CN113600826A - Preparation method of small-size Cu @ Ag core-shell nanoparticles - Google Patents
Preparation method of small-size Cu @ Ag core-shell nanoparticles Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 104
- 239000011258 core-shell material Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 79
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 78
- 239000010949 copper Substances 0.000 claims abstract description 53
- 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 abstract description 41
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 39
- 239000012298 atmosphere Substances 0.000 claims abstract description 14
- 239000011261 inert gas Substances 0.000 claims abstract description 13
- 238000010926 purge Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 239000002245 particle Substances 0.000 description 21
- 238000009826 distribution Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 10
- 238000010586 diagram Methods 0.000 description 7
- 238000003760 magnetic stirring Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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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Abstract
The invention provides a preparation method of small-size Cu @ Ag core-shell nanoparticles, which comprises the following steps: step S1: dissolving copper acetylacetonate in oleylamine solution, and obtaining blue clear and transparent copper acetylacetonate oleylamine solution after completely dissolving the copper acetylacetonate in oleylamine solution; step S2: pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing inert gas into the four-mouth bottle for continuous purging, and reacting at high temperature to obtain a Cu nanoparticle solution; step S3: dissolving silver nitrate in an oleylamine solution to obtain a silver nitrate oleylamine solution; step S4: and (3) dripping silver nitrate oleylamine solution into the low-temperature Cu nano-particle solution, keeping the inert gas atmosphere and continuously reacting to obtain the Cu @ Ag core-shell nano-particles. The Cu @ Ag core-shell nano-particles prepared by the preparation method of the small-size Cu @ Ag core-shell nano-particles have the characteristics of uniform appearance, size smaller than 20nm, good dispersibility, complete core-shell structure and better oxidation resistance.
Description
Technical Field
The invention belongs to the field of synthesis of small-size nano metal particles, and particularly relates to a preparation method of small-size Cu @ Ag core-shell nano particles.
Background
The nano metal material represented by nano metal particles of Ag, Cu and the like has excellent mechanical property, high electric conductivity and heat conduction property, is widely applied to manufacturing interconnection circuits, capacitors or resistance type sensing units of flexible electronic products, and the manufactured flexible electronic products have excellent practicability.
The electrical conductivity and thermal conductivity of Cu are similar to those of Ag, but the cost is only 1% of that of Ag, and Cu is the best substitute material for Ag from the aspect of industrial cost. However, Cu nanoparticles are very easy to oxidize in air atmosphere, and CuO and Cu generated by oxidation are generated2O has a high melting point and a high resistivity, and prevents the diffusion of elements of Cu nanoparticles, making it difficult to sinter at low temperatures. Therefore, the sintering of Cu nanoparticles generally needs to be performed in a reducing atmosphere or a vacuum atmosphere, and the severe sintering process conditions severely restrict the industrial application of Cu nanoparticles.
Disclosure of Invention
In order to solve the problems in the prior art, the application provides a preparation method of small-size Cu @ Ag core-shell nanoparticles, an Ag shell layer is modified on the surface of the Cu nanoparticles to form a Cu @ Ag core-shell structure, the small-size Cu nanoparticles are prevented from being oxidized in the air atmosphere, and the thermal conductivity and the electric conductivity of the small-size Cu @ Ag core-shell nanoparticles are improved.
The invention provides a preparation method of small-size Cu @ Ag core-shell nanoparticles, which comprises the following steps:
step S1: dissolving copper acetylacetonate in oleylamine solution, and obtaining blue clear and transparent copper acetylacetonate oleylamine solution after completely dissolving the copper acetylacetonate in oleylamine solution;
step S2: pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing inert gas into the four-mouth bottle, continuously purging the copper acetylacetonate oleylamine solution, and reacting at high temperature to obtain a Cu nanoparticle solution;
step S3: dissolving silver nitrate in an oleylamine solution to obtain a silver nitrate oleylamine solution; and
step S4: and (3) dripping silver nitrate oleylamine solution into the low-temperature Cu nano-particle solution, keeping the inert gas atmosphere and continuously reacting to obtain the Cu @ Ag core-shell nano-particles.
In a preferred embodiment, the concentration of the copper acetylacetonate oleylamine solution in the step S1 is 0.01 to 0.5 mol/L.
In a preferred embodiment, the reaction temperature of the copper acetylacetonate oleylamine solution in the step S2 is 150 to 300 ℃, and the reaction time is 0.5 to 10 hours.
In a preferred embodiment, the concentration of the silver nitrate oleylamine solution in the step S3 is 0.005-0.5 mol/L.
