CN113732299A - Silver nanowire and preparation method and application thereof - Google Patents
Silver nanowire and preparation method and application thereof Download PDFInfo
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- CN113732299A CN113732299A CN202111011073.7A CN202111011073A CN113732299A CN 113732299 A CN113732299 A CN 113732299A CN 202111011073 A CN202111011073 A CN 202111011073A CN 113732299 A CN113732299 A CN 113732299A
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 122
- 239000002042 Silver nanowire Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 241000241413 Propolis Species 0.000 claims abstract description 106
- 229940069949 propolis Drugs 0.000 claims abstract description 106
- 150000001879 copper Chemical class 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000000284 extract Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000003378 silver Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 214
- 239000000243 solution Substances 0.000 claims description 97
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 41
- 239000000469 ethanolic extract Substances 0.000 claims description 39
- 239000000843 powder Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 24
- 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 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 19
- 239000011550 stock solution Substances 0.000 claims description 16
- 238000007710 freezing Methods 0.000 claims description 14
- 230000008014 freezing Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 238000007873 sieving Methods 0.000 claims description 14
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 11
- 230000001476 alcoholic effect Effects 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000161 silver phosphate Inorganic materials 0.000 claims description 2
- 229940019931 silver phosphate Drugs 0.000 claims description 2
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 2
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000047 product Substances 0.000 abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 11
- 235000013871 bee wax Nutrition 0.000 abstract description 8
- 239000012166 beeswax Substances 0.000 abstract description 8
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000002086 nanomaterial Substances 0.000 abstract description 5
- 230000002194 synthesizing effect Effects 0.000 abstract description 5
- 239000012530 fluid Substances 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 239000004094 surface-active agent Substances 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000002981 blocking agent Substances 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract description 2
- 230000008018 melting Effects 0.000 abstract description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 2
- 229910001431 copper ion Inorganic materials 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 description 67
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 14
- 238000005303 weighing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 101710134784 Agnoprotein Proteins 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 150000005846 sugar alcohols Polymers 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 229920002120 photoresistant polymer Polymers 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- -1 ITO Substances 0.000 description 4
- RTIXKCRFFJGDFG-UHFFFAOYSA-N chrysin Chemical compound C=1C(O)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=CC=C1 RTIXKCRFFJGDFG-UHFFFAOYSA-N 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- IYRMWMYZSQPJKC-UHFFFAOYSA-N kaempferol Chemical compound C1=CC(O)=CC=C1C1=C(O)C(=O)C2=C(O)C=C(O)C=C2O1 IYRMWMYZSQPJKC-UHFFFAOYSA-N 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002070 nanowire Substances 0.000 description 3
- 229920005862 polyol Polymers 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 2
- NYCXYKOXLNBYID-UHFFFAOYSA-N 5,7-Dihydroxychromone Natural products O1C=CC(=O)C=2C1=CC(O)=CC=2O NYCXYKOXLNBYID-UHFFFAOYSA-N 0.000 description 2
- UBSCDKPKWHYZNX-UHFFFAOYSA-N Demethoxycapillarisin Natural products C1=CC(O)=CC=C1OC1=CC(=O)C2=C(O)C=C(O)C=C2O1 UBSCDKPKWHYZNX-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229940043370 chrysin Drugs 0.000 description 2
- 235000015838 chrysin Nutrition 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 2
- 229940114124 ferulic acid Drugs 0.000 description 2
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 2
- 235000001785 ferulic acid Nutrition 0.000 description 2
- 229930003935 flavonoid Natural products 0.000 description 2
- 150000002215 flavonoids Chemical class 0.000 description 2
- 235000017173 flavonoids Nutrition 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- MWDZOUNAPSSOEL-UHFFFAOYSA-N kaempferol Natural products OC1=C(C(=O)c2cc(O)cc(O)c2O1)c3ccc(O)cc3 MWDZOUNAPSSOEL-UHFFFAOYSA-N 0.000 description 2
- 235000008777 kaempferol Nutrition 0.000 description 2
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- PPWHTZKZQNXVAE-UHFFFAOYSA-N Tetracaine hydrochloride Chemical compound Cl.CCCCNC1=CC=C(C(=O)OCCN(C)C)C=C1 PPWHTZKZQNXVAE-UHFFFAOYSA-N 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 229910052927 chalcanthite Inorganic materials 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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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
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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
- B82Y40/00—Manufacture or treatment of nanostructures
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Abstract
The invention provides a silver nanowire and a preparation method and application thereof. The preparation raw materials of the silver nanowire comprise: propolis, copper salts and silver salts. In the whole process of synthesizing the silver nanowires by using the propolis extract, no chemical reagents such as ethylene glycol and the like which pollute the environment are used as solvents, and the product has no chemical reagent residues, thereby ensuring the purity of the silver nanowires. And propolis reaches the melting point to become viscous fluid, and beeswax is separated out. The beeswax is dispersed in water and can be used as a surfactant to guide the interaction between copper ions and intermolecular sugar, so that the growth of a one-dimensional nano structure is promoted, and the growth of longer silver nanowires is facilitated. Meanwhile, PVP is used as a blocking agent instead of the PVP, the surface of the silver nanowire is pure, and the conductivity is good. The introduction of copper ions into the whole reaction system can enable more polytwin seeds to be generated at the initial stage of the reaction, greatly improve the yield of the silver nanowires and generate fewer byproducts such as silver nanoparticles and the like.
