CN114799195A - Preparation method of self-assembled micro-nano structure Cu-Ag nano particles - Google Patents
Preparation method of self-assembled micro-nano structure Cu-Ag nano particles Download PDFInfo
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- 229910017770 Cu—Ag Inorganic materials 0.000 title claims abstract description 51
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- 239000002904 solvent Substances 0.000 claims abstract description 60
- 239000010949 copper Substances 0.000 claims abstract description 55
- 229910052802 copper Inorganic materials 0.000 claims abstract description 45
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 26
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 26
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002244 precipitate Substances 0.000 claims abstract description 15
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001509 sodium citrate Substances 0.000 claims abstract description 14
- 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 abstract description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 9
- 239000012498 ultrapure water Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- -1 polyethylene pyrrolidone Polymers 0.000 claims abstract description 8
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 5
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 claims abstract description 4
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 17
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 7
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 7
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 claims description 3
- 229940071536 silver acetate Drugs 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 80
- 239000002245 particle Substances 0.000 description 42
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- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000001338 self-assembly Methods 0.000 description 5
- 229910017944 Ag—Cu Inorganic materials 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 231100000331 toxic Toxicity 0.000 description 4
- 230000002588 toxic effect Effects 0.000 description 4
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
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- 239000012279 sodium borohydride Substances 0.000 description 2
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- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention discloses a preparation method of self-assembled micro-nano structure Cu-Ag nano particles, which comprises the following steps: adding a copper source into an ethylene glycol solvent to prepare a solution A; adding sodium hypophosphite, polyethylene pyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent to prepare a solution B; heating the solution A in a water bath, magnetically stirring the solution A, dropwise adding the solution B, and reacting to obtain a nano copper solution; adding a silver source into an ethylene glycol solvent to prepare a solution C; respectively adding sodium citrate, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent to prepare a solution D; heating in a water bath, magnetically stirring the nano copper solution, adding the solution C and the solution D, and reacting to obtain a nano copper-silver solution; and (3) washing the precipitate obtained after centrifugal separation of the nano copper-silver solution by using absolute ethyl alcohol and ultrapure water, and drying to obtain the Cu-Ag nano particles. The method is simple, the whole process is finished in the air atmosphere, the reaction condition is mild, and the repeatability is good.
Description
Technical Field
The invention belongs to the technical field of nanoparticle preparation, and particularly relates to a preparation method of self-assembled micro-nano structure Cu-Ag nanoparticles.
Background
Nano copper and nano silver are widely used as conductive ink, electrode material, antibacterial material and the like. However, copper and silver alone have certain disadvantages, such as easy oxidation of elemental copper and high price of silver, which limits their wide application. Researches find that the Cu-Ag bimetallic nano-particles can overcome the defects of copper to a great extent and reduce the cost of silver.
The literature (Na; Rae; Kim; Kihyun; Shin; Inyu; Jung; Moonsub; Shim; Chemistry, H.J.J.O.P., Ag-Cu Bimetallic Nanoparticles with Enhanced Resistance to Oxidation: acidic Experimental and thermal study.2014) reports that Ag-Cu Bimetallic Nanoparticles prepared using an oleylamine-based thermal decomposition process have far better Oxidation Resistance than monometallic Cu Nanoparticles. However, the oleylamine used is expensive, difficult to clean and irritating to the skin. In the literature (Huang, Y.; Wu, F.; Zhou, Z.; Zhou, L.; Liu H.J.N., simulation of transformed Cu-Ag core-shell nanoparticles by composite method and anti-oxidative performance.2020,31 (17)) it was reported that the Cu-Ag core-shell nanoparticles with a size of 8nm were synthesized by a composite method of a displacement reaction and a chemical reduction reaction, but the reducing agent used, sodium borohydride, was extremely toxic and nitrogen gas was introduced to the reaction to prevent oxidation. The Synthesis of Ag-Cu nanoalloys by chemical co-reduction is reported in the literature (Taner, M.; Sayar, N.; yuaug, I.G.; Suzer, S.J.J.o.M.C., Synthesis, chromatography and antibacterial induction of silver-copper nanoalloys, 2011,21.), but highly toxic hydrazine hydrate is also used, and nitrogen is also fed to avoid oxidation of the copper. The method for synthesizing the nanoparticles in the method has complex process or needs inert atmosphere protection in the experimental process, and toxic reducing agents such as oleylamine, sodium borohydride, hydrazine hydrate and the like are often used.