In a preferred embodiment, the reaction temperature of the silver nitrate oleylamine solution and the Cu nanoparticle solution in the step S4 is 50-120 ℃, and the reaction time is 0.5-10 h.
In a preferred embodiment, the Cu nanoparticle solution in step S4 is cooled to below 50 ℃ before reacting with the silver nitrate oleylamine solution.
In a preferred embodiment, the Cu @ Ag core-shell nanoparticles are centrifugally washed with n-hexane or a hot ethanol solution.
In a preferred embodiment, the inert gas comprises one of nitrogen and argon.
The invention relates to a preparation method of small-size Cu @ Ag core-shell nano particles, which adopts a process of continuously preparing the Cu @ Ag core-shell nano particles by a one-pot method, firstly prepares the Cu nano particles with the diameter less than 20nm, then directly injects a silver nitrate solution into a Cu nano particle solution, and finally prepares the Cu @ Ag core-shell nano particles which are uniform in appearance, less than 20nm in size, good in dispersity, complete in core-shell structure, good in oxidation resistance (not oxidized in the air atmosphere of 150 ℃) and capable of being stably stored at room temperature through galvanic displacement reaction. And secondly, by adjusting the thickness of an Ag shell layer of the Cu @ Ag core-shell structure, the Cu nanoparticles can be effectively protected, the particles are prevented from being oxidized and agglomerated, and the storage property of the Cu @ Ag core-shell nanoparticle conductive ink is remarkably improved. And thirdly, the Cu @ Ag core-shell nano-particles have lower manufacturing cost than the current commercialized Ag nano-particles with the same size, and are beneficial to large-scale application. In addition, the sintering temperature of the nano-metal particles is directly related to the particle size, and the smaller the particle size, the lower the sintering temperature. Therefore, the small-sized Cu @ Ag core-shell nano-particles prepared by the method can quickly form a high-performance nano metal sintered body at low temperature in the air atmosphere.
Drawings
The accompanying drawings are included to provide a further understanding of the embodiments and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments and together with the description serve to explain the principles of the invention. Other embodiments and many of the intended advantages of embodiments will be readily appreciated as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numerals designate corresponding similar parts.
FIG. 1 is a flow chart of a method of making small size Cu @ Ag core-shell nanoparticles of an embodiment of the present invention;
FIG. 2 is a diagram of an experimental setup for a method of making small size Cu @ Ag core-shell nanoparticles according to an embodiment of the present invention;
fig. 3 is (a) a Transmission Electron Microscope (TEM) picture of Cu nanoparticles prepared in step S2 of an example of the present invention; (B) a particle size distribution map; (C) x-ray diffraction (XRD) pattern;
FIG. 4 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 1 of the present invention; (B) a particle size distribution map; (C) an area scan Element Distribution (EDS) map; (D) line scan EDS plots;
FIG. 5 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 2 of the present invention; (B) a particle size distribution map; (C) area scan EDS plots; (D) line scan EDS plots;
FIG. 6 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 3 of the present invention; (B) a particle size distribution map; (C) area scan EDS plots; (D) line scan EDS plots;
fig. 7 is a temperature-changing XRD pattern of Cu @ Ag core-shell nanoparticles prepared in example 2 and example 3 of the present invention under air atmosphere.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the present invention will be described in further detail with reference to the accompanying drawings, and it is apparent that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention will be described in detail with reference to the attached drawing 1, and the preparation method of the small-size Cu @ Ag core-shell nano-particles comprises the following steps:
step S1: dissolving copper acetylacetonate in oleylamine solution, and obtaining blue clear and transparent copper acetylacetonate oleylamine solution after completely dissolving the copper acetylacetonate in the oleylamine solution by magnetic stirring;
step S2: pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing inert gas (such as nitrogen) into the four-mouth bottle to continuously blow the copper acetylacetonate oleylamine solution (the whole reaction keeps inert gas atmosphere), then raising the temperature to 150-300 ℃, continuously stirring by magnetic force in the whole process, and reacting for 0.5-10 h at the temperature to obtain a Cu nanoparticle solution;
step S3: under the condition of room temperature and light shielding, dissolving silver nitrate into the oleylamine solution with the assistance of ultrasound to obtain silver nitrate oleylamine solution; and
step S4: reducing the temperature of the reacted Cu nano-particle solution to below 50 ℃ to obtain a low-temperature Cu nano-particle solution; injecting a silver nitrate oleylamine solution into a separating funnel, then dropping a low-temperature Cu nano-particle oleylamine solution, keeping an inert gas atmosphere, after injecting the silver nitrate solution, raising the temperature to 50-120 ℃, reacting for 0.5-10 h, magnetically stirring in the whole process, obtaining Cu @ Ag core-shell nano-particles after the reaction is finished, and finally centrifugally cleaning the Cu @ Ag core-shell nano-particles for three times by using n-hexane.
