CN115255381A - Macroscopic quantity preparation method of water-soluble nano copper powder - Google Patents
Macroscopic quantity preparation method of water-soluble nano copper powder Download PDFInfo
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 150000004699 copper complex Chemical class 0.000 claims abstract description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 239000012046 mixed solvent Substances 0.000 claims abstract description 17
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 150000001879 copper Chemical class 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000012044 organic layer Substances 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 239000012074 organic phase Substances 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 abstract description 14
- 239000010949 copper Substances 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 5
- 229910000881 Cu alloy Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002390 rotary evaporation Methods 0.000 description 4
- 206010028980 Neoplasm Diseases 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical group [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229960001484 edetic acid Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 235000006708 antioxidants Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 102000002260 Alkaline Phosphatase Human genes 0.000 description 1
- 108020004774 Alkaline Phosphatase Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 102000004533 Endonucleases Human genes 0.000 description 1
- 108010042407 Endonucleases Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- -1 polyoxyethylene Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Images
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
- 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
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a macro preparation method of water-soluble nano copper powder, which comprises the steps of taking deionized water as a solvent, adding copper salt, completely dissolving, adding a water-soluble organic ligand, and reacting to obtain a water-soluble copper complex; preparing a mixed solvent by using absolute ethyl alcohol and deionized water; adding a copper complex, magnetically stirring until the copper complex is completely dissolved, adjusting the pH value to 6 to 7, increasing the rotating speed, continuously stirring, adding a reducing agent, continuously stirring until the reaction is completely finished, collecting the nano copper powder, washing, and drying in vacuum to obtain the water-soluble nano copper powder with uniform particle size. The preparation method can prepare the monodisperse water-soluble nano copper powder with excellent quality at room temperature, is a key technology which can bring revolutionary changes to copper and copper alloy, and has important theoretical significance and practical value.
Description
Technical Field
The invention relates to a macroscopic quantity preparation method of water-soluble nano copper powder.
Background
The nano metal powder has a unique microstructure, and has surface effect, quantum size effect and macroscopic tunnel effect, so that the nano metal powder has special physical and chemical properties such as light, electricity, magnetism, catalysis and the like. The nano copper powder is widely applied to the fields of integrated circuits, sterilization technology, battery electrodes and special catalysis due to excellent catalytic activity, electric and thermal conductivity and antibacterial deodorization performance.
Copper is one of trace elements necessary for human bodies, can be metabolized and absorbed by the human bodies, and cannot be enriched in the human bodies, so that the water-soluble nano copper powder can replace toxic heavy metal silver antibacterial agents, and has the sterilization advantages that: has stable property, no toxicity or irritation to human body, can kill bacteria, has antibacterial effect, etc. The water-soluble nano copper powder is also widely applied to nano biotechnology, for example, the nano copper powder can be used as a novel nano probe and has wide application prospect in the fields of analysis and detection of metal ions, biological micromolecules, proteins, nucleic acids and enzymes, cell imaging and the like, researchers synthesize copper nanoclusters by taking DNA as a template, copper sulfate as a raw material and ascorbic acid as a reducing agent, and activity detection of alkaline phosphatase and endonuclease is respectively realized on the basis of the copper nanoclusters. The copper-based nano material can also be applied to the acoustic dynamic tumor treatment, the acoustic dynamic treatment is an effective noninvasive tumor treatment method, the acoustic sensitizer is activated by ultrasonic waves to generate active oxygen, so that tumor cells are killed, and the copper-based nano material has wide prospect in the minimally invasive tumor treatment.
At present, the high-temperature oil phase method can be used for synthesizing stable and uniform nano copper powder, but how to prepare water-soluble nano copper powder on a large scale is always a difficult problem. Therefore, the development of a synthetic method of water-soluble nano copper powder with uniform particle size, the reduction of energy consumption and pollution in the synthetic process, and the search of a green chemical reduction way have great significance for scientific research and industrial production.
Disclosure of Invention
The invention provides a macroscopic preparation method capable of synthesizing a large amount of water-soluble nano copper powder, which has the advantages of low energy consumption, less pollution, greenness and high efficiency, is a key technology for solving the problem of water-soluble nano copper powder copper, and has important practical value.
The technical scheme adopted by the invention is as follows: a macro preparation method of water-soluble nano copper powder comprises the following steps:
1) Preparation of different water-soluble copper complexes:
adding 4mol of copper salt and 1 to 4mol of organic ligand into 2.8L of deionized water, respectively taking the deionized water, the copper salt and the organic ligand, adding the copper salt into the deionized water at room temperature, slowly stirring to completely dissolve the copper salt, adding the organic ligand, carrying out coordination reaction at the temperature of 70 ℃ for refluxing for 4 hours to obtain an organic layer containing the copper complex, washing the organic layer containing the copper complex for at least 3 times by using the deionized water in a separating funnel, and carrying out rotary evaporation on the organic phase to obtain a water-soluble copper complex;
the copper salt is cupric oxalate, anhydrous cupric sulfate, cupric chloride dihydrate, cupric acetate monohydrate or cupric nitrate.