Description
Technical Field
The invention belongs to the technical field of photoelectron, and particularly relates to a silver nanowire as well as a preparation method and application thereof, in particular to a silver nanowire prepared from propolis as well as a preparation method and application thereof.
Background
With the development of the times and the progress of science and technology, people have higher and higher requirements on future electronic products. Future electronic products may be bent, stretched, compressed, twisted and deformed into complex non-planar shapes. At the same time, they must also maintain good performance. The core component of electronic products such as touch screens, liquid crystal displays, organic light-emitting diodes, solar cells and the like is a transparent electrode.
Currently, the most widely used and most demanded transparent electrode material in the global electronic industry is Indium Tin Oxide (ITO). The ITO has good light transmittance, low thickness, easy etching into an electrode pattern, high hardness and wear resistance. Meanwhile, the method also has the defects that the cost is high, the method is not beneficial to producing the bent screen, the toxicity is not beneficial to environmental protection and the like. Therefore, ITO is gradually being replaced by next-generation flexible transparent materials such as Carbon Nanotubes (CNTs), graphene, and metal nanowires. Among the candidate materials, the metal nanowires, especially the silver nanowires, have the advantages of good conductivity, good light transmittance, excellent flexibility, low cost, good stability, no moire and the like compared with materials such as ITO, metal grids, carbon nanotubes, conductive polymers, graphene and the like, and all indexes are all-round.
CN104616833A discloses a method for preparing a silver nanowire transparent electrode in a large area and a silver nanowire transparent electrode, taking a proper amount of silver nanowire solution, separating silver nanowires and a solvent by using a centrifuge, removing the solvent, doping the bottom silver nanowires into photoresist, and oscillating until the silver nanowires are uniformly dispersed therein to form a silver nanowire-photoresist suspension; uniformly spin-coating the suspension on a clean transparent substrate to form a silver nanowire-photoresist film; immersing the transparent substrate coated with the silver nanowire-photoresist film into a photoresist removing solution to remove the surface photoresist; and taking out the transparent substrate, and leaving the silver nanowires on the transparent substrate to form a uniform silver nanowire network, namely the silver nanowire transparent electrode after the surface solution is volatilized.
CN110128883A discloses a conductive ink of an ultra-low haze silver nanowire film, a preparation method and an application thereof, wherein the conductive ink prepared by the preparation method is used for manufacturing the ultra-low haze silver nanowire film, the diameter of a silver nanowire obtained by the preparation method is 20 nanometers, and the length-diameter ratio is 1000; the optical transmittance of the film made of the conductive ink is higher than 95%, and the haze is lower than 0.5%.
CN112893862A discloses a variety of silver nanowires, a preparation method thereof and a conductive film prepared from the silver nanowires, wherein the preparation method of the silver nanowires comprises (1) preparing a PVP polyalcohol solution, a halide salt polyalcohol solution and a silver nitrate polyalcohol solution respectively; (2) adding a part of prepared silver nitrate polyalcohol solution into a halide salt polyalcohol solution to react to prepare seed solution; (3) uniformly mixing the rest silver nitrate polyalcohol solution and PVP polyalcohol solution, dropwise adding the mixed solution into the seed solution for reaction, and standing for reaction after dropwise adding is finished to obtain silver nanowires; and step four, washing the silver nanowires obtained in the step three, and then fixing the volume and dispersing the silver nanowires in a solvent.
The method for synthesizing the silver nanowires of the patent mainly comprises a solvothermal method, a wet chemical synthesis method, an environmental solution phase method, a polyol synthesis method, a hydrothermal method, an ultraviolet irradiation method, a template method, a seed crystal method and the like. The polyol process is currently the most commonly used process. The method has high requirements on reaction conditions, and simultaneously, chemical reagents such as ethylene glycol, PVP and the like which are easy to pollute the environment are inevitably introduced.
Therefore, the synthesis of silver nanowires under mild conditions by using abundant green biomass resources without adding other chemical reagents is one of the directions in which researchers are urgently required to break through.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a silver nanowire and a preparation method and application thereof, in particular to a silver nanowire prepared from propolis and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a silver nanowire, wherein the raw materials for preparing the silver nanowire comprise: propolis, copper salts and silver salts.
In the invention, the propolis extract is used as a reducing agent, and the aqueous solution of ethanol is used as a solvent, so that the use of ethylene glycol, PVP and other chemical reagents which are easy to pollute the environment is avoided, and the environment is protected.
The propolis extract contains abundant flavonoids and phenolic compounds, wherein the more abundant components comprise chrysin, kaempferol, ferulic acid and the like, and hydroxyl in the molecular structures of the compounds ensures that the compounds have certain reducibility, can serve as a reducing agent in the reaction synthesis process, avoids the introduction of chemical reagents such as ethylene glycol and the like which are easy to pollute the environment in a polyol synthesis method, and is more green and environment-friendly.
