CN102211203B - Silver nanoparticles and method for producing silver nanoparticle array - Google Patents
Silver nanoparticles and method for producing silver nanoparticle array Download PDFInfo
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- CN102211203B CN102211203B CN 201010141088 CN201010141088A CN102211203B CN 102211203 B CN102211203 B CN 102211203B CN 201010141088 CN201010141088 CN 201010141088 CN 201010141088 A CN201010141088 A CN 201010141088A CN 102211203 B CN102211203 B CN 102211203B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 32
- 239000004332 silver Substances 0.000 title claims abstract description 32
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 26
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title abstract 6
- 238000004519 manufacturing process Methods 0.000 title description 2
- 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 abstract description 35
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 235000014113 dietary fatty acids Nutrition 0.000 claims abstract description 17
- 239000000194 fatty acid Substances 0.000 claims abstract description 17
- 229930195729 fatty acid Natural products 0.000 claims abstract description 17
- 150000004665 fatty acids Chemical class 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 150000003852 triazoles Chemical class 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229920001600 hydrophobic polymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 4
- 239000003381 stabilizer Substances 0.000 claims abstract description 3
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical group [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 claims description 17
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 16
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 14
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 14
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 14
- 150000003378 silver Chemical class 0.000 claims description 13
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 11
- 229920005989 resin Polymers 0.000 claims description 11
- 239000011347 resin Substances 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229920002521 macromolecule Polymers 0.000 claims description 10
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 10
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 claims description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 claims description 4
- 229960002317 succinimide Drugs 0.000 claims description 4
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 229940074391 gallic acid Drugs 0.000 claims description 3
- 235000004515 gallic acid Nutrition 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims description 2
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 2
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 2
- TVRUTDPQQPQEDW-UHFFFAOYSA-L ClC=1C(=C(C(=C(C1C(=O)[O-])C(=O)[O-])Cl)Cl)Cl.[Ag+2] Chemical compound ClC=1C(=C(C(=C(C1C(=O)[O-])C(=O)[O-])Cl)Cl)Cl.[Ag+2] TVRUTDPQQPQEDW-UHFFFAOYSA-L 0.000 claims description 2
- 235000021360 Myristic acid Nutrition 0.000 claims description 2
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 239000005642 Oleic acid Substances 0.000 claims description 2
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 2
- 235000021314 Palmitic acid Nutrition 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 150000001721 carbon Chemical group 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 229940043237 diethanolamine Drugs 0.000 claims description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 2
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 2
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- LFSXCDWNBUNEEM-UHFFFAOYSA-N phthalazine Chemical class C1=NN=CC2=CC=CC=C21 LFSXCDWNBUNEEM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- -1 silver tolyltriazole salt Chemical class 0.000 claims description 2
- QOVGHSPSIUCXQC-UHFFFAOYSA-M silver;2-carboxyphenolate Chemical compound [Ag+].OC1=CC=CC=C1C([O-])=O QOVGHSPSIUCXQC-UHFFFAOYSA-M 0.000 claims description 2
- YCPUVKXPVYSBAJ-UHFFFAOYSA-M silver;2-phenylacetate Chemical compound [Ag+].[O-]C(=O)CC1=CC=CC=C1 YCPUVKXPVYSBAJ-UHFFFAOYSA-M 0.000 claims description 2
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 claims description 2
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 238000002156 mixing Methods 0.000 abstract description 9
- 238000009826 distribution Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 4
- 239000010949 copper Substances 0.000 abstract description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 2
- 229910052802 copper Inorganic materials 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 229920001477 hydrophilic polymer Polymers 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 32
- 239000000126 substance Substances 0.000 description 9
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 6
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 6
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- XIBQIEXKKBNYOT-UHFFFAOYSA-N phthalic acid;silver Chemical compound [Ag].OC(=O)C1=CC=CC=C1C(O)=O XIBQIEXKKBNYOT-UHFFFAOYSA-N 0.000 description 4
- JUICCGFPFVVOMS-UHFFFAOYSA-N hexanedioic acid;silver Chemical compound [Ag].OC(=O)CCCCC(O)=O JUICCGFPFVVOMS-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 3
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
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Abstract
The invention relates to a preparation method of silver nanoparticles and a preparation method of a silver nanoparticle array with uniform size distribution. Mixing one of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salt and a reduction promoter with a hydrophobic polymer compound solution or a hydrophilic polymer compound aqueous solution serving as a stabilizer, uniformly stirring, carrying out ball milling by a ball mill or ultrasonic dispersion by an ultrasonic instrument, adding a reducing agent, controlling the reaction temperature to be 30-60 ℃ under a stirring state, and carrying out reduction reaction to obtain a dispersion liquid containing silver nanoparticles. And dropwise coating the prepared dispersion liquid containing the silver nanoparticles on a carbon-coated copper net, and drying at room temperature to self-assemble the silver nanoparticles into an orderly-arranged silver nanoparticle array. The silver nanoparticles with small particle size and uniform size distribution can be prepared by the method, and the nanoparticles can be highly orderly arranged on the carbon-coated copper net.