The organic ligand is selected from Ethylene Diamine Tetraacetic Acid (EDTA), citric acid, dicarboxy polyethylene glycol (HOOC-PEG-COOH) or polyoxyethylene diamine (H) 2 N-PEG-NH 2 ）。
) Preparing water-soluble nano copper powder:
respectively taking absolute ethyl alcohol and deionized water according to the volume ratio of 0-1: 10, and uniformly mixing to obtain a mixed solvent; adding 10mol of copper complex into 100L of mixed solvent, respectively taking the mixed solvent and the water-soluble copper complex, and then taking a reducing agent, wherein the molar ratio of the reducing agent to the water-soluble copper complex is 1: 5-100;
adding the copper complex into the mixed solvent at room temperature, magnetically stirring (2000 r/min) to completely dissolve the copper complex, and adjusting the pH value to 6-7 by using a sodium hydroxide solution under the stirring condition; and (3) increasing the rotating speed, continuously stirring, adding a reducing agent, continuously stirring until no bubbles are generated, completely reacting, centrifugally separating and collecting the nano copper powder, washing the nano copper powder for three times by using a mixed solvent, and drying in vacuum to obtain the water-soluble nano copper powder (monodisperse nano copper powder) with uniform particle size.
The reducing agent is sodium phosphite, ascorbic acid or sodium borohydride.
The preparation method prepares the water-soluble copper complex at room temperature, and then reduces the copper complex at room temperature to prepare the water-soluble nano copper powder, wherein the surface of the water-soluble nano copper powder has organic ligands which can play the roles of passivating the surface and stopping oxygen, so the water-soluble nano copper powder has excellent oxidation resistance.
As can be seen from fig. 1, the copper complex is blue in water (fig. 1a is a photograph of a water-soluble copper complex solution), black copper nanoparticles are obtained by green chemical reduction, and the copper nanoparticles are well dispersed in water (fig. 1b is a photograph of water-soluble copper nanoparticles in water, which are well dispersed in water). The preparation method can achieve the preparation of single hectogram-level water-soluble nano copper powder (figure 1c is a real figure of the prepared water-soluble nano copper powder).
FIG. 2 is a transmission electron microscope morphology image of the water-soluble nano copper powder prepared by the preparation method of the present invention, and it can be seen from the image that the nano copper powder prepared by the preparation method of the present invention is water-soluble spherical nano particles and has uniform morphology.
FIG. 3 is a distribution diagram of the particle size of the water-soluble copper nanoparticles prepared by the method of the present invention, and it can be seen that the water-soluble copper nanoparticles have a narrow size distribution range and an average particle size of 4.6 nm.
FIG. 4 is an XRD (X-ray diffraction) pattern of the water-soluble nano-copper powder prepared by the invention, and the sample prepared by the preparation method of the invention has characteristic crystal faces of (111), (200) and (220) of copper, but does not have the characteristic crystal face of copper oxide, thereby indicating that the water-soluble nano-copper powder prepared by the preparation method of the invention has excellent antioxidation and high purity.
Fig. 5 is a diagram showing a real object of the water-soluble copper nanopowder prepared by the present invention dispersed in water, and it can be seen that the copper nanopowder is well dispersed after standing still in water for 7 days, which shows that the copper nanopowder has good water solubility.
According to the preparation method, the copper salt is converted into the copper complex, so that the spatial aggregation phenomenon of copper ions is effectively prevented, and the antioxidant nano-scale water-soluble copper powder with the average particle size of 4.6 nm is directly prepared by slowly adding the reducing agent without adding a dispersing agent and an antioxidant, so that the equipment requirement is low, and the operation method is simple.
The invention provides a preparation method for overcoming and massively synthesizing water-soluble nano copper powder, which has the advantages of low energy consumption, less pollution, greenness and high efficiency, is a key technology for solving the problem of water-soluble nano copper powder and has important practical value.
The preparation method of the invention prepares the water-soluble nano copper powder in water. The water-soluble nano copper powder has the characteristics of small size (average particle size is 4.6 nm), uniform appearance, narrow particle size distribution range, controllable particle size and appearance, high purity and the like. So that the antibacterial material has very high application value in the fields of antibacterial technology and nano biotechnology.
Drawings
FIG. 1 is a photograph of an intermediate product obtained in the production method of the present invention and a water-soluble copper powder.
FIG. 2 is a transmission electron microscope topography of the water-soluble copper powder prepared by the preparation method of the invention.