And propolis melts into viscous fluid at high temperature, and beeswax is separated. The beeswax can be dispersed in water and can serve as a surfactant, can guide the interaction between Cu (II) and intermolecular sugar, support the growth of a one-dimensional nano structure, avoid using PVP which is difficult to remove, and synthesize the silver nanowire with high length, diameter and good conductivity.
And the Cu (II) avoids the dissolution of twin seeds caused by oxidation etching by removing oxygen on the surfaces of the twin seeds, promotes the growth of multi-twin seeds, is beneficial to forming silver nanowires and improves the synthesis yield.
Preferably, the propolis accounts for 5-15% of the total mass of the silver nanowires, and may be, for example, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.
Preferably, the molar ratio of the silver salt to the copper salt is 1 (0.5-3), and may be, for example, 1:0.5, 1:0.6, 1:0.8, 1:1, 1:1.2, 1:1.5, 1:1.7, 1:2, 1:2.2, 1:1.2.5, 1:2.8, 1:3, and the like.
Preferably, the copper salt comprises any one of copper sulfate, basic copper carbonate, copper nitrate or copper chloride or a combination of at least two of them, preferably copper sulfate.
Preferably, the silver salt comprises any one or a combination of at least two of silver nitrate, silver sulfate, silver phosphate or silver chloride, preferably silver nitrate.
Preferably, the silver nanowires have a length of 30-100 μm, such as 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, etc., and a diameter of 20-120nm, such as 20nm, 22nm, 25nm, 28nm, 30nm, 32nm, 35nm, 38nm, 40nm, 45nm, 50nm, 55nm, 60nm, 65nm, 70nm, 75nm, 80nm, 85nm, 90nm, 95nm, 100nm, 105nm, 110nm, 115nm, 120nm, etc.
In a second aspect, the present invention provides a method for preparing silver nanowires according to the first aspect, comprising the steps of:
(1) extracting propolis to obtain propolis ethanol extractive solution; preparing a copper salt into an alcohol solution of the copper salt; preparing silver salt into alcoholic solution of silver salt;
(2) mixing the propolis alcohol extract obtained in the step (1) with an alcohol solution of copper salt, stirring for the first time, then dropwise adding an alcohol solution of silver salt, and stirring for the second time to obtain a mixed solution;
(3) and (3) heating the mixed solution obtained in the step (2) for reaction, and centrifuging to obtain the silver nanowire.
In the invention, in the whole process of synthesizing the silver nanowires by using the propolis extract, no chemical reagent which pollutes the environment such as ethylene glycol is used as a solvent, but ethanol is used as the solvent, the ethanol is completely volatilized in the process of constant-temperature water bath, the product does not have the residue of the chemical reagent, and the purity of the silver nanowires is ensured.
In the present invention, propolis reaches the melting point and becomes a viscous fluid, while beeswax is separated. The beeswax is dispersed in water and can be used as a surfactant to guide the interaction between Cu (II) and intermolecular sugar, so that the growth of a one-dimensional nano structure is promoted, and the growth of longer silver nanowires is facilitated. Meanwhile, PVP is used as a blocking agent instead of the PVP, the surface of the silver nanowire is pure, and the conductivity is good.
In the invention, Cu (II) is introduced into the whole reaction system, so that more polytwin seeds can be generated at the initial stage of the reaction, the yield of the silver nanowires is greatly improved, and the generated silver nanoparticles and other byproducts are less. The preparation method is rapid in preparation process, simple in process, suitable for large-scale industrial production, free of organic reagent residues, and environment-friendly.
Preferably, in the step (1), the propolis alcohol extract is prepared from the following raw materials in parts by weight: 5-8 parts of propolis, 80-120 parts of ethanol and 50-120 parts of water.
In the propolis alcohol extract, the propolis content is 5-8 parts, and may be, for example, 5 parts, 5.2 parts, 5.4 parts, 5.6 parts, 5.8 parts, 6 parts, 6.2 parts, 6.4 parts, 6.6 parts, 6.8 parts, 7 parts, 7.2 parts, 7.4 parts, 7.6 parts, 7.8 parts, 8 parts, etc.
The propolis alcohol extract contains 80-120 parts of ethanol, such as 80, 85, 90, 95, 100, 105, 110, 115, 120, etc.
In the propolis alcohol extract, the water content is 50-120 parts, and may be, for example, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 95 parts, 100 parts, 105 parts, 110 parts, 115 parts, 120 parts, etc.
Preferably, in step (1), the extracting operation is specifically: freezing and pulverizing propolis, and sieving to obtain propolis fine powder; mixing the propolis fine powder with ethanol to obtain propolis ethanol extract; and finally, adding water to dilute the propolis ethanol extract to obtain the propolis ethanol extract.
