CN114226747B - Preparation method of nano silver particles with good ethanol dispersibility - Google Patents
Preparation method of nano silver particles with good ethanol dispersibility Download PDFInfo
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- CN114226747B CN114226747B CN202111562826.3A CN202111562826A CN114226747B CN 114226747 B CN114226747 B CN 114226747B CN 202111562826 A CN202111562826 A CN 202111562826A CN 114226747 B CN114226747 B CN 114226747B
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 98
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000002245 particle Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000010438 heat treatment Methods 0.000 claims abstract description 59
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007787 solid Substances 0.000 claims abstract description 40
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims abstract description 39
- 239000008367 deionised water Substances 0.000 claims abstract description 38
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 38
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 36
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 35
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 claims abstract description 23
- 239000004332 silver Substances 0.000 claims abstract description 23
- 239000000725 suspension Substances 0.000 claims abstract description 21
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002253 acid Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 16
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims abstract description 13
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims abstract description 13
- 229940045803 cuprous chloride Drugs 0.000 claims abstract description 13
- 235000009518 sodium iodide Nutrition 0.000 claims abstract description 13
- CIWBSHSKHKDKBQ-UHFFFAOYSA-N 2-(1,2-dihydroxyethyl)-3,4-dihydroxy-2h-furan-5-one Chemical compound OCC(O)C1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-UHFFFAOYSA-N 0.000 claims abstract description 11
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000013078 crystal Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229960003280 cupric chloride Drugs 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 135
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 230000000844 anti-bacterial effect Effects 0.000 description 5
- 241000894006 Bacteria Species 0.000 description 3
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 206010059866 Drug resistance Diseases 0.000 description 2
- 241000361919 Metaphire sieboldi Species 0.000 description 2
- -1 antibacterial Chemical compound 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 150000003057 platinum Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000006188 syrup Substances 0.000 description 2
- 235000020357 syrup Nutrition 0.000 description 2
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000003042 antagnostic effect Effects 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000036457 multidrug resistance Effects 0.000 description 1
- 239000010956 nickel silver Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
- 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
Abstract
The invention discloses a preparation method of nano silver particles with good ethanol dispersibility, which comprises the following steps: adding simple substance platinum and silver into a solution A and a solution B formed by mixed acid of nitric acid and hydrochloric acid respectively, heating the solution A to obtain an orange transparent solution, and adding a composite solution of cupric chloride and cuprous chloride to obtain a solution I; heating the solution B and the solution A to obtain a solid, adding a composite solution of sodium bromide and sodium iodide to form a suspension, and adding the suspension into the solution I for heating and activating; sequentially adding an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone, a methanol-deionized water solution of glycerol and an ethanol solution of pentaerythritol, respectively heating and stirring for reaction; and cooling the reaction product, adding diethyl ether, centrifuging to obtain a gray brown solid, adding deionized water to obtain an gray white suspension, adding acetone, centrifuging to obtain an gray white solid, and dissolving the gray white solid in ethanol to obtain an ethanol dispersion of the nano silver spheres. The nano silver particles prepared by the method have more uniform particle size distribution, smaller particle size and better dispersibility in ethanol.
Description
Technical Field
The invention relates to the technical field of nano material preparation, in particular to a preparation method of nano silver particles with good ethanol dispersibility.
Background
Bacterial multi-drug resistance is one of global potential crisis, and traditional modes of utilizing antibiotics lead to stronger bacterial drug resistance, so the development of novel antibacterial materials is particularly critical. The nanometer material is a material with at least one dimension in nanometer size in three-dimensional space, and has the shape of cube, sphere, diamond, triangle, etc. The nano silver as a novel polymer material in the 21 st century has wide application prospect in the fields of catalysis, optics, electric conduction, antibiosis, biological materials and the like. Nano silver has excellent photo-thermal activity and good light absorption capacity in the near infrared to ultraviolet region, so that they can raise the local temperature of surrounding medium under the irradiation of near infrared light to realize photo-thermal conversion, thereby thermally inactivating different types of bacteria.