FIG. 3 is a graph showing the distribution of particle sizes of water-soluble copper powder obtained by the production method of the present invention.
Fig. 4 is an XRD pattern of the water-soluble nano-copper powder prepared by the preparation method of the present invention.
FIG. 5 is a diagram showing the dispersion of the water-soluble copper nanoparticles prepared by the method of the present invention in water.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
At room temperature, adding 4mol of anhydrous copper sulfate into 2.8L of deionized water, slowly stirring to completely dissolve the anhydrous copper sulfate, adding 4mol of citric acid, performing coordination reaction at the temperature of 70 ℃ and refluxing for 4 hours to obtain an organic layer containing a copper complex, washing the organic layer containing the copper complex for at least 3 times by using the deionized water in a separating funnel, and performing rotary evaporation on an organic phase to obtain a copper-green water-soluble copper complex; adding 10mol of copper complex into 100L of deionized water, magnetically stirring to completely dissolve the copper complex, adjusting the pH value to 6 by using a sodium hydroxide solution under the stirring condition, increasing the rotating speed to continue the magnetic stirring, adding 0.5mol of ascorbic acid, continuously stirring until no bubbles are generated, completely reacting, centrifugally separating and collecting water-soluble nano copper powder, washing three times by using the deionized water, and performing vacuum drying to obtain the water-soluble nano copper powder with uniform particle size.
Example 2
Adding 4mol of copper oxalate into 2.8L of deionized water at room temperature, slowly stirring to completely dissolve the copper oxalate, adding 3mol of EDTA, carrying out coordination reaction at the temperature of 70 ℃ and refluxing for 4h to obtain an organic layer containing a copper complex, washing the organic layer containing the copper complex for at least 3 times by using the deionized water in a separating funnel, and carrying out rotary evaporation on the organic phase to obtain a copper-green copper complex; respectively taking absolute ethyl alcohol and deionized water according to the volume ratio of 1: 10, uniformly mixing to obtain a mixed solvent, adding 10mol of copper complex into 100L of the mixed solvent, magnetically stirring to completely dissolve the copper complex, adjusting the pH value to 7 with a sodium hydroxide solution under the stirring condition, increasing the rotating speed to continue stirring, adding 1mol of sodium borohydride, continuously stirring until no bubbles are generated, completely reacting, centrifugally separating and collecting water-soluble nano copper powder, washing with the mixed solvent, and drying in vacuum to obtain the water-soluble nano copper powder with uniform particle size.
Example 3
Adding 4mol of copper chloride dihydrate into 2.8L of deionized water at room temperature, slowly stirring to completely dissolve the copper chloride dihydrate, adding 1mol of HOOC-PEG-COOH, carrying out coordination reaction at the temperature of 70 ℃ and refluxing for 4h to obtain an organic layer containing a copper complex, washing the organic layer containing the copper complex for at least 3 times by using the deionized water in a separating funnel, and carrying out rotary evaporation on the organic phase to obtain a copper-green copper complex; respectively taking absolute ethyl alcohol and deionized water according to a volume ratio of 0.5: 10, and uniformly mixing to obtain a mixed solvent; adding 10mol of copper complex into 100L of mixed solvent, stirring by magnetic force to completely dissolve the copper complex, adjusting the pH value to 6.5 by using sodium hydroxide solution under the stirring condition, increasing the rotating speed to continue stirring, adding 2mol of sodium phosphite, continuously stirring until no bubbles are generated, completing the reaction, centrifugally separating and collecting water-soluble nano copper powder, washing by using the mixed solvent, and drying in vacuum to obtain the water-soluble nano copper powder with uniform particle size.
Claims (6)
1. A macro preparation method of water-soluble nano copper powder is characterized by comprising the following steps:
1) Adding 4mol of copper salt and 1 to 4mol of organic ligand into 2.8L of deionized water, and respectively taking the deionized water, the copper salt and the organic ligand; at room temperature, adding copper salt into deionized water to completely dissolve the copper salt, adding an organic ligand, and reacting to obtain a water-soluble copper complex;
2) Preparing a mixed solvent; respectively taking the mixed solvent and the copper complex according to the proportion of adding 10mol of the copper complex into 100L of the mixed solvent; then taking a reducing agent, wherein the molar ratio of the reducing agent to the copper complex is 1: 5-100;
adding the copper complex into the mixed solvent, magnetically stirring to completely dissolve the copper complex, adjusting the pH value to 6-7, increasing the rotating speed of the magnetic stirring, continuously stirring, slowly adding a reducing agent, continuously stirring until the reaction is complete, centrifugally separating to collect the nano copper powder, washing with the mixed solvent, and drying in vacuum to obtain the water-soluble nano copper powder with excellent quality.
