KR20190125764A - Method for preparing silver nanoparticles stabilized with tetraoctylammonium - Google Patents
Method for preparing silver nanoparticles stabilized with tetraoctylammonium Download PDFInfo
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- KR20190125764A KR20190125764A KR1020180049983A KR20180049983A KR20190125764A KR 20190125764 A KR20190125764 A KR 20190125764A KR 1020180049983 A KR1020180049983 A KR 1020180049983A KR 20180049983 A KR20180049983 A KR 20180049983A KR 20190125764 A KR20190125764 A KR 20190125764A
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- silver
- thiosulfate
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- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 17
- CHYBTAZWINMGHA-UHFFFAOYSA-N tetraoctylazanium Chemical compound CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CHYBTAZWINMGHA-UHFFFAOYSA-N 0.000 title abstract description 16
- 150000004764 thiosulfuric acid derivatives Chemical class 0.000 claims abstract description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 21
- 229910052709 silver Inorganic materials 0.000 claims description 21
- 239000004332 silver Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- -1 silver-thiosulfate anion Chemical class 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 17
- 239000012454 non-polar solvent Substances 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 14
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 claims description 13
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002798 polar solvent Substances 0.000 claims description 8
- 230000007704 transition Effects 0.000 claims description 7
- 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 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical group [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 4
- 150000001450 anions Chemical group 0.000 claims description 4
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- RBWNDBNSJFCLBZ-UHFFFAOYSA-N 7-methyl-5,6,7,8-tetrahydro-3h-[1]benzothiolo[2,3-d]pyrimidine-4-thione Chemical compound N1=CNC(=S)C2=C1SC1=C2CCC(C)C1 RBWNDBNSJFCLBZ-UHFFFAOYSA-N 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 3
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- NQXBRQZPHIYOKB-UHFFFAOYSA-N [F].[Ag] Chemical compound [F].[Ag] NQXBRQZPHIYOKB-UHFFFAOYSA-N 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 description 13
- 239000002105 nanoparticle Substances 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 239000003381 stabilizer Substances 0.000 description 10
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000011481 absorbance measurement Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229940006460 bromide ion Drugs 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000005226 mechanical processes and functions Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
-
- B22F1/0003—
-
- 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
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
Description
본 발명은 테트라옥틸암모늄으로 안정화된 은 나노입자의 제조방법에 관한 것이다.The present invention relates to a method for preparing silver nanoparticles stabilized with tetraoctylammonium.
은 (Ag)은 대표적인 귀금속 중 하나지만, 전 세계 생산량의 70 % 이상이 공업용으로 사용되고 있을 만큼 산업적 응용이 매우 큰 물질로서 촉매, 항균 및 탈취 효과뿐만 아니라 높은 전기 전도성을 가지고 있기 때문에, 이러한 성질들을 이용한 은 나노입자는 유기 촉매제, 광학 센서, 각종 전자기기의 결합 소재 및 도전서 도료 등으로 널리 사용되고 있다.Silver (Ag) is one of the most important precious metals, but it is very important for industrial applications as more than 70% of the world's production is used for industrial purposes, and because of its high electrical conductivity as well as catalytic, antibacterial and deodorizing effects, The silver nanoparticles used are widely used as organic catalysts, optical sensors, bonding materials for various electronic devices, conductive paints, and the like.
이러한 은 나노입자를 제조하는 방법으로는 화학적 합성 방법, 기계적 제조 방법 등이 있는데, 기계적 공정을 통해 분쇄하는 기계적 제조 방법의 경우 공정 중 불순물의 혼입 가능성이 굉장히 높고 균일한 나노 크기의 입자 형성이 쉽지 않은 단점이 있고, 화학적 합성 방법의 경우 은 전구체를 이용해 은 입자를 제조하는 방법으로 기상법과 액상 환원법 등이 있는데, 기상법의 경우 매우 고가의 장비가 필요하다는 단점이 있어, 수득률이 높고, 반응 시간 및 온도 조절 등을 통해 비교적 쉽게 다양한 크기의 균일한 나노 입자를 상대적으로 적은 비용으로 얻을 수 있는 액상 환원법이 선호되고 있다. 이러한 액상 환원법을 이용하면 친수성과 소수성 두 종류의 나노입자를 합성할 수 있는데, 소수성 나노입자의 합성시 보다 높은 결정성과 균일한 크기의 나노입자를 합성할 수 있다.Such silver nanoparticles may be prepared by chemical synthesis or mechanical manufacturing. In the case of mechanical manufacturing, which is pulverized by a mechanical process, impurities are very likely to be mixed during the process, and uniform nano-size particles are easily formed. In the case of chemical synthesis method, there are gas phase method and liquid phase reduction method for preparing silver particles using silver precursor, but gas phase method requires a very expensive equipment, and thus yields are high, reaction time and The liquid phase reduction method which can obtain uniform nanoparticles of various sizes relatively easily through temperature control at a relatively low cost is preferred. Using this liquid phase reduction method, two types of nanoparticles may be synthesized, which are hydrophilic and hydrophobic. Synthesis of nanoparticles of higher crystallinity and uniform size may be achieved when hydrophobic nanoparticles are synthesized.