The invention with the application number of 202110340772.X discloses a preparation method of photo-thermal/photo-acoustic/antibacterial multifunctional nano silver balls, which is characterized in that a silver source is mixed with obtained nitrogen-doped graphene quantum dots, ultraviolet light is used for irradiating for 2-4 hours, and redundant nitrogen-doped graphene quantum dots are cleaned, so that nano silver ball clusters wrapped by the graphene quantum dots are obtained. The invention has disclosed a earthworm syrup nanometer silver hydrogel patch and its preparation method of application number 201811328175.X, its core method is to add nanometer silver ion directly in earthworm syrup, thus realize "strong union", make it high-efficient safe and difficult for making the bacterium produce the drug resistance. Li Junyu from Shandong university utilizes antibacterial substances obtained from antagonistic bacteria, marine bacillus subtilis, as a reducing agent to prepare nano silver particles, and the antibacterial substances and the nano silver particles cooperatively play a synergistic effect.
From the foregoing, it is apparent that, although the specific properties of nano-silver such as antibacterial, conductive and special photo-thermal effects have been widely known, the preparation methods of nano-silver are quite different. However, an important disadvantage of nanomaterials is their extreme tendency to agglomerate, which in turn causes them to lose their own unique properties. As for the method of current literature query, in order to prolong the storage period, a coating method is often used, for example, application No. 202110340772.X uses graphene to coat silver nanoparticles, but coating easily causes the loss of the performance of the silver nanoparticles themselves.
Disclosure of Invention
The invention aims to provide a preparation method of nano silver particles with good ethanol dispersibility, which is characterized in that a new silver core is formed on the surface of a platinum core, so that the formed silver particles effectively overcome the defect that the nano silver can be stabilized by coating, the nano silver particles prepared by the preparation method have uniform particle size within the range of 50-200nm, can be directly dispersed in ethanol in the form of nano silver particles, and form a light yellow transparent solution.
The invention adopts the following technical scheme:
a method for preparing nano silver particles with good ethanol dispersibility, the method comprising:
(1) The following solutions were prepared:
solution A: adding the simple substance platinum into mixed acid of nitric acid and hydrochloric acid, and heating to react until the simple substance platinum is dissolved;
solution B: adding elemental silver into mixed acid of nitric acid and hydrochloric acid, and heating to react until the elemental silver is dissolved;
solution C: mixing the solution A and the solution B;
solution D: copper chloride and cuprous chloride are dissolved in deionized water to prepare a composite solution of the copper chloride and the cuprous chloride;
e solution: dissolving sodium bromide and sodium iodide in deionized water to prepare a composite solution of sodium bromide and sodium iodide;
f, solution: 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is dissolved in ethylene glycol to prepare an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone;
solution G: dissolving glycerol in a methanol-deionized water mixed solvent to prepare a methanol-deionized water solution of glycerol;
h solution: dissolving pentaerythritol in ethanol to prepare ethanol solution of pentaerythritol;
(2) Heating the solution A to remove excessive hydrochloric acid and nitric acid to obtain orange-red crystals, dissolving the orange-red crystals with deionized water, and carrying out suction filtration to remove insoluble impurities, wherein the filtrate is orange-yellow transparent solution; uniformly dripping the solution D into an orange transparent solution;
(3) Heating the solution C to remove excessive hydrochloric acid and nitric acid to obtain a solid, adding the solid into the solution E to form a suspension, adding the orange transparent solution obtained in the step (2) under the stirring condition, stirring the obtained mixture under the inert atmosphere, and heating for activation; then adding the solution F, heating and stirring for reaction; then adding the solution G, heating and stirring for reaction; then adding H solution, heating and stirring for reaction;
(4) Cooling the reaction product obtained in the step (3) to room temperature, adding diethyl ether, centrifuging to obtain a gray brown solid, adding deionized water to obtain a gray white suspension, and adding acetone to centrifuge the gray white solid;
(5) And (3) dissolving the off-white solid obtained in the step (4) in ethanol to obtain an ethanol dispersion liquid of the nano silver spheres.