Preferably, the freezing temperature is-20 to-10 ℃, for example, -20 ℃, -18 ℃, -16 ℃, -14 ℃, -12 ℃, -10 ℃ and the like, and the freezing time is 8 to 12 hours, for example, 8 hours, 8.5 hours, 9 hours, 9.5 hours, 10 hours, 10.5 hours, 11 hours, 11.5 hours, 12 hours and the like.
Preferably, the sieving is 80-100 mesh sieving, such as 80 mesh, 85 mesh, 90 mesh, 95 mesh, 100 mesh, etc.
Preferably, the mass-to-volume ratio of the propolis fine powder to ethanol is (5-8) g:100mL, and may be, for example, 5g:100mL, 5.5g:100mL, 6g:100mL, 6.5g:100mL, 7g:100mL, 7.5g:100mL, 8g:100mL, or the like.
Preferably, the concentration of ethanol is 90-100 vol%, for example, may be 90 vol%, 91 vol%, 92 vol%, 93 vol%, 94 vol%, 95 vol%, 96 vol%, 97 vol%, 98 vol%, 99 vol%, 100 vol%.
Preferably, the dilution is to dilute to a concentration of ethanol in the propolis ethanol extract of 50-70 vol%, for example, 50 vol%, 55 vol%, 60 vol%, 65 vol%, 70 vol%, etc.
Preferably, in step (1), the concentration of the alcoholic solution of the copper salt is 8 to 12mmol/L, and may be, for example, 8mmol/L, 8.5mmol/L, 9mmol/L, 9.5mmol/L, 10mmol/L, 10.5mmol/L, 11mmol/L, 11.5mmol/L, 12mmol/L, or the like.
Preferably, in step (1), the concentration of the alcoholic solution of the silver salt is 0.5 to 10mmol/L, and may be, for example, 0.5mmol/L, 1mmol/L, 2mmol/L, 3mmol/L, 4mmol/L, 5mmol/L, 6mmol/L, 7mmol/L, 8mmol/L, 9mmol/L, 10mmol/L or the like.
Preferably, in the step (2), the volume ratio of the alcohol solution of the propolis, the alcohol solution of the copper salt and the alcohol solution of the silver salt is (10-45): (35-65);
wherein, the first "10-45" may be, for example, 10, 15, 20, 25, 30, 35, 40, 45, etc.;
wherein the second "10-45" can be, for example, 10, 15, 20, 25, 30, 35, 40, 45, etc.;
the "35 to 65" may be 35, 40, 45, 50, 55, 60, 65, or the like, for example.
Preferably, in the step (2), the temperature of the primary stirring is 25-30 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, the time of the primary stirring is 8-12h, for example, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h and the like, and the rotation speed of the primary stirring is 600-800rpm, for example, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm and the like.
Preferably, in step (2), the dropping rate of the alcoholic solution of the silver salt is 0.3-0.8mL/min, and may be, for example, 0.3mL/min, 0.4mL/min, 0.5mL/min, 0.6mL/min, 0.7mL/min, 0.8mL/min, or the like.
Preferably, in the step (2), the temperature of the secondary stirring is 25-30 ℃, for example, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃ and the like, the time of the secondary stirring is 2-4h, for example, 2h, 2.5h, 3h, 3.5h, 4h and the like, and the rotation speed of the secondary stirring is 350-550rpm, for example, 350rpm, 400rpm, 450rpm, 500rpm, 550rpm and the like.
Preferably, in the step (3), the temperature of the heating reaction is 65-80 ℃, for example, 65 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 76 ℃, 78 ℃, 80 ℃ and the like, and the time of the heating reaction is 24-72h, for example, 24h, 30h, 35h, 40h, 45h, 50h, 55h, 60h, 65h, 70h, 72h and the like.
Preferably, in step (3), the rotation speed of the centrifugation is 10000-15000rpm, such as 10000rpm, 11000rpm, 12000rpm, 13000rpm, 14000rpm, 15000rpm and the like, and the time of the centrifugation is 5-30min, such as 5min, 6min, 8min, 10min, 12min, 14min, 16min, 18min, 20min, 22min, 24min, 26min, 28min, 30min and the like.
Preferably, in step (3), a solvent is added for the centrifugation treatment, and the solvent comprises acetone and/or ethanol.
Preferably, the preparation method of the silver nanowire comprises the following steps:
(1) freezing propolis at-20 to-10 ℃ for 8 to 12 hours, crushing, and sieving by a sieve of 80 to 100 meshes to obtain propolis fine powder; mixing propolis fine powder with ethanol to obtain 50-80g/L propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract to 50-70 vol% to obtain propolis ethanol extract; mixing copper salt with ethanol to obtain an alcohol solution of the copper salt with the concentration of 8-12 mmol/L; mixing silver salt with ethanol to obtain 0.5-10mmol/L copper salt alcoholic solution;
(2) mixing the propolis alcohol extract obtained in the step (1) with an alcohol solution of a copper salt, stirring at 800rpm for 8-12h at 25-30 ℃, dropwise adding an alcohol solution of a silver salt at the speed of 0.3-0.8mL/min, and stirring at 550rpm for 2-4h at 350-30 ℃ to obtain a mixed solution;
wherein the volume ratio of the propolis alcohol extract to the alcohol solution of the copper salt to the alcohol solution of the silver salt is (10-45): (35-65);
(3) heating the mixed solution obtained in the step (2) at 65-80 ℃ for reaction for 24-72h to obtain silver nanowire stock solution; and centrifuging the silver nanowire stock solution by using acetone and ethanol respectively at 10000-15000rpm for 1-5 times, and each time for 4-6min to obtain the silver nanowire.