소수성 은 나노입자 합성의 경우 말단 기에 아민 기나 싸이올 기를 갖는 긴 탄소 사슬의 안정제가 많이 이용되는데, 특히 싸이올 기를 갖는 안정제를 사용할 경우 나노입자에게 용액 내에서 높은 분산 안정성은 부여할 수 있지만, 싸이올 기와 입자 표면간의 매우 강한 결합에 의해 촉매나 생물학적 분야에서 요구되는 은 나노입자의 기능을 떨어뜨릴 수 있다는 단점이 있다.In the case of hydrophobic silver nanoparticle synthesis, a long carbon chain stabilizer having an amine group or a thiol group at the end group is frequently used. Particularly, a stabilizer having a thiol group can give nanoparticles high dispersion stability in solution. The very strong bonding between the oligomers and the particle surface has the disadvantage that the silver nanoparticles, which are required in the catalyst or biological field, may be impaired.
한편, 금 나노입자의 경우 금속 표면에 대해 상대적으로 약한 결합력을 갖는 테트라옥틸암모늄을 안정제로 이용한 연구가 보고된 바 있으나, 이를 은 나노입자의 합성에 적용한 예는 보고된 바 없다.Meanwhile, in the case of gold nanoparticles, a study using tetraoctylammonium having a relatively weak bonding force to a metal surface as a stabilizer has been reported, but no example of applying this to the synthesis of silver nanoparticles has been reported.
따라서, 입자 표면과 보다 약한 결합력을 가지면서 입자의 높은 분산 안정성을 유지시킬 수 있는 안정제의 사용을 통해 은 나노입자 본연의 특성을 발휘하도록 하기 위한 새로운 은 나노입자의 합성법이 요구되는 실정이다.Therefore, there is a need for a new method of synthesizing silver nanoparticles to exhibit the natural properties of silver nanoparticles through the use of stabilizers capable of maintaining a high dispersion stability of the particles while having a weaker binding force with the particle surface.
본 발명은 전술한 문제점을 해결하기 위해 안출된 것으로, 본 발명에서는 싸이오설페이트염 처리를 통해 테트라옥틸암모늄으로 안정화된 은 나노입자를 제조하는 방법을 제공하고자 한다.The present invention has been made to solve the above-mentioned problems, the present invention is to provide a method for producing silver nanoparticles stabilized with tetraoctyl ammonium through a thiosulfate salt treatment.
또한, 본 발명은 상기 제조방법에 의해 제조된 은 나노입자를 제공하고자 한다.In addition, the present invention is to provide a silver nanoparticles prepared by the above production method.
본 발명은 상기 과제를 해결하기 위하여,The present invention to solve the above problems,
(a) 테트라옥틸암모늄 브로마이드(TOABr)가 용해된 무극성 용매와 은 전구체가 용해된 극성 용매의 혼합물을 제조하는 단계;(a) preparing a mixture of an apolar solvent in which tetraoctylammonium bromide (TOABr) is dissolved and a polar solvent in which silver precursor is dissolved;
(b) 상기 혼합물에 싸이오설페이트염을 첨가하여 무극성 용매 층으로 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)을 상전이시키는 단계; 및(b) adding a thiosulfate salt to the mixture to phase-transfer the silver-thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) to a nonpolar solvent layer; And
(c) 상기 은-싸이오설페이트 음이온이 상전이된 무극성 용매 층을 분리한 후, 환원제를 첨가하는 단계;를 포함하는 은 나노입자의 제조방법을 제공한다.(c) separating the nonpolar solvent layer in which the silver-thiosulfate anion is phase-transferred, and then adding a reducing agent to provide a method for producing silver nanoparticles.
본 발명에 따르면, 상기 (b) 단계에서 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)이 형성된 후, 브롬 이온(Br-)과 음이온 치환 반응을 통해 상기 은-싸이오설페이트 음이온이 상전이될 수 있다.According to the invention, in step (b) is - via a substitution reaction and an anion wherein the silver-thiosulfate anion ([Ag (S 2 O 3 ) 2] 3-) is then formed, a bromine ion (Br) - The thiosulfate anion may be phase shifted.