The preparation of the solution A has an important influence on the diameter of the nano silver ball, and the core mechanism is that the mixed solution of hydrochloric acid and nitric acid is utilized to dissolve simple substance platinum and simple substance silver into the mixed solution so as to form a solution of platinum salt and silver salt, on the basis, ethylene glycol is utilized to reduce silver nitrate into zero-valent silver, the formed zero-valent silver can be used as the core of homogeneous nucleation of the nano silver ball, the platinum salt can be reduced into zero-valent platinum, and the reduced zero-valent platinum is coated on the surface of the zero-valent silver, so that a large number of platinum microspheres are formed on the surface of the platinum microsphere, and further more heterogeneous nucleation centers capable of enabling newly formed zero-valent silver to grow are formed, so that the particle size of the nano silver ball can be effectively reduced.
The principle is as follows:
Ag + →Ag 0
in step (1):
nitric acid and hydrochloric acid are mixed according to the volume ratio of 1:1 to 5:1 are stirred and mixed at the temperature of 0-20 ℃ to obtain mixed acid;
solution A: adding the simple substance platinum into mixed acid with the mass 10-500 times of that of the simple substance platinum, heating to 30-60 ℃, and continuously preserving heat for reaction for 2-5 h when the simple substance platinum is dissolved;
solution B: adding elemental silver into mixed acid with the mass 10-500 times of that of the elemental silver, heating to 60-150 ℃, and continuously preserving heat for reaction for 2-5 h when the elemental platinum is dissolved;
solution C: mixing the solution A and the solution B according to the volume ratio of 100:1-1:100;
the mass ratio of the copper chloride to the cuprous chloride in the solution D is 1:10-10:1, and the solute mass fraction is 0.01-75 wt.%;
the mass ratio of sodium bromide to sodium iodide in the E solution is 1:100-100:1, and the solute mass fraction is 0.001-65 wt.%;
the mass fraction of solute in the F solution is 0.01-10 wt.%;
the mass ratio of the methanol to the deionized water in the solution G is 1:1000-1000:1, and the solute mass fraction is 0.01-50 wt%;
the mass fraction of solute in the H solution is 0.01-20 wt.%;
in step (2): the solution A is a red transparent solution, and excessive hydrochloric acid and nitric acid are continuously removed by heating at 100-120 ℃ to obtain orange red crystals; dissolving with deionized water with the mass 1-10000 times of that of the orange-red crystal; the mass ratio of the orange transparent solution to the D solution is 100:1 to 10:1.
in the step (2), the excess hydrochloric acid and nitric acid are removed by continuous heating to obtain orange-red crystals, and the orange-red crystals are immediately stored in a vacuum glass tube and in a darkroom. (because the orange-red crystals are very hygroscopic and are very decomposable by visible light).
In step (3): continuously heating the solution C at 100-120 ℃ to remove excessive hydrochloric acid and nitric acid to obtain a solid; the addition amount of the solid in the suspension is 1mg/100 g-1 g/100g solution; the addition volume ratio of the suspension to the orange transparent solution is 1:100-100:1.
In step (3): the heating and activating temperature of the obtained mixture is 40-80 ℃ and the activating time is 0.5-5 h.
In step (3): adding the F solution, heating to 80-160 ℃ and vigorously stirring to react for 2-10 h.
In step (3): adding the solution G, heating to 80-160 ℃ and stirring vigorously to react for 2-10 h.
In step (3): adding H solution, heating to 80-160 ℃ and stirring vigorously to react for 2-10H.
In step (3), the excessive hydrochloric acid and nitric acid are removed by continuous heating to obtain a solid, which is immediately stored in a vacuum glass tube and stored in a dark room. (because the solid mixture is very hygroscopic and is very easily decomposed by light);
the addition amount of the solid in the step (3) is not easy to be excessively large, otherwise, the particle size of the nano silver spheres is easy to be increased, and the dispersibility of the nano silver spheres in ethanol is further poor.
In step (4): the volume ratio of the reaction product to the diethyl ether is 1:1-100:1, then the mixture is centrifuged, the rotation speed is controlled to be 2000-1500 rpm, the centrifugation time is 30-600 s, and the supernatant is removed to obtain a gray brown solid; adding deionized water with the addition amount of 1:1-10:1 by mass ratio to obtain an off-white suspension; adding acetone into the suspension, controlling the adding amount to be 1:1-10:1 by volume ratio, centrifuging, controlling the rotating speed to be 2000-1500 rpm, centrifuging for 30-600 s, and removing supernatant to obtain off-white solid.