In a third aspect, the present invention provides a use of silver nanowires as described in the first aspect for the preparation of a transparent electrode.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, propolis is introduced into the raw materials for preparing the silver nanowires, wherein the propolis contains abundant flavonoid and phenolic compounds, more components of the propolis contain chrysin, kaempferol, ferulic acid and the like, and hydroxyl groups in the molecular structures of the compounds enable the compounds to have certain reducibility, so that the compounds can serve as reducing agents in the reaction synthesis process, the introduction of chemical reagents which are easy to pollute the environment, such as ethylene glycol and the like in a polyol synthesis method is avoided, and the preparation method is more green and environment-friendly;
(2) in the preparation process, the propolis is melted into viscous fluid at high temperature, and the beeswax is separated out at the same time. The beeswax can be dispersed in water and can serve as a surfactant, so that the interaction between Cu (II) and intermolecular sugar can be guided, the growth of a one-dimensional nano structure is supported, PVP (polyvinyl pyrrolidone) which is difficult to remove is avoided, and the silver nanowire with high length and diameter and good conductivity is synthesized;
(3) according to the invention, copper salt is introduced in the preparation process, and the Cu (II) removes oxygen on the surface of the twin crystal seeds, so that the twin crystal seeds are prevented from being dissolved due to oxidation etching, the growth of multiple twin crystal seeds is promoted, the formation of silver nanowires is facilitated, and the synthesis yield is improved.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The present embodiment provides a silver nanowire, which is prepared by the following preparation method:
(1) weighing propolis, freezing at-20 deg.C for 10 hr, pulverizing, and sieving with 100 mesh sieve to obtain fine powder; adding 6.5g of the fine powder into 100mL of 95 vol% ethanol solution, and magnetically stirring at room temperature until the fine powder is completely dissolved to obtain 65g/L of propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract until the ethanol concentration is 70 vol% to obtain a propolis ethanol extract; respectively weighing a certain amount of AgNO3And CuSO4·5H2Dissolving O in anhydrous ethanol, and magnetically stirring until completely dissolving to obtain AgNO with concentration of 5mmol/L3Solution and CuSO with concentration of 10mmol/L4·5H2O solution;
(2) mixing propolis ethanol extractive solution with CuSO4·5H2Mixing the O solution, magnetically stirring at the rotation speed of 700rpm for 10 hours at 25 ℃, then dropwise adding a silver nitrate solution at 0.35mL/min, and simultaneously stirring at the rotation speed of 450rpm for 3 hours at 25 ℃ to obtain a mixed solution;
wherein the propolis ethanol extract comprises 25 vol% of CuSO4 & 5H2Ethanol solution of O25 vol%, AgNO350 vol% of an ethanol solution;
(3) heating the mixed solution in a water bath to 70 ℃, and reacting for 72 hours to obtain a silver nanowire stock solution; and centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively, wherein each time is 5min, and dispersing the product in absolute ethyl alcohol for storage to obtain the silver nanowires.
Example 2
The present embodiment provides a silver nanowire, which is prepared by the following preparation method:
(1) weighing propolis, freezing at-15 deg.C for 11 hr, pulverizing, and sieving with 80 mesh sieve to obtain fine powder; then 7.0g of the fine powder was added to 100mL of a 95 vol% ethanol solution, and the mixture was magnetically stirred at room temperatureDissolving completely to obtain 70g/L propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract until the ethanol concentration is 65 vol% to obtain a propolis ethanol extract; respectively weighing a certain amount of AgNO3And CuSO4·5H2Dissolving O in anhydrous ethanol, and magnetically stirring until completely dissolving to obtain AgNO with concentration of 6.5mmol/L3Solution and CuSO with concentration of 10mmol/L4·5H2O solution;
(2) mixing propolis ethanol extractive solution with CuSO4·5H2Mixing the O solution, magnetically stirring at 650rpm at 30 deg.C for 9h, and adding AgNO dropwise at 0.35mL/min3Stirring the solution at the same time at the temperature of 30 ℃ for 4 hours at the rotating speed of 500rpm to obtain a mixed solution;
wherein the propolis ethanol extract comprises 20 vol% and CuSO4·5H2Ethanol solution of O30 vol%, AgNO350 vol% of an ethanol solution;
(3) heating the mixed solution in a water bath to 75 ℃, and reacting for 60 hours to obtain a silver nanowire stock solution; and centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively, wherein each time is 5min, and dispersing the product in absolute ethyl alcohol for storage to obtain the silver nanowires.
