KR20170099797A - A Method for preparing metal oxide nanoparticle and metal hydroxide nanoparticle in aqueous solution - Google Patents
A Method for preparing metal oxide nanoparticle and metal hydroxide nanoparticle in aqueous solution Download PDFInfo
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- KR20170099797A KR20170099797A KR1020170025117A KR20170025117A KR20170099797A KR 20170099797 A KR20170099797 A KR 20170099797A KR 1020170025117 A KR1020170025117 A KR 1020170025117A KR 20170025117 A KR20170025117 A KR 20170025117A KR 20170099797 A KR20170099797 A KR 20170099797A
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- alkylamine
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 71
- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 17
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 15
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 title claims description 7
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 25
- 150000003973 alkyl amines Chemical class 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 13
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical group CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 6
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 4
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000002696 manganese Chemical class 0.000 claims description 3
- 150000002815 nickel Chemical class 0.000 claims description 3
- AIBQNUOBCRIENU-UHFFFAOYSA-N nickel;dihydrate Chemical compound O.O.[Ni] AIBQNUOBCRIENU-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 18
- 239000002904 solvent Substances 0.000 abstract description 5
- 238000007796 conventional method Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000003917 TEM image Methods 0.000 description 10
- 238000002441 X-ray diffraction Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 229910020366 ClO 4 Inorganic materials 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 4
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- UGNSMKDDFAUGFT-UHFFFAOYSA-N 4,4-dimethyl-2-phenyl-5h-1,3-oxazole Chemical compound CC1(C)COC(C=2C=CC=CC=2)=N1 UGNSMKDDFAUGFT-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- BJDJGQJHHCBZJZ-UHFFFAOYSA-L iron(2+);diperchlorate;hydrate Chemical compound O.[Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BJDJGQJHHCBZJZ-UHFFFAOYSA-L 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 description 1
- 239000002616 MRI contrast agent Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- DCWFKWISKOLECJ-UHFFFAOYSA-L O.O.[Ni++].CC([O-])=O.CC([O-])=O Chemical compound O.O.[Ni++].CC([O-])=O.CC([O-])=O DCWFKWISKOLECJ-UHFFFAOYSA-L 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- RJYMRRJVDRJMJW-UHFFFAOYSA-L dibromomanganese Chemical compound Br[Mn]Br RJYMRRJVDRJMJW-UHFFFAOYSA-L 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- ZPKLYVJENOZRAW-UHFFFAOYSA-L iron(2+);dichlorate Chemical compound [Fe+2].[O-]Cl(=O)=O.[O-]Cl(=O)=O ZPKLYVJENOZRAW-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- DEVYBOZJYUYBMC-KVVVOXFISA-N iron;(z)-octadec-9-enoic acid Chemical compound [Fe].CCCCCCCC\C=C/CCCCCCCC(O)=O DEVYBOZJYUYBMC-KVVVOXFISA-N 0.000 description 1
- WKPSFPXMYGFAQW-UHFFFAOYSA-N iron;hydrate Chemical compound O.[Fe] WKPSFPXMYGFAQW-UHFFFAOYSA-N 0.000 description 1
- UQLLJPLUKUGLNR-UHFFFAOYSA-L manganese(2+);dichloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Mn+2] UQLLJPLUKUGLNR-UHFFFAOYSA-L 0.000 description 1
- QVRFMRZEAVHYMX-UHFFFAOYSA-L manganese(2+);diperchlorate Chemical compound [Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O QVRFMRZEAVHYMX-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000013507 mapping Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
본 발명은 산화금속 및 수산화금속 나노입자의 제조방법에 관한 것으로, 구체적으로 수용액 중에서 금속염을 폴리에틸렌아민 및 알킬아민과 반응시키는 것을 특징으로 하는 산화금속 및 수산화금속 나노입자의 제조방법에 관한 것이다. The present invention relates to a method for producing metal oxide and metal hydroxide nanoparticles, and more particularly, to a method for producing metal oxide and metal hydroxide nanoparticles, which comprises reacting a metal salt with polyethyleneamine and alkylamine in an aqueous solution.