2. The macro preparation method of water-soluble nano copper powder according to claim 1, wherein in step 1), after the organic ligand is added, the organic layer containing the copper complex is obtained by the coordination reaction and reflux for 4h at the temperature of 70 ℃, the organic layer containing the copper complex is washed for at least 3 times by deionized water in a separating funnel, and the organic phase is rotated and evaporated to obtain the water-soluble copper complex.
3. The macro preparation method of water-soluble nano copper powder as claimed in claim 1, wherein in the step 2), the organic solvent is prepared from ethanol and deionized water according to a volume ratio of 0-1: 10.
4. The macro-preparation method of water-soluble copper nanopowder as claimed in claim 1, wherein in step 1), copper sulfate, copper chloride, copper acetate or copper nitrate is used as copper salt.
5. The macro-preparation method of water-soluble nano copper powder according to claim 1, wherein in the step 1), the organic ligand is EDTA, citric acid, HOOC-PEG-COOH or H 2 N-PEG-NH 2 。
6. The macro-preparation method of water-soluble nano copper powder according to claim 1, wherein in the step 2), sodium phosphite, ascorbic acid or sodium borohydride is used as a reducing agent.
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| CN117160459A (en) * | 2023-07-20 | 2023-12-05 | 淮安中顺环保科技有限公司 | Metal nano material and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709617A (en) * | 2004-06-18 | 2005-12-21 | 中国科学院兰州化学物理研究所 | Method for preparing nano copper particle |
| JP2009256779A (en) * | 2008-03-27 | 2009-11-05 | Furukawa Electric Co Ltd:The | Method for producing copper fine particle-dispersed aqueous solution, and method for storing the copper fine particle-dispersed aqueous solution |
| CN101811192A (en) * | 2010-03-09 | 2010-08-25 | 上海师范大学 | Water-soluble monodisperse iron-nickel magnetic nanoparticles and application thereof |
| US20170068019A1 (en) * | 2015-09-04 | 2017-03-09 | Novartis Ag | Method for producing contact lenses with durable lubricious coatings thereon |
| US20180297121A1 (en) * | 2015-12-30 | 2018-10-18 | Universidad De Chile | Method for producing copper nanoparticles and use of said particles |
| CN109568578A (en) * | 2018-11-22 | 2019-04-05 | 广西师范大学 | Natural biomass quantum dot and biomass quantum dot-copper nano-complex preparation method and applications |
| CN113600829A (en) * | 2021-08-24 | 2021-11-05 | 兰州大学 | Macroscopic quantity preparation method of ultra-small size nanometer copper powder |
| CN114433864A (en) * | 2022-01-17 | 2022-05-06 | 淮安中顺环保科技有限公司 | Preparation method of nano nickel powder |
| CN114749676A (en) * | 2022-04-26 | 2022-07-15 | 淮安中顺环保科技有限公司 | High-flux preparation method of copper-nickel alloy nanoparticles |
-
2022
- 2022-08-08 CN CN202210944486.9A patent/CN115255381B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1709617A (en) * | 2004-06-18 | 2005-12-21 | 中国科学院兰州化学物理研究所 | Method for preparing nano copper particle |
| JP2009256779A (en) * | 2008-03-27 | 2009-11-05 | Furukawa Electric Co Ltd:The | Method for producing copper fine particle-dispersed aqueous solution, and method for storing the copper fine particle-dispersed aqueous solution |
| CN101811192A (en) * | 2010-03-09 | 2010-08-25 | 上海师范大学 | Water-soluble monodisperse iron-nickel magnetic nanoparticles and application thereof |
| US20170068019A1 (en) * | 2015-09-04 | 2017-03-09 | Novartis Ag | Method for producing contact lenses with durable lubricious coatings thereon |
| US20180297121A1 (en) * | 2015-12-30 | 2018-10-18 | Universidad De Chile | Method for producing copper nanoparticles and use of said particles |
| CN109568578A (en) * | 2018-11-22 | 2019-04-05 | 广西师范大学 | Natural biomass quantum dot and biomass quantum dot-copper nano-complex preparation method and applications |
| CN113600829A (en) * | 2021-08-24 | 2021-11-05 | 兰州大学 | Macroscopic quantity preparation method of ultra-small size nanometer copper powder |
| CN114433864A (en) * | 2022-01-17 | 2022-05-06 | 淮安中顺环保科技有限公司 | Preparation method of nano nickel powder |
| CN114749676A (en) * | 2022-04-26 | 2022-07-15 | 淮安中顺环保科技有限公司 | High-flux preparation method of copper-nickel alloy nanoparticles |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117160459A (en) * | 2023-07-20 | 2023-12-05 | 淮安中顺环保科技有限公司 | Metal nano material and preparation method and application thereof |
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