Example 3
The present embodiment provides a silver nanowire, which is prepared by the following preparation method:
(1) weighing propolis, freezing at-12 deg.C for 9 hr, pulverizing, and sieving with 90 mesh sieve to obtain fine powder; adding 5.0g of the fine powder into 100mL of 95% ethanol solution, and magnetically stirring at room temperature until completely dissolving to obtain 50g/L propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract until the ethanol concentration is 60 percent to obtain propolis ethanol extract; respectively weighing a certain amount of AgNO3And CuSO4·5H2Dissolving O in anhydrous ethanol, and magnetically stirring until completely dissolving to obtain AgNO with concentration of 3mmol/L3Solution and CuSO with concentration of 10mmol/L4·5H2O solution;
(2) mixing propolis ethanol extractive solution with CuSO4·5H2O solution is mixed inMagnetically stirring at 25 deg.C and 600rpm for 10 hr, and adding AgNO dropwise at 0.35mL/min3Stirring the solution at the same time at the rotation speed of 400rpm for 2 hours at the temperature of 25 ℃ to obtain a mixed solution;
wherein the propolis ethanol extract comprises 20 vol% and CuSO4·5H220 vol% of ethanol solution of O, AgNO360 vol% of an ethanol solution;
(3) heating the mixed solution in a water bath to 80 ℃, and reacting for 48 hours to obtain a silver nanowire stock solution; and centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively, wherein each time is 5min, and dispersing the product in absolute ethyl alcohol for storage to obtain the silver nanowires.
Example 4
The present embodiment provides a silver nanowire, which is prepared by the following preparation method:
(1) weighing propolis, freezing at-10 deg.C for 12 hr, pulverizing, and sieving with 90 mesh sieve to obtain fine powder; adding 8.0g of the fine powder into 100mL of 95 vol% ethanol solution, and magnetically stirring at room temperature until the fine powder is completely dissolved to obtain 80g/L propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract until the ethanol concentration is 50 vol% to obtain a propolis ethanol extract; respectively weighing a certain amount of AgNO3And CuSO4·5H2Dissolving O in anhydrous ethanol, and magnetically stirring until completely dissolving to obtain AgNO with concentration of 8mmol/L3Solution and CuSO with concentration of 10mmol/L4·5H2O solution;
(2) mixing propolis ethanol extractive solution with CuSO4·5H2Mixing the O solution, magnetically stirring for 10h, and then dropwise adding AgNO at 0.35mL/min3Uniformly stirring the solution to obtain a mixed solution;
wherein the propolis ethanol extract is 23 vol%, and CuSO4·5H2Ethanol solution of O (11 vol%), AgNO366 vol% of an ethanol solution;
(3) heating the mixed solution in a water bath to 65 ℃, and reacting for 72 hours to obtain a silver nanowire stock solution; and centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively, wherein each time is 5min, and dispersing the product in absolute ethyl alcohol for storage to obtain the silver nanowires.
Example 5
This example provides silver nanowires, differing from example 1 only in that CuSO is added4·5H2Replacement of O by Cu (CH)3COO)2·H2O, the other steps are the same as in example 1.
Example 6
This example provides a silver nanowire, which is different from example 1 only in that silver nitrate is replaced with silver chloride, and the other steps are the same as example 1.
Example 7
This example provides a silver nanowire, which is different from example 1 only in that the preparation method of the propolis ethanol extract is different: weighing propolis, freezing at-20 deg.C for 10 hr, pulverizing, and sieving with 100 mesh sieve to obtain fine powder; adding 6.5g of the fine powder into 200mL of 70 vol% ethanol solution, and magnetically stirring at room temperature until completely dissolved to obtain propolis ethanol extract.
Example 8
This example provides silver nanowires, which are different from example 1 only in that, in the step (1), the propolis ethanol extract is diluted to a concentration of 40 vol% of ethanol in the propolis ethanol extract during the preparation process.
Example 9
This example provides silver nanowires, which are different from example 1 only in that, in the step (1), the propolis ethanol extract is diluted to a concentration of 80 vol% of ethanol in the propolis ethanol extract during the preparation process.
Example 10
This example provides silver nanowires, which are different from example 1 only in that, in step (1), the concentration of the copper salt in the alcohol solution is 8 mmol/L.
Example 11
This example provides silver nanowires, which are different from example 1 only in that, in step (1), the concentration of the copper salt in the alcohol solution is 12 mmol/L.
Example 12
This example provides silver nanowires, which are different from example 1 only in that, in step (2), the dropping rate is 0.2 mL/min.
Example 13
This example provides silver nanowires, which are different from example 1 only in that, in step (2), the dropping rate is 0.9 mL/min.
Comparative example 1
The comparative example provides a method for preparing silver nanowires without propolis, the method specifically comprising the steps of:
(1) respectively weighing a certain amount of AgNO3And CuSO4·5H2Dissolving O in anhydrous ethanol, and magnetically stirring until completely dissolving to obtain AgNO with concentration of 5mmol/L3Solution and CuSO with concentration of 10mmol/L4·5H2O solution;
(2) mixing AgNO3Solution and CuSO4·5H2Mixing the O solution, and uniformly stirring to obtain a mixed solution;
wherein, AgNO350 vol% of an ethanol solution of (1), CuSO4·5H250 vol% of an ethanol solution of O;
(3) heating the mixed solution in a water bath to 70 ℃, and reacting for 72 hours to obtain a silver nanowire stock solution; and centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively, wherein each time is 5min, and dispersing the product in absolute ethyl alcohol for storage.