Description
Technical field
The present invention relates to a kind of preparation method of Nano silver grain, and a kind of preparation method of silver nanoparticle array of even size distribution.
Background technology
Nano silver grain demonstrates unique light, electricity, thermal and magnetic character because having higher specific area and surface-active, might obtain in fields such as nano electron device, effective catalyst, novel conductive and biomedical composite, high-performance conductive inks extensive use.
The pattern of nano particle, size, distribution of sizes and preparation method are closely related.At present, Nano silver grain has multiple preparation method, and such as microemulsion method, reverse micelle method, but these method preparation process are loaded down with trivial details, and control procedure is complicated.Chemical reduction method is a kind of preparation method commonly used, and its advantage is that step is simple, and can prepare in the short period of time a large amount of nano particles, but still there are a lot of shortcomings in this method at present, and is large such as prepared nano particle diameter, particle size distribution is unequal.
Summary of the invention
The object of the invention is to overcome the shortcoming that exists among the above-mentioned existing preparation method, a kind of preparation method of the simple to operate and prepared Nano silver grain that the Nano silver grain size is little, particle diameter is evenly distributed is provided, and the method that described Nano silver grain is prepared into the silver nanoparticle array of ordered arrangement.
The preparation method of Nano silver grain of the present invention is: with a kind of and reduction accelerator in fatty acid silver salt, aromatic carboxylic acid silver salt or the triazole organic silver salts and as the aqueous solution of the hydrophobic polymer compound solution of stabilizing agent or hydrophilic macromolecular compounds and stir, after ball mill ball milling or the ultrasonic dispersion of Ultrasound Instrument (general ball milling or ultrasonic time are 1～4 hour), adding reducing agent and control reaction temperature under stirring is 30 ℃～60 ℃, carry out reduction reaction, obtain containing the dispersion liquid of Nano silver grain.
It is 6 to 22 straight chain and/or branched carboxylic acids root that fatty acid radical in the described fatty acid silver salt is selected from carbon chain lengths.
A kind of during aliphatic acid silver in the described fatty acid silver salt is selected from silver stearate, Silver behenate, laurate silver, myristic acid is silver-colored, palmitic acid is silver-colored, oleic acid is silver-colored, adipic acid is silver-colored, decanedioic acid is silver-colored etc.
Described aromatic carboxylic acid silver salt is selected from a kind of in benzoic acid silver salt, phenylacetic acid silver salt, O-phthalic acid silver salt, tetrachlorophthalic acid silver salt, the salicylic acid silver salt etc.
Described triazole organic silver salts is selected from a kind of in BTA silver salt, the silver tolyltriazole salt etc.
Described reduction accelerator is selected from a kind of in phthalazines, succinimide, phthalimide, the triphenyl phosphorus etc., and the addition of reduction accelerator is 5%～100% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts molal quantity.