In view of the above, it is necessary to research a method for preparing self-assembled micro-nano structure Cu-Ag nanoparticles to solve the above technical problems.
Disclosure of Invention
The invention aims to provide a preparation method of self-assembled micro-nano structure Cu-Ag nano particles, and aims to solve the technical problems that the process of the preparation method of the Ag-Cu nano particles is complex, inert atmosphere protection is required in the experimental process, and a toxic reducing agent is used in the experimental process.
In order to achieve the aim, the preparation method of the self-assembled micro-nano structure Cu-Ag nano particles comprises the following steps:
(1) adding a copper source into an ethylene glycol solvent, and performing ultrasonic oscillation until the copper source is completely dissolved in the ethylene glycol solvent to prepare a solution A;
(2) respectively adding sodium hypophosphite, polyethylene pyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent, and carrying out an ultrasonic oscillator until the sodium hypophosphite, the polyethylene pyrrolidone and the hexadecyl trimethyl ammonium bromide are completely dissolved in the ethylene glycol solvent to prepare a solution B;
(3) heating in a water bath, magnetically stirring the solution A prepared in the step (1), dropwise adding the solution B in the step (2), and reacting to obtain a nano copper solution;
(4) adding a silver source into an ethylene glycol solvent, and performing ultrasonic oscillation until the silver source is completely dissolved in the ethylene glycol solvent to prepare a solution C;
(5) respectively adding sodium citrate, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent, and carrying out an ultrasonic oscillator until the sodium citrate, the polyvinylpyrrolidone and the hexadecyl trimethyl ammonium bromide are completely dissolved in the ethylene glycol solvent to prepare a solution D;
(6) heating in a water bath, magnetically stirring the nano-copper solution prepared in the step (3), dropwise adding the solution C in the step (4) and the solution D in the step (5), and reacting to obtain a nano-copper-silver solution;
(7) and (5) carrying out centrifugal separation on the nano copper-silver solution in the step (6) for a plurality of times, washing the precipitate after the centrifugal separation for a plurality of times with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying to obtain the Cu-Ag nano particles.
Preferably, the copper source in step (1) is any one of copper sulfate pentahydrate, copper chloride dihydrate, copper nitrate trihydrate and anhydrous copper acetate.
Preferably, the molar ratio of the sodium hypophosphite in the step (2) to the copper source in the step (1) is 2-4: 1, the molar ratio of the polyethylene pyrrolidone in the step (2) to the copper source in the step (1) is 0.3-0.4: 1, the mole ratio of the hexadecyl trimethyl ammonium bromide in the step (2) to the copper source in the step (1) is 0.2-0.3: 1.
preferably, the temperature of the water bath heating and magnetic stirring in the step (3) is 70-90 ℃, and the reaction time of the solution A and the solution B is 40-60 min.
Preferably, the silver source in step (4) is any one of silver nitrate, silver acetate, silver sulfate and silver chloride.
Preferably, the molar ratio of the sodium citrate in the step (5) to the silver source in the step (4) is 1-2: 1, the molar ratio of the polyvinyl pyrrolidone in the step (5) to the silver source in the step (4) is 0.3-0.4: 1, the molar ratio of the hexadecyl trimethyl ammonium bromide in the step (5) to the silver source in the step (4) is 0.2-0.3: 1.
preferably, the molar ratio of the copper source in the step (1) to the silver source in the step (4) is 1: 0.2 to 0.4.
Preferably, the water bath heating and magnetic stirring temperature in the step (6) is 70-80 ℃, and the reaction time of the nano copper solution with the solution C and the solution D is 1.5-2.5 h.
Preferably, the drying temperature in the step (7) is 60-80 ℃, and the drying time is 18-26 h.