본 발명에 따르면, 상기 무극성 용매는 벤젠(benzene), 헥세인(hexane), 톨루엔(toluene), 이황화탄소(CS2), 사염화탄소(CCl4), 클로로포름(CHCl3), 디클로로메탄(CH2Cl2) 및 옥타데센(Octadecene) 중에서 선택된 1종 이상일 수 있다.According to the present invention, the nonpolar solvent is benzene, hexane, toluene, toluene, carbon disulfide (CS 2 ), carbon tetrachloride (CCl 4 ), chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ) and octadecene (Octadecene) may be one or more selected.
본 발명에 따르면, 상기 은 전구체는 질산은(AgNO3), 과염소산은(AlClO4), 염소산은(AgClO3), 탄산은(Ag2CO3), 황산은(Ag2SO4), 염화은(AgCl), 브롬화은(AgBr) 및 불소은(AgF)으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.According to the present invention, the silver precursor is silver nitrate (AgNO 3 ), silver perchlorate (AlClO 4 ), silver chlorate (AgClO 3 ), silver carbonate (Ag 2 CO 3 ), silver sulfate (Ag 2 SO 4 ), silver chloride (AgCl ), Silver bromide (AgBr) and fluorine silver (AgF) may be one or more selected from the group consisting of.
본 발명에 따르면, 상기 극성 용매는 물, 알코올 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상일 수 있다.According to the present invention, the polar solvent may be at least one selected from the group consisting of water, alcohols and mixtures thereof.
본 발명에 따르면, 상기 싸이오설페이트염은 소듐싸이오설페이트, 암모늄싸이오설페이트, 실버싸이오설페이트 및 포타슘싸이오설페이트로 이루어진 군에서 선택된 1종 이상일 수 있다.According to the present invention, the thiosulfate salt may be at least one selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, silver thiosulfate and potassium thiosulfate.
본 발명에 따르면, 상기 환원제는 수소화붕소나트륨, 하이드라진, 아스코브르산, 아스코브르산 나트륨 및 이들의 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다.According to the present invention, the reducing agent may be at least one selected from the group consisting of sodium borohydride, hydrazine, ascorbic acid, sodium ascorbate and mixtures thereof.
또한, 본 발명은 상기 제조방법에 따라 제조된 은 나노입자를 제공한다.The present invention also provides a silver nanoparticles prepared according to the above production method.
본 발명에 따르면 싸이오설페이트염 처리를 통해 테트라옥틸암모늄으로 안정화되어 높은 분산 안정성을 가지는 소수성 은 나노입자를 제공할 수 있다.According to the present invention, it is possible to provide hydrophobic silver nanoparticles having high dispersion stability by stabilizing with tetraoctylammonium through a thiosulfate salt treatment.
도 1은 본 발명에 따른 은 나노입자의 제조 공정을 개략적으로 나타낸 도면이다.
도 2는 본 발명에 따라 싸이오설페이트염을 첨가하여 상전이가 일어난 무극성 용매층의 1H NMR 분석 결과를 나타낸 것이다.
도 3은 본 발명의 실시예 1에 따라 톨루엔 중에 분산된, 싸이오설페이트염 처리를 통해 테트라옥틸암모늄으로 안정화된 은 나노입자(TOAS-Ag NPs)의 HR-TEM 이미지이다.
도 4는 도 3의 HR-TEM 이미지로부터 측정된 TOAS-Ag NPs의 크기 분포를 나타낸 그래프이다.
도 5는 본 발명의 비교예 1에 따라 합성된 은 나노입자의 HR-TEM 이미지이다.
도 6은 본 발명의 실시에 1에 따라 합성된 TOAS-Ag NPs의 합성 5일 후 TEM 이미지를 나타낸 것이다.
도 7은 본 발명의 실시에 1에 따라 합성된 TOAS-Ag NPs의 UV 흡광도를 나타낸 그래프이다.1 is a view schematically showing a manufacturing process of silver nanoparticles according to the present invention.
Figure 2 shows the results of the 1 H NMR analysis of a non-polar solvent layer in which the phase transition by adding a thiosulfate salt in accordance with the present invention.
3 is an HR-TEM image of silver nanoparticles (TOAS-Ag NPs) stabilized with tetraoctylammonium through thiosulfate salt treatment, dispersed in toluene according to Example 1 of the present invention.
FIG. 4 is a graph showing the size distribution of TOAS-Ag NPs measured from the HR-TEM image of FIG. 3.
5 is an HR-TEM image of silver nanoparticles synthesized according to Comparative Example 1 of the present invention.
FIG. 6 shows a TEM image after 5 days of synthesis of TOAS-Ag NPs synthesized according to Example 1 of the present invention.
7 is a graph showing the UV absorbance of TOAS-Ag NPs synthesized according to Example 1 of the present invention.