Described hydrophobic polymer compound solution is dissolved in the organic solvent by the hydrophobic polymer compound and obtains; Described organic solvent is selected from a kind of in ethanol, propyl alcohol, n-butanol, the n-amyl alcohol etc.; Described hydrophobic polymer compound is selected from a kind of in polyvinyl formal, the polyvinyl butyral resin etc.; The consumption of described hydrophobic polymer compound is preferably 0.5%～20% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts quality.
The described hydrophilic macromolecular compounds aqueous solution is dissolved in the deionized water by hydrophilic macromolecular compounds and obtains; Described hydrophilic macromolecular compounds is selected from a kind of in polyvinyl alcohol, polyacrylic acid, the polyvinylpyrrolidone etc.; The consumption of described hydrophilic macromolecular compounds is preferably 5%～40% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts quality.
Described reducing agent is selected from a kind of in the phenolic compound shown in gallic acid, pyrogallic acid, hydroquinones, monoethanolamine, diethanol amine, triethanolamine, hydrazine hydrate, ascorbic acid, following formula 1 or the formula 2;
Formula 1
Formula 2
In the formula, R is that hydrogen atom or carbon atom quantity are 1～5 alkyl, and L is methylene or ethylidene,
Described reducing agent consumption is 1%～50% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts molal quantity.
The present invention also provides a kind of preparation method of silver nanoparticle array, and the method is that the dispersant liquid drop that contains Nano silver grain with above-mentioned preparation is coated in and covers on the carbon copper mesh, and after the drying at room temperature, Nano silver grain is self-assembled into the silver nanoparticle array of ordered arrangement.
In the present invention, fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts are reduced into the method for Nano silver grain and the method for silver nanoparticle array of preparation ordered arrangement, simple to operate, need not special test equipment, reaction condition is gentle, and by transmission electron microscope observing, gained Nano silver grain size is little and be evenly distributed, particle size is about 5nm, and the silver nanoparticle array of the ordered arrangement of preparing has been realized the high-sequential arrangement.
Description of drawings
Fig. 1 is the transmission electron microscope photo of the Nano silver grain of the embodiment of the invention 1;
Fig. 2 is the transmission electron microscope photo of the silver nanoparticle array of the embodiment of the invention 1.
The specific embodiment
The present invention is described in detail below in conjunction with embodiment and accompanying drawing.
Embodiment 1
Take by weighing silver stearate 10g, take by weighing triphenyl phosphorus by 5% of silver stearate molal quantity; Take by weighing 0.05g polyvinyl butyral resin (Xing Jin chemical plant, Beijing, butyraldehyde base content 40～50%, viscosity 80～100 seconds) and be dissolved in the 9.95g n-butanol by 0.5% of silver stearate quality, be mixed with the butanol solution of polyvinyl butyral resin; In the solution that the silver stearate that takes by weighing and triphenyl phosphorus are joined the polyvinyl butyral resin of preparing and stir; Then use planetary gear ball mill (Nanjing Univ. Instrument Factory, QM-ISP-2-CL) ball milling disperseed 1 hour; Add gallic acid and stir by 1% of silver stearate molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 60 ℃, reacts 1 hour, can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain be coated in cover the carbon copper mesh (the auspicious technology in Beijing emerging hundred Co., Ltd, G300-Cu) on, after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.(the FDAC electronics, JEM2100) photo as shown in Figure 1 and Figure 2 for the transmission electron microscope of prepared Nano silver grain and silver nanoparticle array.