In summary, compared with the prior art, the invention has the beneficial effects that:
1. the invention adopts ethylene glycol as solvent and adopts sodium hypophosphite and sodium citrate with mild reducibility as reducing agents, thereby not only being environment-friendly, but also having good operability; by adding polyethylene pyrrolidone (PVP) and Cetyl Trimethyl Ammonium Bromide (CTAB) as dispersing agents in the reaction system, the agglomeration phenomenon of the particles is reduced.
2. The Cu-Ag nano-particles prepared by the method are spherical, small particles with the particle size of 5-10 nm are wrapped by macromolecular organic matters to form large particles with the particle size of about 150nm, a self-assembly structure is formed, the nano-structure can keep the activity of the nano-particles, and the micro-structure can ensure the stability and has the characteristics of uniform appearance, good dispersibility and better oxidation resistance.
3. The preparation method of the invention has simple operation, the whole process is completed in air atmosphere, and the reaction condition is mild.
Description of the drawings:
FIG. 1 is an XRD pattern of Cu-Ag nanoparticles obtained in example 1;
FIG. 2 is an XRD pattern of Cu-Ag nanoparticles obtained in example 2;
FIG. 3 is an XRD pattern of Cu-Ag nanoparticles obtained in example 3;
FIG. 4 is a TEM image of Cu-Ag nanoparticles obtained in example 3;
Detailed Description
The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without any inventive step, are within the scope of the present invention. Techniques, methods, and apparatus known to those of ordinary skill in the relevant art may not be discussed in detail but are intended to be part of the specification where appropriate. Furthermore, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
The specific embodiment provides a preparation method of self-assembled micro-nano structure Cu-Ag nano particles, which comprises the following steps:
step 1, preparing a nano copper solution:
1.1 weighing 1mmol of copper sulfate pentahydrate by an electronic balance and adding the copper sulfate pentahydrate into a 150mL beaker, measuring 30mL of glycol solvent by a measuring cylinder, adding the solvent into the beaker, and oscillating by ultrasonic until the copper sulfate pentahydrate is completely dissolved in the solvent glycol to prepare a solution A dissolved with the copper sulfate pentahydrate.
1.2 taking another beaker, weighing 30mL of ethylene glycol solvent by using a measuring cylinder, and respectively weighing 3mmol of sodium hypophosphite, 0.35mmol of polyvinyl pyrrolidone (PVP) and 0.2mmol of hexadecyl trimethyl ammonium bromide (CTAB) into the solvent by using an electronic balance; and putting the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol solvent to prepare a solution B.
1.3, putting the beaker dissolved with the solution A of the blue copperas obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 80 ℃; and (3) dropwise adding the solution B obtained in the step 1.2 into a beaker by using a rubber dropper at a proper rotating speed, and reacting for 60min to obtain the nano-copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added to each beaker, 0.2mmol of sodium citrate, 0.35mmol of polyvinylpyrrolidone (PVP) and 0.2mmol of cetyltrimethylammonium bromide (CTAB) were added to one beaker, and 0.2mmol of silver nitrate was weighed to the other beaker and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain a solution C, D.
2.2, putting the beaker of the nano-copper solution in the step (1) into a magnetic water bath heating pot, setting the temperature at 75 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 2 hours.
And 2.3 transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate for a plurality of times by using absolute ethyl alcohol and ultrapure water, and drying the precipitate for 24 hours in a drying oven at the temperature of 60 ℃ to obtain the Cu-Ag nano particles.
The XRD pattern of the prepared Cu-Ag nano-particles is shown in figure 1. And (3) map display: diffraction peaks for Cu appeared at 43.3 °, 50.4 ° and 74.1 °, which correspond to the (111), (200) and (220) crystal planes of the face centered cubic Cu standard spectrum (JCPDS No. 04-0836). In addition, the diffraction peaks of silver appear at 38.1 °, 44.3 °, 64.4 ° and 77.4 °, corresponding to the (111), (200), (220) and (311) crystal planes of face centered cubic silver (JCPDS No. 04-0783). The pure Cu-Ag bimetal is successfully prepared, and the (111) crystal face of Cu is the strongest peak in an XRD pattern.