The controlled addition of acetone in step (4) should not be too great, otherwise it would easily lead to a decrease in the yield of nanosilver spheres.
In step (5): the addition amount of the ethanol is controlled to be 100:1-10000:1.
The nano silver ball prepared by the invention has the diameter of 50-200nm, good dispersibility in ethanol and capability of forming micro/yellowish transparent solution.
Compared with the prior art, the nano silver particles prepared by the preparation method provided by the invention have more uniform particle size distribution, smaller particle size and better dispersibility in ethanol, and can form a light yellow transparent solution in ethanol, so that the nano silver does not need to be coated and exists in the form of nano silver directly, and the effective performance of the nano silver can be ensured.
Drawings
FIG. 1 is an ethanol dispersion of nano silver spheres prepared in example 1;
fig. 2 is an SEM image of the nano silver spheres prepared in example 1.
Detailed Description
The invention will be further described with reference to specific examples and figures of the specification.
Example 1
Solution A: adding 1g of elemental platinum into 50g of mixed acid of nitric acid and hydrochloric acid (the volume ratio of the hydrochloric acid to the nitric acid is 3:1) at room temperature, heating the system to 50 ℃, stirring and reacting until the elemental platinum is completely dissolved, and continuing to perform heat preservation reaction for 2h;
solution B: adding 1g of elemental silver into 50g of mixed acid of nitric acid and hydrochloric acid (the volume ratio of the hydrochloric acid to the nitric acid is 3:1) at room temperature, heating the system to 50 ℃ to react, and continuing to perform heat preservation reaction for 2h after the elemental silver is dissolved;
solution C: taking 5g A solution and 5g B solution, and stirring and mixing the solution A and the solution B at room temperature;
solution D: 1g of cupric chloride and 1g of cuprous chloride are dissolved in 100ml of deionized water under the condition of room temperature to prepare a compound solution of cupric chloride and cuprous chloride;
e solution: dissolving 0.5g of sodium bromide and 0.5g of sodium iodide in 100ml of deionized water at room temperature to prepare a composite solution of sodium bromide and sodium iodide;
f, solution: 1g of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was dissolved in 100ml of ethylene glycol to prepare an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone;
solution G: dissolving 10ml of glycerol in a methanol-deionized water mixed solvent (wherein the volume of methanol is 50ml and the volume of water is 50 ml) to prepare a methanol-deionized water solution of glycerol;
h solution: 1g of pentaerythritol is dissolved in 100ml of ethanol to prepare an ethanol solution of pentaerythritol;
heating 10g of solution A to 105 ℃, removing excessive hydrochloric acid and nitric acid to obtain orange red crystals, filtering with deionized water solvent, and removing insoluble impurities, wherein the filtrate is orange yellow transparent solution; taking 10g of D solution, and uniformly dripping the D solution into the orange transparent solution by a peristaltic pump at room temperature;
taking 0.05g of orange solid obtained by heating the solution C to remove excessive hydrochloric acid and nitric acid, adding 10ml of E solution to form suspension, adding 10ml of orange transparent solution obtained in the step (2) under stirring, stirring the obtained mixture under the protection of high-purity nitrogen, and heating to 60 ℃ to activate for 0.5h; then adding 20ml of F solution, heating to 100 ℃ and stirring for reaction for 2 hours; then adding 20ml of G solution, heating to 120 ℃ and stirring for reaction for 2 hours; then adding 20ml of H solution, heating to 140 ℃ and stirring for reaction for 2 hours;
cooling the reaction product obtained in the step (3) to room temperature, adding 100ml of diethyl ether, controlling the centrifugation speed to be 1500rpm, centrifuging the system for 30s to obtain a gray brown solid, adding 10ml of deionized water to obtain a gray white suspension, adding 100ml of acetone, and controlling the centrifugation speed to be 1500rpm, centrifuging the system for 30s to obtain the gray white solid;
taking 0.2g of the off-white solid, and dispersing the off-white solid in 100ml of ethanol to obtain ethanol dispersion liquid of light yellow transparent nano silver balls.