FIG. 2 is a diagram of an experimental apparatus for the preparation method of small-sized Cu @ Ag core-shell nanoparticles, as shown in FIG. 2, an experimental reaction vessel is a four-mouth bottle, one of the mouths is an inlet and an outlet of inert gas, a real-time temperature detection sensor and a temperature protection sensor are respectively inserted into two mouths, the sensors are protected by glass sleeves to prevent contact with a reaction solution, the remaining mouth in the middle is inserted into a separating funnel, and the whole apparatus is kept closed except for an inert gas outlet.
Fig. 3 is (a) a Transmission Electron Microscope (TEM) picture of Cu nanoparticles prepared in step S2 of the present invention; (B) a particle size distribution map; (C) x-ray diffraction (XRD) pattern. Cu nanoparticles in the TEM picture have good dispersibility and uniform appearance, and the particles are basically spherical. The particle size distribution diagram intuitively shows that the average size of the Cu nanoparticles is 17nm, the distribution range is narrow, and the size is small. According to XRD results, in addition to a diffraction peak containing simple substance Cu, a diffraction peak corresponding to Cu exists at 37 DEG in a Cu nanoparticle sample2The diffraction peak of the (111) crystal face of O shows that the Cu nanoparticles are very easy to oxidize in the air atmosphere when not protected by the Ag shell layer.
Example 1
5mmol of copper acetylacetonate is dissolved in 100ml of oleylamine solution and after complete dissolution by magnetic stirring, a blue, clear and transparent solution of copper acetylacetonate oleylamine is obtained. Pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing nitrogen gas for washing (introducing nitrogen gas continuously in the whole reaction), then raising the temperature to 240 ℃, keeping magnetic stirring in the whole process, and reacting for 3 hours at the temperature to obtain the Cu nanoparticle solution. And reducing the temperature of the reacted Cu nano-particle solution to be below 50 ℃ to obtain the low-temperature Cu nano-particle solution.
Under the condition of room temperature and light protection, 0.625mmol of silver nitrate is dissolved into 50ml of oleylamine solution with the assistance of ultrasound, and the silver nitrate oleylamine solution is obtained. Injecting silver nitrate oleylamine solution into a separating funnel, then dripping low-temperature Cu nano-particle oleylamine solution, after injecting the silver nitrate solution, raising the temperature to 80 ℃, preserving the temperature for 3 hours, magnetically stirring the whole process, and obtaining Cu @ Ag core-shell nano-particles after the reaction is finished. And (3) centrifugally cleaning the Cu @ Ag core-shell nanoparticles for three times by using n-hexane.
FIG. 4 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 1 of the present invention; (B) a particle size distribution map; (C) an area scan Element Distribution (EDS) map; (D) line scan EDS plots. According to a TEM image and a particle size distribution diagram, the Cu @ Ag core-shell nano particles are very uniform in appearance, free of obvious agglomeration, good in dispersity, 16nm in average particle size and narrow in distribution range; based on the surface scanning and line scanning EDS diagrams, the Ag shell layer is completely wrapped outside the Cu nanoparticles, and a relatively complete Cu @ Ag core-shell structure is formed.
Example 2
8mmol of copper acetylacetonate is dissolved in 100ml of oleylamine solution, and after complete dissolution by magnetic stirring, a blue, clear and transparent copper acetylacetonate oleylamine solution is obtained. Pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing nitrogen gas for washing (introducing nitrogen gas continuously in the whole reaction), raising the temperature to 240 ℃, keeping magnetic stirring in the whole process, and reacting for 3 hours at the temperature to obtain the CuNPs solution. And (3) reducing the temperature of the reacted CuNPs solution to be below 50 ℃ to obtain the low-temperature CuNPs solution.
Under the condition of room temperature and light protection, 1mmol of silver nitrate is dissolved into 50ml of oleylamine solution with the assistance of ultrasound, and the silver nitrate oleylamine solution is obtained. Injecting silver nitrate oleylamine solution into a separating funnel, then dropping low-temperature CuNPs oleylamine solution, keeping nitrogen atmosphere, after injecting silver nitrate solution, raising the temperature to 80 ℃, preserving heat for 3 hours, magnetically stirring in the whole process, and obtaining Cu @ Ag core-shell nano particles after the reaction is finished. And (3) centrifugally cleaning the Cu @ Ag core-shell nanoparticles for three times by using n-hexane.