Example 2
Step 1, preparing a nano copper solution:
1.1 weighing 1mmol of copper sulfate pentahydrate by an electronic balance and adding the copper sulfate pentahydrate into a 150mL beaker, measuring 30mL of glycol solvent by a measuring cylinder, adding the solvent into the beaker, and oscillating by ultrasonic until the copper sulfate pentahydrate is completely dissolved in the solvent glycol to prepare a solution A dissolved with the copper sulfate pentahydrate.
1.2 another beaker is taken, 30mL of ethylene glycol solvent is measured by a measuring cylinder, and 3mmol of sodium hypophosphite, 0.35mmol of PVP and 0.2mmol of CTAB are respectively measured by an electronic balance and added into the solvent. And putting the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol to prepare a solution B.
1.3, putting the beaker dissolved with the solution A of the blue copperas obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 80 ℃; and (3) dropwise adding the solution B obtained in the step 1.2 into a beaker by using a rubber dropper at a proper rotating speed, and reacting for 60min to obtain the nano-copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added to each beaker, 0.3mmol of sodium citrate, 0.35mmol of PVP and 0.2mmol of CTAB were added to one beaker, and 0.3mmol of silver nitrate was weighed into the other beaker and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain C, D.
2.2, putting the beaker of the nano-copper solution in the step (1) into a magnetic water bath heating pot, setting the temperature at 75 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 2 hours.
And 2.3 transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate for a plurality of times by using absolute ethyl alcohol and ultrapure water, and drying the precipitate for 24 hours in a drying oven at the temperature of 60 ℃ to obtain the Cu-Ag nano particles.
The XRD pattern of the prepared Cu-Ag nano-particles is shown in figure 2. And (3) map display: diffraction peaks for Cu appeared at 43.3 °, 50.4 ° and 74.1 °, which correspond to the (111), (200) and (220) crystal planes of the face centered cubic Cu standard spectrum (JCPDS No. 04-0836). In addition, the diffraction peaks of silver appear at 38.1 °, 44.3 °, 64.4 ° and 77.4 °, corresponding to the (111), (200), (220) and (311) crystal planes of face centered cubic silver (JCPDS No. 04-0783). The pure Cu-Ag bimetal is successfully prepared, compared with the example 1, the diffraction intensity of the Ag (111) crystal face is enhanced, and the Ag (111) crystal face becomes the strongest peak.
Example 3
Step 1, preparing Cu nanoparticles:
1.1 weighing 1mmol of copper sulfate pentahydrate by using an electronic balance and adding the copper sulfate pentahydrate into a 150mL beaker, measuring 30mL of glycol solvent by using a measuring cylinder, and adding the solvent into the beaker; and (3) using ultrasonic oscillation until the copper sulfate pentahydrate is completely dissolved in the solvent ethylene glycol to prepare a solution A in which the copper sulfate pentahydrate is dissolved.
1.2 another beaker is taken, 30mL of ethylene glycol solvent is measured by a measuring cylinder, and 3mmol of sodium hypophosphite, 0.35mmol of PVP and 0.2mmol of CTAB are respectively measured by an electronic balance and added into the solvent. And then placing the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol to prepare a solution B.
1.3, putting the beaker dissolved with the solution A of the blue copperas obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 80 ℃; and (3) dropwise adding the solution B obtained in the step (1.2) into a beaker by using a rubber head dropper at a proper rotating speed, and reacting for 60min to obtain a nano copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added to each beaker, 0.4mmol of sodium citrate, 0.35mmol of PVP and 0.2mmol of CTAB were added to one beaker, and 0.4mmol of silver nitrate was weighed into the other beaker and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain C, D.
2.2 placing the beaker of the nano-copper solution into a magnetic water bath heating pot, setting the temperature at 75 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 2 hours.
And 2.3, transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying the precipitate in a drying oven at the temperature of 60 ℃ for 24 hours to obtain the Cu-Ag nano particles.
