoparticle |
| CN102941350A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | Preparation method of copper nanoparticles |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
| CN107146821A (en) * | 2017-05-02 | 2017-09-08 | 武汉大学 | The controllable preparation of different draw ratio nano silver wires and flexible transparent electrode preparation method |
| CN109352206A (en) * | 2018-11-17 | 2019-02-19 | 华中科技大学 | A kind of alloy nanoparticle soldering paste and preparation method thereof |
| CN109665557A (en) * | 2019-03-01 | 2019-04-23 | 西北工业大学 | A kind of flower-shaped copper oxide and its preparation method and application |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100716201B1 (en) * | 2005-09-14 | 2007-05-10 | 삼성전기주식회사 | Metal nanoparticles and method for manufacturing thereof |
| KR20070080467A (en) * | 2006-02-07 | 2007-08-10 | 삼성전자주식회사 | Copper nano particle, method of manufacturing the same and method of manufacturing the copper coating film using the same |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102407344A (en) * | 2011-11-13 | 2012-04-11 | 西安科技大学 | Industrial production method of copper nanoparticle |
| CN102941350A (en) * | 2012-11-06 | 2013-02-27 | 南京工业大学 | Preparation method of copper nanoparticles |
| CN103087582A (en) * | 2013-01-25 | 2013-05-08 | 天津理工大学 | Preparation method of low-temperature sintering nano copper conductive ink |
| CN107146821A (en) * | 2017-05-02 | 2017-09-08 | 武汉大学 | The controllable preparation of different draw ratio nano silver wires and flexible transparent electrode preparation method |
| CN109352206A (en) * | 2018-11-17 | 2019-02-19 | 华中科技大学 | A kind of alloy nanoparticle soldering paste and preparation method thereof |
| CN109665557A (en) * | 2019-03-01 | 2019-04-23 | 西北工业大学 | A kind of flower-shaped copper oxide and its preparation method and application |
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