산화금속과 수산화금속 나노입자에 대한 연구는 다양한 응용 가능성 때문에 주목을 받아오고 있고 현재도 활발하게 진행되고 있다. 특히 산화철 나노입자의 경우에는 생체적합성이 높아 MRI 조영제 같은 의학적 용도로도 사용이 가능하며, 산화망간 나노입자는 센서나 촉매 등으로도 사용이 가능하다. 또한, 수산화금속 나노입자는 에너지 저장을 할 수 있는 캐패시터나 배터리에도 응용이 되고 있다.Studies on metal oxides and metal hydroxide nanoparticles have been attracting attention due to their diverse application possibilities, and they are actively undergoing. In particular, iron oxide nanoparticles are highly biocompatible and can be used for medical purposes such as MRI contrast agents. Manganese oxide nanoparticles can also be used as sensors and catalysts. In addition, metal hydroxide nanoparticles are also being applied to capacitors and batteries capable of energy storage.
현재까지 산화금속과 수산화금속 나노입자를 만들기 위하여 수열합성법, 화학증기를 이용한 증착법, 졸겔법 등 많은 방법에 의해 제조되고 있다. 그러나 이러한 방법들을 사용하기 위해서는 100 ℃ 이상의 온도가 요구되거나 수십기압의 고압 하에서 제조가 되어야 한다. 혹은 3시간보다 더 긴 반응시간을 필요로 하거나 유해한 유기 용매상에서 반응이 진행되기도 하고, 합성과정이 복잡하여 대량생산이 적합하지 않았다. To date, metal hydroxides and metal hydroxide nanoparticles have been prepared by a number of methods including hydrothermal synthesis, chemical vapor deposition, and sol-gel method. However, in order to use these methods, a temperature of 100 ° C or higher is required, or a high pressure of several tens of atmospheres is required. Or a reaction time longer than 3 hours is required or the reaction proceeds in a harmful organic solvent, and the synthesis process is complicated, and mass production is not suitable.
예를 들어, 한국공개특허 제2012-0013519호는 올레산철 착물의 열분해를 기반으로 산화철 나노입자를 제조하는 방법을 개시하고 있으나, 상기 방법은 비활성 환경에서 300℃ 정도의 온도에서 유기용매를 사용하여 합성되므로 제조비용이 많이 드는 문제점이 있었다.For example, Korean Patent Publication No. 2012-0013519 discloses a method for producing iron oxide nanoparticles based on thermal decomposition of an oleic acid iron complex, but the method uses an organic solvent at an inert atmosphere at a temperature of about 300 ° C There is a problem in that the manufacturing cost is increased.
또한, 한국등록특허 제1423563호는 폴리에틸렌이민을 환원제 및 안정제로 사용하는 나노입자 제조방법을 개시하고 있으나, 폴리에틸렌만을 사용할 경우 산화철 나노입자의 결정 구조를 완벽하게 제어할 수 없는 단점이 있었다.Korean Patent Registration No. 1423563 discloses a method for producing nanoparticles using polyethyleneimine as a reducing agent and a stabilizer, but it has a disadvantage in that crystal structure of iron oxide nanoparticles can not be completely controlled when only polyethylene is used.
이에 본 발명자는 상기와 같은 종래 기술의 문제점을 해결하기 위하여 예의 연구 노력한 결과, 폴리에틸렌이민과 알킬아민을 사용하고 물과 같이 취급이 용이한 용매를 사용하여 100℃ 이하의 온도에서 산화금속 및 수산화금속 금속 나노입자를 제조할 수 있어 제조공정을 획기적으로 단순화할 수 있으며, 작업환경 또한 개선할 수 있음을 확인하고 본 발명을 완성하게 되었다.Accordingly, the present inventors have made intensive investigations to solve the problems of the prior art as described above. As a result, the present inventors have found that the use of a polyethyleneimine and an alkylamine, and a solvent that is easy to handle, such as water, It is possible to remarkably simplify the manufacturing process and to improve the working environment since the metal nanoparticles can be produced, and the present invention has been completed.
본 발명의 목적은 단순하고 안전하며 높은 생산효율을 갖는 산화금속 및 수산화금속 나노입자 제조방법을 제공하는데 있다.It is an object of the present invention to provide a simple and safe method for producing metal oxide and metal hydroxide nanoparticles having high production efficiency.
본 발명은 수용액 중에서 금속염을 폴리에틸렌이민 및 알킬아민과 반응시키는 단계를 포함하는 산화금속 또는 수산화금속 나노입자의 제조방법을 제공한다.The present invention provides a process for preparing metal oxide or metal hydroxide nanoparticles comprising the step of reacting a metal salt with a polyethyleneimine and an alkylamine in an aqueous solution.