Embodiment 2
Take by weighing silver stearate 10g, take by weighing triphenyl phosphorus by 100% of silver stearate molal quantity; Take by weighing 2g polyvinyl butyral resin (Xing Jin chemical plant, Beijing, butyraldehyde base content 40～50%, viscosity 80～100 seconds) and be dissolved in the 8g n-butanol by 20% of silver stearate quality, be mixed with the butanol solution of polyvinyl butyral resin; In the solution that the silver stearate that takes by weighing and triphenyl phosphorus are joined the polyvinyl butyral resin of preparing and stir; Then use planetary gear ball mill (the same) ball milling to disperse 4 hours; Add catechol and stir by 50% of silver stearate molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 30 ℃, reacts 3 hours, can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 3
Take by weighing silver stearate 10g, take by weighing triphenyl phosphorus by 50% of silver stearate molal quantity; Take by weighing 0.5g polyvinyl butyral resin (Xing Jin chemical plant, Beijing, butyraldehyde base content 40～50%, viscosity 80～100 seconds) and be dissolved in the 9.5g n-butanol by 5% of silver stearate quality, be mixed with the butanol solution of polyvinyl butyral resin; In the solution that the silver stearate that takes by weighing and triphenyl phosphorus are joined the polyvinyl butyral resin of preparing and stir; Then use the ultrasonic dispersion of Ultrasound Instrument 2 hours; Add as shown in Equation 2 compound (production of Fluka company) and stir by 10% of silver stearate molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 40 ℃, and ultrasonic its reaction 1 hour that makes simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 4
Take by weighing Silver behenate 2g, take by weighing phthalimide by 25% of Silver behenate molal quantity; Take by weighing 0.5g polyacrylic acid (number-average molecular weight 2000) and be dissolved in the 9.5g deionized water by 25% of Silver behenate quality, be mixed with the polyacrylic aqueous solution; Join the Silver behenate that takes by weighing and phthalimide in the polyacrylic aqueous solution of preparing and stir; Then disperseed 3 hours with the planetary gear ball mill ball milling; Add pyrogallic acid and stir by 5% of Silver behenate molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 30 ℃, and ultrasonic its reaction 2 hours that make simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 5
Take by weighing adipic acid silver 5g, take by weighing succinimide by 10% of Silver behenate molal quantity, (average degree of polymerization is 1788+50 to take by weighing the 2g polyvinyl alcohol by 40% of the silver amount of adipic acid, chemical pure, Xu Dong chemical plant, Beijing) and be dissolved in the 18g deionized water, be mixed with the aqueous solution of polyvinyl alcohol; Join the adipic acid silver that takes by weighing and succinimide in the polyvinyl alcohol water solution of preparing and stir; Then used the ball mill ball milling 2 hours; Add triethanolamine and stir by 100% of adipic acid silver molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 50 ℃, and ultrasonic its reaction 2 hours that make simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 6
Take by weighing phthalic acid silver 5g, take by weighing triphenyl phosphorus by 50% of phthalic acid silver molal quantity; Take by weighing the 0.25g polyvinyl alcohol and be dissolved in the 4.75g deionized water by 5% of the silver amount of phthalic acid, be mixed with the aqueous solution of polyvinyl alcohol; In the aqueous solution that the phthalic acid silver that takes by weighing and triphenyl phosphorus are joined the polyvinyl alcohol of preparing and stir; Then used the ball mill ball milling 3 hours; Add pyrogallic acid and stir by 10% of phthalic acid silver molal quantity; Under the mixing speed of 3500rpm, the control reaction temperature is 30 ℃, and ultrasonic its reaction 3 hours that make simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 7