이하, 본 발명을 보다 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
종래 소수성 은 나노입자 합성의 경우 말단 기에 아민 기나 싸이올 기를 갖는 긴 탄소 사슬의 안정제가 많이 이용되어 왔는데, 특히 싸이올 기를 갖는 안정제를 사용할 경우 나노입자에게 용액 내에서 높은 분산 안정성은 부여할 수 있지만, 싸이올 기와 입자 표면간의 매우 강한 결합에 의해 촉매나 생물학적 분야에서 요구되는 은 나노입자의 기능을 떨어뜨릴 수 있다는 단점이 있다.Conventional hydrophobic silver nanoparticle synthesis has long been used a long carbon chain stabilizer having an amine group or a thiol group at the end group, especially when using a stabilizer having a thiol group can give nanoparticles a high dispersion stability in solution As a result, the strong bonding between the thiol group and the particle surface can impair the function of the silver nanoparticles, which are required in the catalyst or biological field.
이러한 문제로 인해 금속 표면에 대해 상대적으로 약한 결합력을 갖는 테트라옥틸암모늄을 안정제로 이용하여 금 나노입자를 합성하는 연구가 보고된 바 있으나, 은 나노입자의 경우 은 전구체의 원활한 상전이가 이루어지지 않는 문제로 인해 테트라옥틸암모늄을 안정제로 이용한 합성예는 보고된 바 없다.Due to these problems, studies have been made to synthesize gold nanoparticles using tetraoctylammonium having a relatively weak bonding strength to the metal surface as a stabilizer, but in the case of silver nanoparticles, a smooth phase transition of the silver precursor is not achieved. Due to this, no synthesis examples using tetraoctylammonium as a stabilizer have been reported.
이러한 기술적 배경 하에서 본 발명자들은 테트라옥틸암모늄을 안정제로 이용하여 입자 표면과 보다 약한 결합력을 가지면서도 입자의 분산 안정성을 높이는 방법에 대해 연구하던 중, 합성 과정 중에 싸이오설페이트염을 처리할 경우 테트라옥틸암모늄으로 안정화되어 높은 분산 안정성을 가지는 소수성 은 나노입자를 합성할 수 있음을 확인하고 본 발명을 완성하였다.Under these technical backgrounds, the present inventors are studying how to increase the dispersion stability of the particles while having a weaker binding force with the particle surface by using tetraoctylammonium as a stabilizer. The present invention was completed by confirming that hydrophobic silver nanoparticles stabilized with ammonium having high dispersion stability can be synthesized.
이에, 본 발명에서는 (a) 테트라옥틸암모늄 브로마이드(TOABr)가 용해된 무극성 용매와 은 전구체가 용해된 극성 용매의 혼합물을 제조하는 단계; (b) 상기 혼합물에 싸이오설페이트염을 첨가하여 무극성 용매 층으로 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)을 상전이시키는 단계; 및 (c) 상기 은-싸이오설페이트 음이온이 상전이된 무극성 용매 층을 분리한 후, 환원제를 첨가하는 단계;를 포함하는 은 나노입자의 제조방법을 제공한다.Thus, the present invention comprises the steps of (a) preparing a mixture of a polar solvent in which tetraoctylammonium bromide (TOABr) is dissolved and a silver precursor is dissolved; (b) adding a thiosulfate salt to the mixture to phase-transfer the silver-thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) to a nonpolar solvent layer; And (c) separating the nonpolar solvent layer in which the silver-thiosulfate anion is phase-transferred, and then adding a reducing agent.
구체적으로 상기 (a) 단계는 테트라옥틸암모늄 브로마이드(TOABr)가 용해된 무극성 용매와 은 전구체가 용해된 극성 용매의 혼합물을 제조하는 단계이다. 상기 (a) 단계를 통해 상기 혼합물은 TOABr이 용해된 무극성 용매층과 은 전구체가 용해된 극성 용매층을 형성하게 된다.Specifically, step (a) is a step of preparing a mixture of a polar solvent in which tetraoctylammonium bromide (TOABr) is dissolved and a silver precursor are dissolved. Through the step (a), the mixture forms a polar solvent layer in which TOABr is dissolved and a silver precursor is dissolved.