The product obtained was checked for the absence of silver nanowires.
Comparative example 2
The comparative example provides a method for preparing silver nanowires without adding copper salt, the method specifically comprising the steps of:
(1) weighing propolis, freezing at-20 deg.C for 10 hr, pulverizing, and sieving with 100 mesh sieve to obtain fine powder; adding 6.5g of the fine powder into 100mL of 95 vol% ethanol solution, and magnetically stirring at room temperature until the fine powder is completely dissolved to obtain 65g/L of propolis ethanol extract; weighing a certain amount of AgNO3Dissolving in anhydrous ethanol, magnetically stirring until completely dissolving to obtain a solution with a concentration of5mmol/L AgNO3A solution;
(2) mixing propolis ethanol extractive solution with AgNO3Mixing the solutions, and uniformly stirring to obtain a mixed solution;
wherein the propolis ethanol extract is 25 vol%, AgNO375 vol% of the solution;
(3) heating the mixed solution in a water bath to 70 ℃, and reacting for 72 hours to obtain a silver nanowire stock solution; centrifuging the silver nanowire stock solution twice at 12000rpm by using acetone and ethanol respectively for 5min each time, and dispersing the product in absolute ethanol for storage;
the product obtained by inspection is silver nano-particles with larger particle size, and no silver nano-wires are generated.
Comparative example 3
This comparative example provides a method for preparing silver nanowires, which is different from example 1 only in that the propolis ethanol extract solution is replaced with 1mg/mL of 1-ethyl-3-methylimidazolium chloride ethanol solution.
Performance testing
The following tests were carried out on the products shown in examples 1 to 13 and comparative examples 1 to 3, and the specific test methods were as follows:
(1) silver nano length, diameter and aspect ratio: scanning electron microscope (manufacturer: Nippon Hitachi, model: SU8020) was used;
(2) purity: scanning electron microscope (manufacturer: Nippon Hitachi, model: SU8020) was used;
(3) yield: the product silver wire is weighed after drying divided by the mass of silver nitrate times 108 divided by 169;
the specific test results are shown in table 1 below ("-" represents no nanowire formed):
TABLE 1
As shown in the test data in Table 1, the silver nanowire of the present invention has a length of 30-100 μm, a diameter of 20-120nm, an aspect ratio of 350-4000, a purity of 90% or more, and a yield of 95% or more. Therefore, the method for synthesizing the silver nanowires by using the propolis extract is green and environment-friendly, low in cost and simple in process, and the silver nanowires with high yield and high length-diameter ratio are prepared by using the propolis extract as a reducing agent and using an aqueous solution of ethanol as a solvent and avoiding using ethylene glycol, PVP and other chemical reagents which are easy to pollute the environment.
As can be seen from the comparison between example 1 and examples 5-6, the copper salt is copper sulfate, and the silver salt is silver nitrate, which promotes the growth of the one-dimensional nano-structure and is more beneficial to the generation of longer silver nanowires.
As is clear from the comparison of example 1 and examples 7 to 9, the propolis extract obtained without dilution, directly dissolved with relatively dilute ethanol, or diluted to an extent outside the range of the present application, has a low content of effective components, which in turn results in not being excellent as a reducing agent for synthesizing silver nanowires.
As is clear from the comparison between example 1 and examples 10 to 11, the alcohol solution of copper salt is too dilute or too concentrated, and thus it is impossible to form more polytwinned seeds at the initial stage of the reaction, and the yield of silver nanowires is lowered, and by-products such as silver nanoparticles are generated more.
As is clear from comparison between example 1 and examples 12 and 13, the dropping speed is in the range of 0.3-0.8mL/min, and the obtained silver nanowires have a small and long diameter, i.e., a large aspect ratio, and cannot grow well even if the dropping speed is too fast or too slow.
As can be seen from the comparison of example 1 and comparative example 1, no reducing agent was added, and the product obtained by the examination had no silver nanowires formed.
As can be seen from the comparison between example 1 and comparative example 2, the product was silver nanoparticles having a large particle size without adding copper salt, and no silver nanowires were formed.
As can be seen from the comparison of example 1 and comparative example 3, the addition of other types of reducing agents failed to perform the reaction at a lower temperature, and no silver nanowires were generated.
The applicant states that the present invention is illustrated by the above embodiments, but the present invention is not limited to the above embodiments, i.e. it does not mean that the present invention must rely on the above embodiments to be implemented. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The silver nanowire is characterized in that the raw materials for preparing the silver nanowire comprise: propolis, copper salts and silver salts.
2. The silver nanowires of claim 1, wherein the propolis accounts for 5-15% of the total mass of the silver nanowires;
preferably, the molar ratio of the silver salt to the copper salt is 1 (0.5-3).