The XRD pattern of the prepared Cu-Ag nano-particles is shown in figure 3. And (3) map display: diffraction peaks for Cu appeared at 43.3 °, 50.4 ° and 74.1 °, which correspond to the (111), (200) and (220) crystal planes of the face centered cubic Cu standard spectrum (JCPDS No. 04-0836). In addition, the diffraction peaks of silver appear at 38.1 °, 44.3 °, 64.4 ° and 77.4 °, corresponding to the (111), (200), (220) and (311) crystal planes of face centered cubic silver (JCPDS No. 04-0783). The pure Cu-Ag bimetal is successfully prepared, compared with the example 1 and the example 2, the diffraction intensity of the Ag (111) crystal face is enhanced, and the diffraction peak intensity of Ag is obviously higher than that of Cu.
A TEM image of Cu-Ag nanoparticles prepared in example 3 is shown in fig. 4. As can be seen from FIG. 4, the prepared nanoparticles are observed to be spherical, the large particles contain many small particles, the particle size of the large particles is about 150nm, and the particle size of the small particles is 5-10 nm. The polymer organic matter wraps the small particles to form round large particles with uniform shapes, and the round large particles become self-assembly structures. The small round particles are dark parts and the light parts are organic.
Example 4
Step 1, preparing a nano copper solution:
1.1 weighing 1mmol of copper chloride dihydrate by using an electronic balance, adding the copper chloride dihydrate into a 150mL beaker, measuring 30mL of glycol solvent by using a measuring cylinder, adding the solvent into the beaker, and oscillating by using ultrasonic waves until the copper chloride dihydrate is completely dissolved in the glycol solvent to prepare a solution A dissolved with the copper chloride dihydrate.
1.2 taking another beaker, weighing 30mL of ethylene glycol solvent by using a measuring cylinder, and respectively weighing 2mmol of sodium hypophosphite, 0.3mmol of polyvinyl pyrrolidone (PVP) and 0.3mmol of hexadecyl trimethyl ammonium bromide (CTAB) by using an electronic balance and adding into the solvent; and putting the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol solvent to prepare a solution B.
1.3, putting the beaker dissolved with the solution A of the copper chloride dihydrate obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 70 ℃; and (3) dropwise adding the solution B obtained in the step 1.2 into a beaker by using a rubber head dropper at a proper rotating speed, and reacting for 40min to obtain the nano-copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added thereto, respectively, one beaker was added with 0.2mmol of sodium citrate, 0.3mmol of polyvinylpyrrolidone (PVP) and 0.3mmol of cetyltrimethylammonium bromide (CTAB), and the other beaker was weighed with 0.2mmol of silver acetate and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain a solution C, D.
2.2, putting the beaker of the nano-copper solution in the step (1) into a magnetic water bath heating pot, setting the temperature at 70 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 2.5 hours.
And 2.3, transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate for a plurality of times by using absolute ethyl alcohol and ultrapure water, and drying the precipitate for 18 hours in a drying oven at the temperature of 80 ℃ to obtain the Cu-Ag nano particles.
The Cu-Ag nano-particles prepared in the embodiment 4 are spherical, large particles comprise a plurality of small particles, the particle size of the large particles is about 150nm, and the particle size of the small particles is 5-10 nm; the polymer organic matter wraps the small particles to form round large particles with uniform shapes, and the round large particles become self-assembly structures.
Example 5
Step 1, preparing a nano copper solution:
1.1 weighing 1mmol of copper nitrate trihydrate by using an electronic balance, adding the copper nitrate trihydrate into a 150mL beaker, measuring 30mL of glycol solvent by using a measuring cylinder, adding the solvent into the beaker, and oscillating by using ultrasonic until the copper nitrate trihydrate is completely dissolved in the glycol solvent to prepare a solution A in which the copper nitrate trihydrate is dissolved.
1.2 another beaker is taken, 30mL of ethylene glycol solvent is measured by a measuring cylinder, and 4mmol of sodium hypophosphite, 0.4mmol of PVP and 0.25mmol of CTAB are respectively measured by an electronic balance and added into the solvent. And putting the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol to prepare a solution B.