다음으로, 상기 (b) 단계는 상기 혼합물에 싸이오설페이트염을 첨가하여 무극성 용매 층으로 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)을 상전이시키는 단계이다. 테트라옥틸암모늄 브로마이드(TOABr)는 Au 및 Pd NP와 같은 소수성 금속 NP를 합성하는데 광범위하게 사용되었지만, TOA+Br- 및 Ag 전구체 이온(예를 들어 Ag+NO3-) 사이의 상대적으로 낮은 친화성 때문에 소수성 은 나노입자 합성을 위한 안정제로는 사용되지 못하였으나, 상기 혼합물에 싸이오설페이트염이 첨가될 경우 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)이 형성되고, 상기 은-싸이오설페이트 음이온은 브롬 이온(Br-)과 음이온 치환 반응을 통해 무극성 용매층으로 상전이가 일어나게 되며, 상기 상전이된 은-싸이오설페이트 음이온은 TOA+와 복합체를 형성하게 된다.Next, step (b) is a phase transition of the silver thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) to a nonpolar solvent layer by adding a thiosulfate salt to the mixture. Tetra-octyl-ammonium bromide (TOABr) has been widely used to synthesize the hydrophobic metal NP, such as Au and Pd NP, TOA + Br - and Ag precursor ion (e.g. Ag + NO3 -) due to the relatively low affinity between Although not used as a stabilizer for the synthesis of hydrophobic silver nanoparticles, when a thiosulfate salt is added to the mixture, a silver-thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) is formed, The silver-thiosulfate anion is phase shifted to a non-polar solvent layer through bromine ions (Br − ) and an anion substitution reaction, and the phase-transferred silver-thiosulfate anion forms a complex with TOA + .
[반응식][Scheme]
Ag+ (aq)S2O3 2 - (aq) ≪ Ag(S2O3)- ( aq) k1=7.4x108 (1) Ag + (aq) S 2 O 3 2 - (aq) «Ag (S 2 O 3) - (aq) k 1 = 7.4x10 8 (1)
Ag(S2O3)- (aq) + S2O3 2 - (aq) ≪ [Ag(S2O3)2]3 - ( aq) k2=3.9x104 (2) Ag (S 2 O 3) - (aq) + S 2 O 3 2 - (aq) «[Ag (S 2 O 3) 2] 3 - (aq)
마지막으로, 상기 (c) 단계는 상기 은-싸이오설페이트 음이온이 상전이된 무극성 용매 층을 분리한 후, 환원제를 첨가하는 단계로, 상기 (c) 단계의 환원을 통해 최종적으로 소수성 은 나노입자를 수득할 수 있다.Finally, step (c) is to separate the non-polar solvent layer in which the silver-thiosulfate anion is phase transition, and then add a reducing agent. Finally, the hydrophobic silver nanoparticles are finally reduced through the reduction of the step (c). Can be obtained.
이때, 상기 ToABr은 상기 은 전구체 대비 2-4 배의 당량비로 혼합되는 것이 바람직하다. 상기 ToABr의 당량비가 상기 하한치 미만이거나 상기 상한치를 초과할 경우 입자의 크기가 너무 크거나 작게되고, 상대적으로 불균일하게 합성된다는 문제가 있다.At this time, the ToABr is preferably mixed in an equivalent ratio of 2-4 times the silver precursor. If the equivalent ratio of ToABr is less than the lower limit or exceeds the upper limit, the size of the particles becomes too large or small, and there is a problem of relatively uneven synthesis.
또한, 상기 무극성 용매는 벤젠(benzene), 헥세인(hexane), 톨루엔(toluene), 이황화탄소(CS2), 사염화탄소(CCl4), 클로로포름(CHCl3), 디클로로메탄(CH2Cl2) 및 옥타데센(Octadecene) 중에서 선택된 1종 이상일 수 있다.In addition, the nonpolar solvent is benzene, hexane, toluene, carbon disulfide (CS 2 ), carbon tetrachloride (CCl 4 ), chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ) and It may be at least one selected from octadecene (Octadecene).
또한, 상기 은 전구체는 질산은(AgNO3), 과염소산은(AlClO4), 염소산은(AgClO3), 탄산은(Ag2CO3), 황산은(Ag2SO4), 염화은(AgCl), 브롬화은(AgBr) 및 불소은(AgF)으로 이루어진 군으로부터 선택된 1종 이상일 수 있다.In addition, the silver precursor is silver nitrate (AgNO 3 ), silver perchlorate (AlClO 4 ), silver chlorate (AgClO 3 ), silver carbonate (Ag 2 CO 3 ), silver sulfate (Ag 2 SO 4 ), silver chloride (AgCl), silver bromide (AgBr) and fluorine may be one or more selected from the group consisting of (AgF).
또한, 상기 극성 용매는 물, 알코올 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상일 수 있다. 이때, 상기 알코올은 프로판올(propanol), 부탄올(butanol), 펜탄올(pentanol), 헥산올(hexanol) 및 이들의 혼합물로 이루어진 군으로부터 선택될 수 있다.In addition, the polar solvent may be at least one selected from the group consisting of water, alcohols, and mixtures thereof. At this time, the alcohol may be selected from the group consisting of propanol, butanol, butanol, pentanol, hexanol, and mixtures thereof.