본 발명의 나노입자의 제조방법은 수용액 상에서 실시할 수 있다. 즉 물을 주 용매로 사용할 수 있다. 기존의 제조방법은 유기용매와 같은 인체에 유해하거나 환경오염문제를 수반하는 용매를 사용하는 경우가 대부분인데, 본 발명에 따르면 이러한 문제를 획기적으로 개선할 수 있다. 또한 이에 따라 별도의 폐수처리 설비, 대기정화 설비 등이 필요하지 않다는 장점도 있다. 이는 산업상 매우 큰 장점이 될 수 있을 뿐만 아니라 환경적으로도 매우 유익한 것이다.The method for producing nanoparticles of the present invention can be carried out in an aqueous solution. That is, water can be used as the main solvent. In the conventional manufacturing method, a solvent which is harmful to a human body such as an organic solvent or accompanies an environmental pollution problem is used in most cases, but the present invention can drastically improve such a problem. In addition, there is also the advantage that there is no need for separate wastewater treatment facilities and atmospheric purification facilities. This is not only a great advantage in industry, but also very beneficial to the environment.
상기 금속염은 전이금속을 포함하는 염으로 철염, 망간염, 니켈염, 코발트염 또는 이들의 혼합물을 사용할 수 있으나, 이에 제한되지는 않는다.The metal salt may include, but is not limited to, an iron salt, a manganese salt, a nickel salt, a cobalt salt, or a mixture thereof, including a transition metal.
상기 철염은 아세트산철, 할로겐화철, 질산철, 황산철, 수산화철, 염소산철, 과염소산철, 이들의 수화물 및 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다. 바람직하게는 과염소산철 일수화물(Fe(ClO4)2·4H2O)을 사용할 수 있다.The iron salt may be at least one selected from the group consisting of iron acetate, iron halide, iron nitrate, iron sulfate, iron hydroxide, iron chlorate, iron perchlorate, hydrates thereof and mixtures thereof. Preferably, iron perchlorate monohydrate (Fe (ClO 4 ) 2 .4H 2 O) can be used.
상기 망간염은 황산망간(MnSO4), 질산망간(Mn(NO3)3), 초산망간(Mn(CO2CH3)2), 염화망간(MnCl2), 브롬화망간(MnBr2) 및 과염소산망간(Mn(ClO4)2), 이들의 수화물 및 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다. 바람직하게는 염화망간 사수화물(MnCl2·4H2O)을 사용할 수 있다.The manganese salt may be selected from the group consisting of manganese sulfate (MnSO4), manganese nitrate (Mn (NO3) 3), manganese nitrate (MnCO2CH3) 2, manganese chloride (MnCl2), manganese bromide (MnBr2) and manganese perchlorate ), Hydrates thereof, and mixtures thereof. Preferably, manganese chloride tetrahydrate (MnCl 2 .4H 2 O) can be used.
상기 니켈염은 황산니켈, 염화니켈, 아세트산니켈, 탄산니켈, 수산화니켈, 이들의 수화물 및 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다. 바람직하게는 아세트산니켈 사수화물을 사용할 수 있다.The nickel salt may be at least one selected from the group consisting of nickel sulfate, nickel chloride, nickel acetate, nickel carbonate, nickel hydroxide, hydrates thereof and mixtures thereof. Preferably, nickel acetate dihydrate can be used.
상기 코발트염은 황산코발트, 염화코발트, 아세트산코발트, 탄산코발트, 수산화코발트, 이들의 수화물 및 혼합물로 이루어진 군에서 선택된 1종 이상일 수 있다. 바람직하게는 아세트산코발트 사수화물을 사용할 수 있다.The cobalt salt may be at least one selected from the group consisting of cobalt sulfate, cobalt chloride, cobalt acetate, cobalt carbonate, cobalt hydroxide, hydrates thereof, and mixtures thereof. Preferably, cobalt acetate saponate can be used.
본 발명에서 폴리에틸렌이민은 안정제 내지 캐핑제로서 형성된 나노입자가 나노사이즈를 유지하게 하도록 할 수 있다. In the present invention, the polyethyleneimine can make the nanoparticles formed as a stabilizer or a capping agent maintain the nano-size.