FIG. 5 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 2 of the present invention; (B) a particle size distribution map; (C) area scan EDS plots; (D) line scan EDS plots. The concentration ratios of the copper acetylacetonate oleylamine solution and the silver nitrate oleylamine solution of this example and example 1 were the same and were 4: 1. the difference is that the concentration of the copper acetylacetonate oleylamine solution of example 2 was 0.08mol/L and the concentration of the copper acetylacetonate oleylamine solution of example 1 was 0.05 mol/L. According to a TEM image and a particle size distribution diagram, the Cu @ Ag core-shell nanoparticles prepared in example 2 are more uniform in morphology, have excellent dispersibility and have an average particle size of only 12.5 nm; EDS (enhanced data system) images of line scanning and surface scanning prove that the Cu @ Ag core-shell structure has better integrity.
Example 3
8mmol of copper acetylacetonate is dissolved in 100ml of oleylamine solution, and after complete dissolution by magnetic stirring, a blue, clear and transparent copper acetylacetonate oleylamine solution is obtained. Pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing nitrogen gas for washing (introducing nitrogen gas continuously in the whole reaction), then raising the temperature to 240 ℃, keeping magnetic stirring in the whole process, and reacting for 3 hours at the temperature to obtain the Cu nanoparticle solution. And reducing the temperature of the reacted Cu nano-particle solution to be below 50 ℃ to obtain the low-temperature Cu nano-particle solution.
Under the condition of room temperature and light protection, 0.8mmol of silver nitrate is dissolved into 50ml of oleylamine solution with the assistance of ultrasound to obtain silver nitrate oleylamine solution. Injecting silver nitrate oleylamine solution into a separating funnel, then dripping low-temperature Cu nano-particle oleylamine solution, keeping the nitrogen atmosphere, after injecting silver nitrate solution, raising the temperature to 80 ℃, preserving the temperature for 3 hours, magnetically stirring the whole process, and obtaining Cu @ Ag core-shell nano-particles after the reaction is finished. And (3) centrifugally cleaning the Cu @ Ag core-shell nanoparticles for three times by using n-hexane.
FIG. 6 is (A) TEM picture of Cu @ Ag core-shell nanoparticles prepared in example 3 of the present invention; (B) a particle size distribution map; (C) area scan EDS plots; (D) line scan EDS plots. The concentration of the copper acetylacetonate oleylamine solution of example 3 was 0.08mol/L, and the concentration ratio of the copper acetylacetonate oleylamine solution to the silver nitrate oleylamine solution was 5: 1. according to a TEM image and a particle size distribution diagram, the average particle size of the Cu @ Ag core-shell nanoparticles prepared in example 3 is 13 nm; EDS (enhanced data system) images of line scanning and surface scanning prove that the core-shell structure of the Cu @ Ag core-shell nano-particles is basically complete.
Fig. 7 is a temperature-changing XRD pattern of Cu @ Ag core-shell nanoparticles prepared in example 2 and example 3 of the present invention under air atmosphere. Wherein the initial particle samples in (a) and (B) were derived from example 2 (i.e., the ratio of the concentrations of copper acetylacetonate oleylamine solution to silver nitrate oleylamine solution was 4: 1) and example 3 (i.e., the ratio of the concentrations of copper acetylacetonate oleylamine solution to silver nitrate oleylamine solution was 5: 1), respectively. When the concentration ratio of the copper acetylacetonate oleylamine solution to the silver nitrate oleylamine solution is 4: 1, the Ag shell layer of the obtained Cu @ Ag core-shell nano-particles is relatively thick, and no obvious Cu is still observed when the Cu @ Ag core-shell nano-particles are heated to 160 DEG C2An O diffraction peak; when the heating temperature reached 190 ℃, Cu was first observed at 37 °2Diffraction peak of O (111) plane; as the temperature continuesIncreasing, gradually sharpening diffraction peak of Ag, Cu2The diffraction peak of O is continuously enhanced, which shows that Ag gradually separates from the surface of the Cu core and is partially gathered, and the Cu core loses the protection of the Ag shell layer and is gradually oxidized. When the concentration ratio of the copper acetylacetonate oleylamine solution to the silver nitrate oleylamine solution is 5: 1, the obtained Cu @ Ag core-shell nano-particles have relatively thin Ag shell layers, and the Cu @ Ag core-shell nano-particles have no obvious oxidation peak at room temperature, but when the temperature is increased to 100 ℃, the Cu is added2The diffraction peak of O begins to appear; with increasing temperature, Cu2O is further oxidized to CuO. Compared with example 2, the oxidation resistance of the Cu @ Ag core-shell nanoparticles obtained in example 3 is slightly poor. Therefore, the Cu @ Ag core-shell nano-particles obtained in the embodiment 2 can achieve a better anti-oxidation effect, and the production cost can be continuously reduced by optimizing the thickness of the Ag shell layer.