또한, 상기 싸이오설페이트염은 소듐싸이오설페이트, 암모늄싸이오설페이트, 실버싸이오설페이트 및 포타슘싸이오설페이트로 이루어진 군에서 선택된 1종 이상일 수 있다.In addition, the thiosulfate salt may be at least one selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, silver thiosulfate and potassium thiosulfate.
또한, 상기 환원제는 수소화붕소나트륨, 하이드라진, 아스코브르산, 아스코브르산 나트륨 및 이들의 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다.In addition, the reducing agent may be at least one selected from the group consisting of sodium borohydride, hydrazine, ascorbic acid, sodium ascorbate, and mixtures thereof.
이하에서는 바람직한 실시예 등을 들어 본 발명을 더욱 상세하게 설명한다. 그러나 이들 실시예 등은 본 발명을 보다 구체적으로 설명하기 위한 것으로, 본 발명의 범위가 이에 의하여 제한되지 않는다는 것은 당업계의 통상의 지식을 가진 자에게 자명할 것이다.Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. However, these examples and the like are intended to explain the present invention in more detail, and it will be apparent to those skilled in the art that the scope of the present invention is not limited thereto.
실시예Example 1. One. 싸이오설페이트염Thiosulfate salt 처리를 통해 Through treatment 테트라옥틸암모늄으로With tetraoctylammonium 안정화된 은 나노입자( Stabilized silver nanoparticles ( TOASTOAS -- AgAg NPs)의 합성 Synthesis of NPs)
먼저, 8 mL의 DI water 중의 0.3 mmol의 은 전구체(AgNO3)및 8 mL의 톨루엔에 용해된 0.75 mmol(은 전구체 대비 2.5배 당량비)의 테트라옥틸암모늄 브로마이드 (TOABr)를 반응 플라스크에서 혼합하였다. 상기 반응 혼합물을 실온에서 10분 동안 교반한 후에 1.2 mmol의 소듐싸이오설페이트(Na2S2O3)를 첨가함으로써, 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)이 형성한 후 음이온 치환을 통해 톨루엔 층으로 상전이 시켰다. 이러한 상전이는 탁한 반응 혼합물 용액이 투명 용액이 되는 것을 관찰함으로써 확인하였다. 10분 후 상전이된 톨루엔 층을 분리하였으며, 환원제인 수소화붕소나트륨(NaBH4) 0.45 mmol을 DI water 8 mL에 넣은 후 상기 상전이된 톨루엔 용액과 혼합 및 10분 동안 격렬히 교반하였다. 환원제 첨가 및 교반을 통해 투명한 톨루엔 용액이 진한 갈색으로 변함을 확인하였으며, 이를 통해 테트라옥틸암모늄으로 안정화된 은 나노입자(TOAS-Ag NPs)가 형성됨을 확인하였다. 반응 후 상기 진한 갈색의 TOAS-Ag NP를 분리하고, DI water, 10 mM HCl 및 10 mM NaOH로 세척하였으며, 원심 분리(10 분 동안 8,000 rpm)를 통해 균일한 크기의 TOAS-Ag NP를 수득하였다.First, 0.3 mmol of silver precursor (AgNO 3 ) in 8 mL of DI water and 0.75 mmol (2.5-equivalent ratio of silver precursor) dissolved in 8 mL of toluene were mixed in a reaction flask. The reaction mixture was stirred at room temperature for 10 minutes and then 1.2 mmol of sodium thiosulfate (Na 2 S 2 O 3 ) was added to the mixture to form a silver-thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) Was formed and then phase-transferred to the toluene layer through anion substitution. This phase transition was confirmed by observing the turbid reaction mixture solution becoming a clear solution. After 10 minutes, the phase-transferred toluene layer was separated, and 0.45 mmol of sodium borohydride (NaBH 4 ) as a reducing agent was added to 8 mL of DI water, mixed with the phase-transferred toluene solution, and stirred vigorously for 10 minutes. It was confirmed that the transparent toluene solution turned dark brown through addition of a reducing agent and stirring, thereby forming silver nanoparticles stabilized with tetraoctylammonium (TOAS-Ag NPs). After reaction, the dark brown TOAS-Ag NP was separated, washed with DI water, 10 mM HCl and 10 mM NaOH, and centrifuged (8,000 rpm for 10 minutes) to obtain TOAS-Ag NP of uniform size. .
비교예Comparative example 1. One.
8 mL의 톨루엔에 용해된 1.5 mmol(은 전구체 대비 5배 당량비)의 테트라옥틸암모늄 브로마이드 (TOABr)를 사용한 것을 제외하고는 상기 실시예 1과 동일한 방법을 통해 은 나노입자를 합성하였다.Silver nanoparticles were synthesized in the same manner as in Example 1, except that 1.5 mmol (5 equivalents to silver precursor) of tetraoctylammonium bromide (TOABr) dissolved in 8 mL of toluene was used.