3. The silver nanowires of claim 1 or 2, wherein the copper salt comprises any one of copper sulfate, copper hydroxycarbonate, copper nitrate or copper chloride or a combination of at least two thereof, preferably copper sulfate;
preferably, the silver salt comprises any one or a combination of at least two of silver nitrate, silver sulfate, silver phosphate or silver chloride, preferably silver nitrate.
4. The silver nanowires of any one of claims 1 to 3, wherein the silver nanowires have a length of 30 to 100 μm and a diameter of 20 to 120 nm.
5. The method for preparing silver nanowires according to any one of claims 1 to 4, comprising the steps of:
(1) extracting propolis to obtain propolis ethanol extractive solution; preparing a copper salt into an alcohol solution of the copper salt; preparing silver salt into alcoholic solution of silver salt;
(2) mixing the propolis alcohol extract obtained in the step (1) with an alcohol solution of copper salt, stirring for the first time, then dropwise adding an alcohol solution of silver salt, and stirring for the second time to obtain a mixed solution;
(3) and (3) heating the mixed solution obtained in the step (2) for reaction, and centrifuging to obtain the silver nanowire.
6. The method for preparing silver nanowires of claim 5, wherein in the step (1), the propolis alcohol extract is prepared from the following raw materials in parts by weight: 5-8 parts of propolis, 80-120 parts of ethanol and 50-120 parts of water;
preferably, in step (1), the extracting operation is specifically: freezing and pulverizing propolis, and sieving to obtain propolis fine powder; mixing the propolis fine powder with ethanol to obtain propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract to obtain propolis ethanol extract;
preferably, the freezing temperature is-20 to-10 ℃, and the freezing time is 8 to 12 hours;
preferably, the sieving is 80-100 mesh sieving;
preferably, the mass volume ratio of the propolis fine powder to the ethanol is (5-8) g:100 mL;
preferably, the concentration of the ethanol is 90-100 vol%;
preferably, the dilution is to a concentration of ethanol in the propolis ethanol extract of 50 to 70 vol%;
preferably, in the step (1), the concentration of the alcoholic solution of the copper salt is 8-12 mmol/L;
preferably, in the step (1), the concentration of the alcoholic solution of the silver salt is 0.5-10 mmol/L.
7. The method for preparing silver nanowires of claim 5 or 6, wherein in the step (2), the volume ratio of the propolis alcohol extract, the copper salt alcohol solution and the silver salt alcohol solution in the step (2) is (10-45): (35-65);
preferably, in the step (2), the temperature of the primary stirring is 25-30 ℃, the time of the primary stirring is 8-12h, and the rotation speed of the primary stirring is 600-800 rpm;
preferably, in the step (2), the dropping speed of the alcoholic solution of the silver salt is 0.3-0.8 mL/min;
preferably, in the step (2), the temperature of the secondary stirring is 25-30 ℃, the time of the secondary stirring is 2-4h, and the rotation speed of the secondary stirring is 350-550 rpm.
8. The method for preparing silver nanowires according to any one of claims 5 to 7, wherein in the step (3), the temperature of the heating reaction is 65 to 80 ℃, and the time of the heating reaction is 24 to 72 hours;
preferably, in the step (3), the rotation speed of the centrifugal treatment is 10000-;
preferably, in step (3), a solvent is added for the centrifugation treatment, and the solvent comprises acetone and/or ethanol.
9. The method for preparing silver nanowires according to any one of claims 5 to 8, wherein the method for preparing silver nanowires comprises the steps of:
(1) freezing propolis at-20 to-10 ℃ for 8 to 12 hours, crushing, and sieving by a sieve of 80 to 100 meshes to obtain propolis fine powder; mixing propolis fine powder with ethanol to obtain 50-80g/L propolis ethanol extract; finally, adding water to dilute the propolis ethanol extract to 50-70 vol% to obtain propolis ethanol extract; mixing copper salt with ethanol to obtain an alcohol solution of the copper salt with the concentration of 8-12 mmol/L; mixing silver salt with ethanol to obtain 0.5-10mmol/L copper salt alcoholic solution;
(2) mixing the propolis alcohol extract obtained in the step (1) with an alcohol solution of a copper salt, stirring at 800rpm for 8-12h at 25-30 ℃, dropwise adding an alcohol solution of a silver salt at the speed of 0.3-0.8mL/min, and stirring at 550rpm for 2-4h at 350-30 ℃ to obtain a mixed solution;
wherein the volume ratio of the propolis alcohol extract to the alcohol solution of the copper salt to the alcohol solution of the silver salt is (10-45): (35-65);
(3) heating the mixed solution obtained in the step (2) at 65-80 ℃ for reaction for 24-72h to obtain silver nanowire stock solution; and centrifuging the silver nanowire stock solution by using acetone and ethanol respectively at 10000-15000rpm for 1-5 times, and each time for 4-6min to obtain the silver nanowire.
10. Use of silver nanowires according to any of claims 1-4 for the preparation of transparent electrodes and/or antimicrobial materials.
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