1.3, putting the beaker dissolved with the solution A of the copper nitrate trihydrate obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 90 ℃; and (3) dropwise adding the solution B obtained in the step 1.2 into a beaker by using a rubber dropper at a proper rotating speed, and reacting for 50min to obtain the nano-copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added to each beaker, 0.6mmol of sodium citrate, 0.4mmol of PVP and 0.25mmol of CTAB were added to one beaker, and 0.3mmol of silver sulfate was weighed into the other beaker and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain a solution C, D.
2.2, placing the beaker of the nano-copper solution obtained in the step (1) into a magnetic water bath heating pot, setting the temperature to be 80 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 1.5 hours.
And 2.3 transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying the precipitate in a drying oven at 70 ℃ for 26 hours to obtain the Cu-Ag nano particles.
The Cu-Ag nano-particles prepared in the embodiment 5 are spherical, large particles comprise a plurality of small particles, the particle size of the large particles is about 150nm, and the particle size of the small particles is 5-10 nm; the polymer organic matter wraps the small particles to form round large particles with uniform shapes, and the round large particles become self-assembly structures.
Example 6
The specific embodiment provides a preparation method of self-assembled micro-nano structure Cu-Ag nano particles, which comprises the following steps:
step 1, preparing a nano copper solution:
1.1 weighing 1mmol of anhydrous copper acetate by an electronic balance, adding the anhydrous copper acetate into a 150mL beaker, measuring 30mL of glycol solvent by using a measuring cylinder, adding the solvent into the beaker, and using ultrasonic oscillation until the anhydrous copper acetate is completely dissolved in the solvent glycol to prepare a solution A dissolved with the anhydrous copper acetate.
1.2 taking another beaker, weighing 30mL of ethylene glycol solvent by using a measuring cylinder, and respectively weighing 3mmol of sodium hypophosphite, 0.35mmol of polyvinyl pyrrolidone (PVP) and 0.2mmol of hexadecyl trimethyl ammonium bromide (CTAB) into the solvent by using an electronic balance; and putting the beaker containing the mixed solution into an ultrasonic oscillator for ultrasonic treatment for a certain time until the reagent is completely dissolved in the glycol solvent to prepare a solution B.
1.3, placing the beaker dissolved with the anhydrous copper acetate solution A obtained in the step 1.1 into a magnetic water bath heating pot with the temperature set at 80 ℃; and (3) dropwise adding the solution B obtained in the step 1.2 into a beaker by using a rubber dropper at a proper rotating speed, and reacting for 60min to obtain the nano-copper solution.
Step 2, preparation of Cu-Ag nano particles
2.1 two beakers were taken and 30mL of ethylene glycol was added thereto, respectively, one beaker was added with 0.3mmol of sodium citrate, 0.35mmol of polyvinylpyrrolidone (PVP) and 0.2mmol of cetyltrimethylammonium bromide (CTAB), and the other beaker was weighed with 0.2mmol of silver chloride and shaken with ultrasound until completely dissolved in the solvent ethylene glycol to obtain a solution C, D.
2.2, putting the beaker of the nano-copper solution in the step (1) into a magnetic water bath heating pot, setting the temperature at 75 ℃, adding the solution C, D into the beaker by a dropper at a certain rotating speed, and reacting for 2 hours.
And 2.3 transferring the reacted solution into a centrifuge tube, centrifuging the solution in the centrifuge tube for a plurality of times, washing the obtained precipitate with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying the precipitate in a drying oven at the temperature of 60 ℃ for 22 hours to obtain the Cu-Ag nano particles.
The Cu-Ag nano-particles prepared in the embodiment 6 are spherical, large particles comprise a plurality of small particles, the particle size of the large particles is about 150nm, and the particle size of the small particles is 5-10 nm; the polymer organic matter wraps the small particles to form round large particles with uniform shapes, and the round large particles become self-assembly structures.