실험예Experimental Example 1. One. 1One H NMR 분석H NMR analysis
도 2는 본 발명에 따라 싸이오설페이트염을 첨가하여 상전이가 일어난 무극성 용매층의 1H NMR 분석 결과를 나타낸 것이다.Figure 2 shows the results of the 1 H NMR analysis of a non-polar solvent layer in which the phase transition by adding a thiosulfate salt in accordance with the present invention.
분석 결과, 테트라옥틸암모늄 분자의 N+로부터의 첫 번째 메틸기(*) 신호가 상향 전이(upfield shift)됨을 확인할 수 있었는바, 이를 통해 싸이오설페이트염 첨가시 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)이 형성되고, 상기 은-싸이오설페이트 음이온이 브롬 이온(Br-)과 음이온 치환 반응을 통해 무극성 용매층으로 상전이가 일어나게 됨을 확인하였다.As a result, it was confirmed that the first methyl group (*) signal from N + of the tetraoctyl ammonium molecule was upfield shifted. Thus, silver-thiosulfate anion ([Ag ( S 2 O 3) 2] 3- ) it is formed, and above-confirmed that) and negative ions occurs a phase change to the non-polar solvent layer with a metathesis-thiosulfate anion is bromide ion (Br.
실험예Experimental Example 2. 2. TOASTOAS -- AgAg NPs의NPs HR- HR- TEMTEM 이미지 및 크기 분포 측정 Image and size distribution measurements
도 3은 본 발명의 실시예 1에 따라 톨루엔 중에 분산된, 싸이오설페이트염 처리를 통해 테트라옥틸암모늄으로 안정화된 은 나노입자(TOAS-Ag NPs)의 HR-TEM 이미지이고, 도 4는 상기 도 2의 HR-TEM 이미지로부터 측정된 TOAS-Ag NPs의 크기 분포를 나타낸 그래프이며, 도 5는 비교예 1에 따라 합성된 은 나노입자의 HR-TEM 이미지이다.FIG. 3 is an HR-TEM image of silver nanoparticles stabilized with tetraoctyl ammonium (TOAS-Ag NPs) through a thiosulfate salt treatment, dispersed in toluene according to Example 1 of the present invention, and FIG. Figure 2 is a graph showing the size distribution of TOAS-Ag NPs measured from the HR-TEM image of 2, Figure 5 is an HR-TEM image of silver nanoparticles synthesized according to Comparative Example 1.
이를 통해 은 전구체 대비 5배 당량비로 ToABr을 사용한 비교예 1의 경우 입자의 평균 직경이 약 5 nm이며 상대적으로 불균일하게 합성되는 반면, 은 전구체 대비 2.5배 당량비로 ToABr을 사용한 실시예 1의 경우 균일한 크기의 구형 은 나노입자가 안정적으로 제조됨을 확인하였으며, 구체적으로 평균 직경 약 8.29 nm의 균일한 크기 분포를 가지는 은 나노입자가 제조됨을 확인하였다.This resulted in Comparative Example 1 using ToABr at a 5 times equivalence ratio of silver precursor, while the average diameter of the particles was about 5 nm and synthesized relatively nonuniformly, whereas Example 1 using ToABr at 2.5 times equivalent ratio of silver precursor was uniform. It was confirmed that spherical silver nanoparticles of one size were stably prepared, and specifically, silver nanoparticles having a uniform size distribution having an average diameter of about 8.29 nm were prepared.
실험예Experimental Example 3. 3. TOASTOAS -- AgAg NPs의NPs 안정성 측정 Stability measurement
도 6은 실시예 1에 따라 합성된 TOAS-Ag NPs의 합성 5일 후 TEM 이미지를 나타낸 것이다.6 shows a TEM image after 5 days of synthesis of TOAS-Ag NPs synthesized according to Example 1. FIG.
이를 통해 본 발명에 따라 싸이오설페이트염 처리를 통해 테트라옥틸암모늄으로 안정화된 은 나노입자는 싸이오설페이트 음이온의 처리 및 S 함유 분자와 은 표면의 상호 작용으로 인하여 합성 5일 후에도 매우 안정적인 상태를 유지한다는 것을 확인하였다.The silver nanoparticles stabilized with tetraoctyl ammonium through the thiosulfate salt treatment according to the present invention maintain a very stable state even after 5 days of synthesis due to the treatment of the thiosulfate anion and the interaction of the S-containing molecule with the silver surface. It was confirmed that.