The Cu nanoparticles prepared by the preparation method of the small-size Cu @ Ag core-shell nanoparticles and the Cu @ Ag core-shell nanoparticles have the diameter of less than 20nm, narrow particle size distribution, basically spherical particle appearance, good dispersibility and no agglomeration phenomenon; the Cu @ Ag core-shell nano-particles have complete core-shell structures, are good in oxidation resistance and have no obvious oxidation phenomenon at 150 ℃; the Ag shell layer of the Cu @ Ag core-shell nano particles can change the thickness of the Ag shell layer by changing the concentration of injected silver nitrate, and the oxidation resistance and the cost of Cu @ Ag are adjusted; the invention only needs three materials, oleylamine is used as a solvent and a surfactant, excessive experimental materials are not needed, high pressure is not needed in the experiment, and the method is safe and simple; the invention uses a 'one-pot' continuous preparation process, does not need centrifugal cleaning after synthesizing the Cu nano particles, can effectively avoid the oxidation of the Cu nano particles, reduces the experimental operation flow and the cost, and is beneficial to industrial production.
While the principles of the invention have been described in detail in connection with the preferred embodiments thereof, it will be understood by those skilled in the art that the foregoing embodiments are merely illustrative of exemplary implementations of the invention and are not limiting of the scope of the invention. The details of the embodiments are not to be interpreted as limiting the scope of the invention, and any obvious changes, such as equivalent alterations, simple substitutions and the like, based on the technical solution of the invention, can be interpreted without departing from the spirit and scope of the invention.
Claims (8)
1. A preparation method of small-size Cu @ Ag core-shell nanoparticles is characterized by comprising the following steps:
step S1: dissolving copper acetylacetonate in oleylamine solution, and obtaining blue clear and transparent copper acetylacetonate oleylamine solution after completely dissolving the copper acetylacetonate in oleylamine solution;
step S2: pouring the copper acetylacetonate oleylamine solution into a four-mouth bottle, introducing inert gas into the four-mouth bottle, continuously purging the copper acetylacetonate oleylamine solution, and reacting at high temperature to obtain a Cu nanoparticle solution;
step S3: dissolving silver nitrate in the oleylamine solution to obtain a silver nitrate oleylamine solution; and
step S4: and dripping the silver nitrate oleylamine solution into the low-temperature Cu nano-particle solution, keeping the inert gas atmosphere and continuously reacting to obtain the Cu @ Ag core-shell nano-particles.
2. The preparation method of small-sized Cu @ Ag core-shell nanoparticles as claimed in claim 1, wherein the concentration of the copper acetylacetonate oleylamine solution in step S1 is 0.01-0.5 mol/L.
3. The preparation method of small-size Cu @ Ag core-shell nanoparticles as claimed in claim 1, wherein the reaction temperature of the copper acetylacetonate oleylamine solution in step S2 is 150-300 ℃ and the reaction time is 0.5-10 h.
4. The preparation method of small-size Cu @ Ag core-shell nanoparticles as claimed in claim 1, wherein the concentration of the silver nitrate oleylamine solution in the step S3 is 0.005-0.5 mol/L.
5. The preparation method of small-size Cu @ Ag core-shell nanoparticles as claimed in claim 1, wherein the reaction temperature of the silver nitrate oleylamine solution and the Cu nanoparticle solution in step S4 is 50-120 ℃, and the reaction time is 0.5-10 h.
6. The method for preparing small-size Cu @ Ag core-shell nanoparticles according to claim 1, wherein the Cu nanoparticle solution in the step S4 is cooled to below 50 ℃ before being reacted with the silver nitrate oleylamine solution.
7. The method for preparing small-size Cu @ Ag core-shell nanoparticles according to claim 1, wherein the Cu @ Ag core-shell nanoparticles are centrifugally cleaned by n-hexane or a hot ethanol solution.
8. The method of making small-sized Cu @ Ag core-shell nanoparticles of claim 1, wherein the inert gas comprises one of nitrogen and argon.
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| Publication number | Priority date | Publication date | Assignee | Title |
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