Take by weighing silver benzotriazole 2g, take by weighing triphenyl phosphorus by 80% of silver benzotriazole molal quantity; Take by weighing 0.1g polyvinyl alcohol (average degree of polymerization is 1788 ± 50, chemical pure, Xu Dong chemical plant, Beijing) and be dissolved in the deionized water of 9.9g by 5% of silver benzotriazole quality, be mixed with the aqueous solution of polyvinyl alcohol; In the aqueous solution that the silver benzotriazole that takes by weighing and triphenyl phosphorus are joined the polyvinyl alcohol of preparing and stir; Then used the ball mill ball milling 3 hours; Add pyrogallic acid and stir by 15% of silver benzotriazole molal quantity; Under the mixing speed of 4000rpm, the control reaction temperature is 60 ℃, and ultrasonic its reaction 3 hours that make simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Embodiment 8
Take by weighing silver tolyltriazole 2g, take by weighing triphenyl phosphorus by 100% of silver tolyltriazole molal quantity; Take by weighing 0.2g polyvinyl alcohol (average degree of polymerization is 1788 ± 50, chemical pure, Xu Dong chemical plant, Beijing) and be dissolved in the 9.8g deionized water by 10% of silver tolyltriazole quality, be mixed with the aqueous solution of polyvinyl alcohol; In the aqueous solution that the silver tolyltriazole that takes by weighing and triphenyl phosphorus are joined the polyvinyl alcohol of preparing and stir; Then used the ball mill ball milling 4 hours; Add pyrogallic acid and stir by 20% of silver benzotriazole molal quantity; Under the mixing speed of 3700rpm, the control reaction temperature is 60 ℃, and ultrasonic its reaction 4 hours that make simultaneously can obtain containing the dispersion liquid of Nano silver grain; Filter, can obtain Nano silver grain.Get dispersant liquid drop that above-mentioned 1ml contains Nano silver grain and be coated in and cover on the carbon copper mesh (the same), after the drying at room temperature, Nano silver grain just is self-assembled into the silver nanoparticle array of ordered arrangement.
Claims (10)
1. the preparation method of a Nano silver grain, it is characterized in that: with a kind of and reduction accelerator in fatty acid silver salt, aromatic carboxylic acid silver salt or the triazole organic silver salts and as the aqueous solution of the hydrophobic polymer compound solution of stabilizing agent or hydrophilic macromolecular compounds and stir, after ball mill ball milling or the ultrasonic dispersion of Ultrasound Instrument, adding reducing agent and control reaction temperature under stirring is 30 ℃～60 ℃, carry out reduction reaction, obtain containing the dispersion liquid of Nano silver grain.
2. the preparation method of Nano silver grain according to claim 1 is characterized in that: described fatty acid silver salt is that carbon chain lengths is 6 to 22 straight chain and/or branched carboxylic acids silver.
3. the preparation method of Nano silver grain according to claim 2 is characterized in that: described fatty acid silver salt is selected from silver stearate, Silver behenate, laurate silver, myristic acid is silver-colored, palmitic acid is silver-colored, oleic acid is silver-colored, adipic acid is silver-colored, a kind of in silver-colored of decanedioic acid.
4. the preparation method of Nano silver grain according to claim 1 is characterized in that: described aromatic carboxylic acid silver salt is selected from a kind of in benzoic acid silver salt, phenylacetic acid silver salt, O-phthalic acid silver salt, tetrachlorophthalic acid silver salt, the salicylic acid silver salt.
5. the preparation method of Nano silver grain according to claim 1 is characterized in that: described triazole organic silver salts is selected from a kind of in BTA silver salt, the silver tolyltriazole salt.
6. the preparation method of Nano silver grain according to claim 1 is characterized in that: described reduction accelerator is selected from a kind of in phthalazines, succinimide, phthalimide, the triphenyl phosphorus; The addition of reduction accelerator is 5%～100% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts molal quantity.
7. the preparation method of Nano silver grain according to claim 1, it is characterized in that: described hydrophobic polymer compound solution is dissolved in the organic solvent by the hydrophobic polymer compound and obtains, and described organic solvent is selected from a kind of in ethanol, propyl alcohol, n-butanol, the n-amyl alcohol; Described hydrophobic polymer compound is selected from a kind of in polyvinyl formal, the polyvinyl butyral resin; The consumption of described hydrophobic polymer compound is 0.5%～20% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts quality.