실험예Experimental Example 4. 4. TOASTOAS -- AgAg NPs의NPs UV 흡광도 측정 UV absorbance measurement
도 7은 실시예 1에 따라 합성된 TOAS-Ag NPs의 UV 흡광도를 나타낸 그래프이다.7 is a graph showing UV absorbance of TOAS-Ag NPs synthesized according to Example 1. FIG.
측정 결과 418 nm에서 표면 플라즈몬 흡수 피크가 관찰되었는바, 이를 통해 본 발명에 따라 합성된 은 나노입자는 종래 보고된 은 나노입자(Yang et al., Langmuir (2003))의 고유 특성을 잃지 않고 안정적으로 유지하고 있음을 확인하였다.Bar doeeotneun measurements Surface plasmon absorption band at 418 nm is observed, the This was synthesized according to the present invention the nanoparticles are nanoparticles prior reported (Yang et al., Langmuir ( 2003 ), it is confirmed that it is stable without losing its inherent characteristics.
Claims (8)
(b) 상기 혼합물에 싸이오설페이트염을 첨가하여 무극성 용매 층으로 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)을 상전이시키는 단계; 및
(c) 상기 은-싸이오설페이트 음이온이 상전이된 무극성 용매 층을 분리한 후, 환원제를 첨가하는 단계;를 포함하는 은 나노입자의 제조방법.(a) preparing a mixture of a nonpolar solvent in which tetraoctylammonium bromide (TOABr) is dissolved and a polar solvent in which silver precursor is dissolved;
(b) adding a thiosulfate salt to the mixture to phase-transfer the silver-thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) to a nonpolar solvent layer; And
(c) separating the nonpolar solvent layer in which the silver-thiosulfate anion is phase-transferred, and then adding a reducing agent.
상기 (b) 단계에서 은-싸이오설페이트 음이온([Ag(S2O3)2]3-)이 형성된 후, 브롬 이온(Br-)과 음이온 치환 반응을 통해 상기 은-싸이오설페이트 음이온이 상전이되는 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
In the step (b), after the silver thiosulfate anion ([Ag (S 2 O 3 ) 2 ] 3- ) is formed, the silver thiosulfate anion is subjected to an anion substitution reaction with bromine ion (Br − ). Method for producing silver nanoparticles, characterized in that the phase transition.
상기 무극성 용매는 벤젠(benzene), 헥세인(hexane), 톨루엔(toluene), 이황화탄소(CS2), 사염화탄소(CCl4), 클로로포름(CHCl3), 디클로로메탄(CH2Cl2) 및 옥타데센(Octadecene) 중에서 선택된 1종 이상인 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
The nonpolar solvent is benzene, hexane, toluene, carbon disulfide (CS 2 ), carbon tetrachloride (CCl 4 ), chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ) and octadecene (Octadecene) A method for producing silver nanoparticles, characterized in that at least one selected from.
상기 은 전구체는 질산은(AgNO3), 과염소산은(AlClO4), 염소산은(AgClO3), 탄산은(Ag2CO3), 황산은(Ag2SO4), 염화은(AgCl), 브롬화은(AgBr) 및 불소은(AgF)으로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
The silver precursor is silver nitrate (AgNO 3 ), silver perchlorate (AlClO 4 ), silver chlorate (AgClO 3 ), silver carbonate (Ag 2 CO 3 ), silver sulfate (Ag 2 SO 4 ), silver chloride (AgCl), silver bromide (AgBr ) And fluorine silver (AgF) is at least one member selected from the group consisting of.
상기 극성 용매는 물, 알코올 및 이들의 혼합물로 이루어진 군으로부터 선택된 1종 이상인 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
The polar solvent is a method for producing silver nanoparticles, characterized in that at least one selected from the group consisting of water, alcohols and mixtures thereof.
상기 싸이오설페이트염은 소듐싸이오설페이트, 암모늄싸이오설페이트, 실버싸이오설페이트 및 포타슘싸이오설페이트로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
The thiosulfate salt is a method for producing silver nanoparticles, characterized in that at least one selected from the group consisting of sodium thiosulfate, ammonium thiosulfate, silver thiosulfate and potassium thiosulfate.
상기 환원제는 수소화붕소나트륨, 하이드라진, 아스코브르산, 아스코브르산 나트륨 및 이들의 혼합물로 이루어진 군에서 선택된 1종 이상인 것을 특징으로 하는 은 나노입자의 제조방법.The method of claim 1,
The reducing agent is a method for producing silver nanoparticles, characterized in that at least one selected from the group consisting of sodium borohydride, hydrazine, ascorbic acid, sodium ascorbate and mixtures thereof.
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| PCT/KR2019/005210 WO2019212231A1 (en) | 2018-04-30 | 2019-04-30 | Method for preparing silver nanoparticles stabilized with tetraoctylammonium, and method for producing electrically conductive thin film by using silver nanoparticles prepared by same |
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