The ethanol dispersion liquid of the nano silver spheres prepared in the embodiment is shown in fig. 1, the SEM image of the nano silver spheres is shown in fig. 2, and it is not difficult to see that the particle size is uniformly distributed in the range of 50-200nm in fig. 2, which shows that the nano silver spheres with uniform particle size can be prepared by the method.
Example 2
Solution A: adding 2.0g of elemental platinum into a mixed acid of 65g of nitric acid and hydrochloric acid (the volume ratio of the hydrochloric acid to the nitric acid is 4:1) at room temperature, heating the system to 65 ℃, stirring and reacting until the elemental platinum is completely dissolved, and continuing to perform heat preservation reaction for 3 hours;
solution B: adding 2.0g of elemental silver into a mixed acid of 65g of nitric acid and hydrochloric acid (the volume ratio of the hydrochloric acid to the nitric acid is 4:1) at room temperature, heating the system to 65 ℃ to react, and continuing to perform heat preservation reaction for 3 hours after the elemental silver is dissolved;
solution C: taking 5.5g A solution and 5.5g B solution, and stirring and mixing the solution A and the solution B at room temperature;
solution D: 1.5g of cupric chloride and 1.5g of cuprous chloride are dissolved in 150ml of deionized water at room temperature to prepare a compound solution of cupric chloride and cuprous chloride;
e solution: 1.0g of sodium bromide and 1.0g of sodium iodide are dissolved in 200ml of deionized water at room temperature to prepare a composite solution of sodium bromide and sodium iodide;
f, solution: 1.5g of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was dissolved in 100ml of ethylene glycol to prepare an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone;
solution G: dissolving 10ml of glycerol in a methanol-deionized water mixed solvent (wherein the volume of methanol is 60ml and the volume of water is 60 ml) to prepare a methanol-deionized water solution of glycerol;
h solution: 1.5g of pentaerythritol was dissolved in 100ml of ethanol to prepare an ethanol solution of pentaerythritol;
heating 10g of solution A to 105 ℃, removing excessive hydrochloric acid and nitric acid to obtain orange red crystals, filtering with deionized water solvent, and removing insoluble impurities, wherein the filtrate is orange yellow transparent solution; taking 10g of D solution, and uniformly dripping the D solution into the orange transparent solution by a peristaltic pump at room temperature;
taking 0.2g of orange solid obtained by heating the solution C to remove excessive hydrochloric acid and nitric acid, adding 10ml of E solution to form suspension, adding 10ml of orange transparent solution obtained in the step (2) under stirring, stirring the obtained mixture under the protection of high-purity nitrogen, and heating to 65 ℃ to activate for 1.5h; then adding 20ml of F solution, heating to 105 ℃ and stirring for reaction for 2.5h; then adding 20ml of G solution, heating to 115 ℃ and stirring for reaction for 2.5h; then adding 20ml of H solution, heating to 140 ℃ and stirring for reaction for 2.5H;
cooling the reaction product obtained in the step (3) to room temperature, adding 110ml of diethyl ether, controlling the centrifugation speed to 1600rpm, centrifuging the system for 100s to obtain a gray brown solid, adding 15ml of deionized water to obtain a gray white suspension, adding 110ml of acetone, and controlling the centrifugation speed to 1600rpm, centrifuging the system for 1000s to obtain the gray white solid;
taking 0.2g of the off-white solid, and dispersing the off-white solid in 100ml of ethanol to obtain ethanol dispersion liquid of light yellow transparent nano silver balls.