8. the preparation method of Nano silver grain according to claim 1, it is characterized in that: the described hydrophilic macromolecular compounds aqueous solution is dissolved in the deionized water by hydrophilic macromolecular compounds and obtains; Described hydrophilic macromolecular compounds is selected from a kind of in polyvinyl alcohol, polyacrylic acid, the polyvinylpyrrolidone; The consumption of described hydrophilic macromolecular compounds is 5%～40% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts quality.
9. the preparation method of Nano silver grain according to claim 1 is characterized in that: described reducing agent is selected from a kind of in the phenolic compound shown in gallic acid, pyrogallic acid, hydroquinones, monoethanolamine, diethanol amine, triethanolamine, hydrazine hydrate, ascorbic acid, following formula 1 or the formula 2;
Formula 1
Formula 2
In the formula, R is that hydrogen atom or carbon atom quantity are 1～5 alkyl, and L is methylene or ethylidene,
Described reducing agent consumption is 1%～50% of fatty acid silver salt, aromatic carboxylic acid silver salt or triazole organic silver salts molal quantity.
10. the preparation method of a silver nanoparticle array, it is characterized in that: the method is the dispersant liquid drop that contains Nano silver grain prepared in claim 1～9 any one to be coated in cover on the carbon copper mesh, after the drying at room temperature, Nano silver grain is self-assembled into the silver nanoparticle array of ordered arrangement.
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| JP6001861B2 (en) * | 2012-01-11 | 2016-10-05 | 株式会社ダイセル | Silver nanoparticle production method, silver nanoparticle, and silver coating composition |
| TWI635918B (en) * | 2012-08-07 | 2018-09-21 | 大賽璐股份有限公司 | Method for manufacturing silver nanoparticles and silver nanoparticles |
| CN102886527B (en) * | 2012-10-12 | 2015-06-03 | 东华大学 | Method for preparing cubic crystal form nano-silver material by using oleic acid silver as raw material based on oil-water interface method |
| CN102896326A (en) * | 2012-10-30 | 2013-01-30 | 东华大学 | Method for preparing cubic crystal type nano-silver material by utilizing oil-water interface method of oleic acid |
| CN103302306A (en) * | 2013-06-19 | 2013-09-18 | 东南大学 | Method for reducing and preparing functionalized nano-silver based on polyphenol |
| CN103588164A (en) * | 2013-10-08 | 2014-02-19 | 上海交通大学 | Copper-silver micro-nano multi-stage structure super-hydrophobic surface and production method thereof |
| CN103611940B (en) * | 2013-11-29 | 2015-08-05 | 江苏瑞德新能源科技有限公司 | A kind of preparation method of conductive silver paste flake silver powder |
| JP6428339B2 (en) | 2015-02-13 | 2018-11-28 | 三菱マテリアル株式会社 | Silver powder and paste-like composition and method for producing silver powder |
| CN105268994A (en) * | 2015-12-02 | 2016-01-27 | 广东南海启明光大科技有限公司 | Preparation method for emulsion containing nano-silver particles |
| CN107084997B (en) * | 2017-04-10 | 2020-02-14 | 中国乐凯集团有限公司 | Method for detecting morphology of silver behenate crystal in silver salt imaging material |
| CN110181074B (en) * | 2019-06-26 | 2022-04-12 | 江苏汇诚医疗科技有限公司 | Method for green preparation of high-length-diameter-ratio silver nanowires by composite soft template method |
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| CN1266761A (en) * | 2000-03-23 | 2000-09-20 | 南京大学 | Process for preparing nm-class silver powder |
| CN1817515A (en) * | 2006-01-09 | 2006-08-16 | 四川大学 | Method of dispersing nanometer silver powder |
| CN101384388A (en) * | 2006-03-10 | 2009-03-11 | 三井金属矿业株式会社 | Process for production of ultrafine silver particles and ultrafine silver particles produced by the process |
| CN101013257A (en) * | 2007-01-17 | 2007-08-08 | 中国科学院理化技术研究所 | Application of metal organic acid salt as developing accelerator |
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