The previous description is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. A preparation method of self-assembled micro-nano structure Cu-Ag nano particles is characterized by comprising the following steps:
(1) adding a copper source into an ethylene glycol solvent, and performing ultrasonic oscillation until the copper source is completely dissolved in the ethylene glycol solvent to prepare a solution A;
(2) respectively adding sodium hypophosphite, polyethylene pyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent, and carrying out an ultrasonic oscillator until the sodium hypophosphite, the polyethylene pyrrolidone and the hexadecyl trimethyl ammonium bromide are completely dissolved in the ethylene glycol solvent to prepare a solution B;
(3) heating in a water bath, magnetically stirring the solution A prepared in the step (1), dropwise adding the solution B prepared in the step (2), and reacting to obtain a nano copper solution;
(4) adding a silver source into an ethylene glycol solvent, and performing ultrasonic oscillation until the silver source is completely dissolved in the ethylene glycol solvent to prepare a solution C;
(5) respectively adding sodium citrate, polyvinylpyrrolidone and hexadecyl trimethyl ammonium bromide into an ethylene glycol solvent, and carrying out an ultrasonic oscillator until the sodium citrate, the polyvinylpyrrolidone and the hexadecyl trimethyl ammonium bromide are completely dissolved in the ethylene glycol solvent to prepare a solution D;
(6) heating in a water bath, magnetically stirring the nano-copper solution prepared in the step (3), dropwise adding the solution C in the step (4) and the solution D in the step (5), and reacting to obtain a nano-copper-silver solution;
(7) and (4) carrying out centrifugal separation on the nano copper-silver solution in the step (6) for a plurality of times, washing the precipitate after the centrifugal separation for a plurality of times with absolute ethyl alcohol and ultrapure water for a plurality of times, and drying to obtain the Cu-Ag nano particles.
2. The method for preparing self-assembled micro-nano structure Cu-Ag nanoparticles according to claim 1, wherein the copper source in step (1) is any one of copper sulfate pentahydrate, copper chloride dihydrate, copper nitrate trihydrate and anhydrous copper acetate.
3. The preparation method of self-assembled micro-nano structure Cu-Ag nanoparticles according to claim 1, wherein the molar ratio of sodium hypophosphite in the step (2) to the copper source in the step (1) is 2-4: 1, the molar ratio of the polyethylene pyrrolidone in the step (2) to the copper source in the step (1) is 0.3-0.4: 1, the mole ratio of the hexadecyl trimethyl ammonium bromide in the step (2) to the copper source in the step (1) is 0.2-0.3: 1.
4. the preparation method of self-assembled micro-nano structure Cu-Ag nanoparticles according to claim 1, wherein the temperature of water bath heating and magnetic stirring in the step (3) is 70-90 ℃, and the reaction time of the solution A and the solution B is 40-60 min.
5. The preparation method of the self-assembled micro-nano structure Cu-Ag nanoparticle according to claim 1, wherein the silver source in the step (4) is any one of silver nitrate, silver acetate, silver sulfate and silver chloride.
6. The preparation method of the self-assembled micro-nano structure Cu-Ag nano particles according to claim 1, wherein the molar ratio of the sodium citrate in the step (5) to the silver source in the step (4) is 1-2: 1, the molar ratio of the polyvinyl pyrrolidone in the step (5) to the silver source in the step (4) is 0.3-0.4: 1, the molar ratio of the hexadecyl trimethyl ammonium bromide in the step (5) to the silver source in the step (4) is 0.2-0.3: 1.
7. the method for preparing self-assembled micro-nano structure Cu-Ag nanoparticles according to claim 1, wherein the molar ratio of the copper source in the step (1) to the silver source in the step (4) is 1: 0.2 to 0.4.
8. The preparation method of the self-assembled micro-nano structure Cu-Ag nanoparticles according to claim 1, wherein the water bath heating magnetic stirring temperature in the step (6) is 70-80 ℃, and the reaction time of the nano copper solution with the solution C and the solution D is 1.5-2.5 h.
9. The preparation method of the self-assembled micro-nano structure Cu-Ag nano particles according to claim 1, wherein the drying temperature in the step (7) is 60-80 ℃, and the drying time is 18-26 h.
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