Example 3
Solution A: adding 1.5g of elemental platinum into 60g of mixed acid of nitric acid and hydrochloric acid (the volume ratio of the hydrochloric acid to the nitric acid is 3.5:1) at room temperature, heating the system to 60 ℃, stirring and reacting until the elemental platinum is completely dissolved, and continuing to perform heat preservation reaction for 2.5h;
solution B: adding 1.5g of elemental silver into a mixed acid of nitric acid and hydrochloric acid with the mass of 60g (the volume ratio of the hydrochloric acid to the nitric acid is 3.5:1) at room temperature, heating the system to 60 ℃ to react, and continuing to perform heat preservation reaction for 2.5h after the elemental silver is dissolved;
solution C: taking a 6g A solution and a 6g B solution, and stirring and mixing the solution A and the solution B at room temperature;
solution D: 1.2g of cupric chloride and 1.2g of cuprous chloride are dissolved in 150ml of deionized water at room temperature to prepare a compound solution of cupric chloride and cuprous chloride;
e solution: dissolving 0.6g of sodium bromide and 0.6g of sodium iodide in 150ml of deionized water at room temperature to prepare a composite solution of sodium bromide and sodium iodide;
f, solution: 1.2g of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone was dissolved in 120ml of ethylene glycol to prepare an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone;
solution G: 15ml of glycerol is dissolved in a mixed solvent of methanol and deionized water (wherein the volume of the methanol is 60ml and the volume of the water is 60 ml) to prepare a methanol-deionized water solution of the glycerol;
h solution: 1.5g of pentaerythritol was dissolved in 150ml of ethanol to prepare an ethanol solution of pentaerythritol;
heating 15g of solution A to 110 ℃, removing excessive hydrochloric acid and nitric acid to obtain orange red crystals, filtering with deionized water solvent, and removing insoluble impurities, wherein the filtrate is orange yellow transparent solution; taking 15g of D solution, and uniformly dripping the D solution into the orange transparent solution by a peristaltic pump at the temperature of 30 ℃;
taking 0.1g of orange solid obtained by heating the solution C to remove excessive hydrochloric acid and nitric acid, adding the orange solid into 15ml of solution E to form a suspension, adding 15ml of orange transparent solution obtained in the step (2) under the stirring condition, stirring the obtained mixture under the protection of high-purity nitrogen, and heating to 70 ℃ to activate for 1h; then 25ml of F solution is added, the temperature is raised to 105 ℃ and the mixture is stirred for 2.5h; then 25ml of G solution is added, the temperature is raised to 125 ℃ and the mixture is stirred for 2.5h; then 25ml of H solution is added, the temperature is raised to 145 ℃ and the mixture is stirred for 2.5H;
cooling the reaction product obtained in the step (3) to room temperature, adding 150ml of diethyl ether, controlling the centrifugation speed to 1700rpm, centrifuging the system for 60s to obtain a gray brown solid, adding 15ml of deionized water to obtain a gray white suspension, adding 150ml of acetone, and controlling the centrifugation speed to 1700rpm, centrifuging the system for 60s to obtain the gray white solid;
taking 0.2g of the off-white solid, and dispersing the off-white solid in 100ml of ethanol to obtain ethanol dispersion liquid of light yellow transparent nano silver balls.
The above embodiments are only for illustrating the inventive concept of the present invention and not for limiting the protection of the claims of the present invention, and any simple modification, equivalent variation and modification of the above embodiments according to the technical and method substance of the present invention still fall within the scope of the technical and method aspects of the present invention.
Claims (10)
1. A method for preparing nano silver particles with good ethanol dispersibility, which is characterized by comprising the following steps:
(1) The following solutions were prepared:
solution A: adding the simple substance platinum into mixed acid of nitric acid and hydrochloric acid, and heating to react until the simple substance platinum is dissolved;
solution B: adding elemental silver into mixed acid of nitric acid and hydrochloric acid, and heating to react until the elemental silver is dissolved;
solution C: mixing the solution A and the solution B;
solution D: copper chloride and cuprous chloride are dissolved in deionized water to prepare a composite solution of the copper chloride and the cuprous chloride;
e solution: dissolving sodium bromide and sodium iodide in deionized water to prepare a composite solution of sodium bromide and sodium iodide;
f, solution: 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone is dissolved in ethylene glycol to prepare an ethylene glycol solution of 2,3,5, 6-tetrahydroxy-2-hexene-4-lactone;
solution G: dissolving glycerol in a methanol-deionized water mixed solvent to prepare a methanol-deionized water solution of glycerol;
h solution: dissolving pentaerythritol in ethanol to prepare ethanol solution of pentaerythritol;
(2) Heating the solution A to remove excessive hydrochloric acid and nitric acid to obtain orange-red crystals, dissolving the orange-red crystals with deionized water, and carrying out suction filtration to remove insoluble impurities, wherein the filtrate is orange-yellow transparent solution; uniformly dripping the solution D into an orange transparent solution;
(3) Heating the solution C to remove excessive hydrochloric acid and nitric acid to obtain a solid, adding the solid into the solution E to form a suspension, adding the orange transparent solution obtained in the step (2) under the stirring condition, stirring the obtained mixture under the inert atmosphere, and heating for activation; then adding the solution F, heating and stirring for reaction; then adding the solution G, heating and stirring for reaction; then adding H solution, heating and stirring for reaction;
(4) Cooling the reaction product obtained in the step (3) to room temperature, adding diethyl ether, centrifuging to obtain a gray brown solid, adding deionized water to obtain a gray white suspension, and adding acetone to centrifuge the gray white solid;
(5) And (3) dissolving the off-white solid obtained in the step (4) in ethanol to obtain an ethanol dispersion liquid of the nano silver spheres.
2. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (1):
nitric acid and hydrochloric acid are mixed according to the volume ratio of 1:1 to 5:1 are stirred and mixed at the temperature of 0-20 ℃ to obtain mixed acid;
solution A: adding the simple substance platinum into mixed acid with the mass 10-500 times of that of the simple substance platinum, heating to 30-60 ℃, and continuously preserving heat for reaction for 2-5 h when the simple substance platinum is dissolved;
solution B: adding elemental silver into mixed acid with the mass 10-500 times of that of the elemental silver, heating to 60-150 ℃, and continuously preserving heat for reaction for 2-5 h when the elemental platinum is dissolved;
solution C: mixing the solution A and the solution B according to the volume ratio of 100:1-1:100;
the mass ratio of the copper chloride to the cuprous chloride in the solution D is 1:10-10:1, and the solute mass fraction is 0.01-75 wt.%;
the mass ratio of sodium bromide to sodium iodide in the E solution is 1:100-100:1, and the solute mass fraction is 0.001-65 wt.%;
the mass fraction of solute in the F solution is 0.01-10 wt.%;
the mass ratio of the methanol to the deionized water in the solution G is 1:1000-1000:1, and the solute mass fraction is 0.01-50 wt%;
the mass fraction of solute in the H solution is 0.01-20 wt.%.
3. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (2): the solution A is a red transparent solution, and excessive hydrochloric acid and nitric acid are continuously removed by heating at 100-120 ℃ to obtain orange red crystals; dissolving with deionized water with the mass 1-10000 times of that of the orange-red crystal; the mass ratio of the orange transparent solution to the D solution is 100:1 to 10:1.
4. the method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (3): continuously heating the solution C at 100-120 ℃ to remove excessive hydrochloric acid and nitric acid to obtain a solid; the addition amount of the solid in the suspension is 1mg/100 g-1 g/100g solution; the addition volume ratio of the suspension to the orange transparent solution is 1:100-100:1.
5. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (3): the heating and activating temperature of the obtained mixture is 40-80 ℃ and the activating time is 0.5-5 h.
6. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (3): adding the F solution, heating to 80-160 ℃ and stirring for reaction for 2-10 h.
7. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (3): adding the solution G, heating to 80-160 ℃ and stirring for reaction for 2-10 h.
8. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (3): adding H solution, heating to 80-160 ℃ and stirring for reaction for 2-10H.
9. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (4): the volume ratio of the reaction product to the diethyl ether is 1:1-100:1, then the mixture is centrifuged, the rotation speed is controlled to be 2000-1500 rpm, the centrifugation time is 30-600 s, and the supernatant is removed to obtain a gray brown solid; adding deionized water with the addition amount of 1:1-10:1 by mass ratio to obtain an off-white suspension; adding acetone into the suspension, controlling the adding amount to be 1:1-10:1 by volume ratio, centrifuging, controlling the rotating speed to be 2000-1500 rpm, centrifuging for 30-600 s, and removing supernatant to obtain off-white solid.
10. The method for preparing nano-silver particles having good ethanol dispersibility according to claim 1, wherein in step (5): the addition amount of the ethanol is controlled to be 100:1-10000:1.
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