폴리에틸렌이민(PEI)은 아민기와 알킬기로 구성된 고분자로 금속이온에 대해 chelation effect와 환원력, 그리고 캐핑력을 갖는다. 이와 같은 이유로 금속이온의 높은 농도 조건에서도 금속을 이온상태로 붙잡고 있다가 환원 및 캐핑을 동시다발적으로 일으킨다. 폴리에틸렌이민은 분자 구조 상 크게 분지형(branched)과 선형(linear)으로 나뉜다. 분지형 폴리에틸렌이민(branched polyethylenimine, B-PEI)의 경우 대표적으로 아래의 화학식 1으로 표시될 수 있으며, 선형 폴리에틸렌이민(linear polyethylenimine, L-PEI)의 경우 아래 화학식 2로 표시될 수 있다. 본 발명에서는 B-PEI와 L-PEI 모두 응집현상 없이 균일한 크기의 나노입자를 제조할 수 있다.Polyethyleneimine (PEI) is a polymer composed of an amine group and an alkyl group, and has a chelating effect, a reducing power, and a capping power for a metal ion. For this reason, even at high concentration of metal ions, the metal is caught in the ionic state, which simultaneously causes reduction and capping. Polyethyleneimine is divided into branched and linear in molecular structure. The branched polyethylenimine (B-PEI) may be represented by the following general formula (1) and the linear polyethylenimine (L-PEI) may be represented by the following general formula (2). In the present invention, both B-PEI and L-PEI can produce nanoparticles of uniform size without agglomeration.
[화학식 1] B-PEI[Chemical Formula 1] B-PEI
[화학식 2] L-PEI[Chemical Formula 2] L-PEI
본 발명의 나노입자 제조방법에서 PEI의 분자량(중합정도)은 크게 중요한 요소가 아닌 것으로 판단된다. 시중에서 판매되는 각각의 분자량이 25,000, 70,000, 750,000인 PEI를 대상으로 실험한 결과, 분자량이 다르더라도 제조된 나노입자의 특성 차이는 거의 없는 것으로 나타났다. 따라서 분자량에 관계없이 모든 PEI를 사용할 수 있을 것으로 판단되나, 비제한적인 예로 20,000 내지 1,000,000의 분자량을 갖는 PEI를 사용하는 것이 바람직할 것이다. The molecular weight (degree of polymerization) of PEI is not considered to be a major factor in the method of the present invention for producing nanoparticles. As a result of experiments on PEI having molecular weights of 25,000, 70,000 and 750,000, which are commercially available, there was little difference in the characteristics of the prepared nanoparticles even when the molecular weights were different. Accordingly, it is considered that all PEI can be used regardless of the molecular weight, but it is preferable to use PEI having a molecular weight of 20,000 to 1,000,000 as a non-limiting example.
본 발명에서 알킬아민은 반응용액의 pH 값을 증가시켜 졸 겔 반응을 유도하여 산화금속 또는 수산화금속 나노입자를 형성하게 할 수 있다.In the present invention, the alkylamine may increase the pH value of the reaction solution to induce a sol-gel reaction to form metal oxide or metal hydroxide nanoparticles.
도 7에서 보는 바와 같이 합성 중에 반응의 pH 값이 감소함을 관찰하였다. 또한, 헥실아민 대신 NaOH가 반응 용액의 pH를 증가시키는데 사용되었을 때, 생성물의 XRD 패턴은 α-Fe2O3 (JCPDS file no. 80-2377) 및 iron hydroxide (JCPDS file no. 81-2022)의 일부를 갖는 Fe3O4 결정 구조의 형성됨을 확인하였다(도 8). 즉, 알킬아민도 NaOH와 같이 반응용액의 pH를 증가시키는 역할을 할 수 있다. As shown in FIG. 7, it was observed that the pH value of the reaction decreased during the synthesis. In addition, when NaOH instead of hexylamine was used to increase the pH of the reaction solution, the XRD pattern of the product was confirmed by α-Fe 2 O 3 (JCPDS file no. 80-2377) and iron hydroxide (JCPDS file no. 81-2022) (Fig. 8). It was confirmed that the Fe 3 O 4 crystal structure having a part of the Fe 3 O 4 crystal structure was formed. That is, alkylamine can also act to increase the pH of the reaction solution like NaOH.
특히 본 발명에서 알킬아민은 산화철 나노입자의 제조시 반응제로서 Fe3O4 (magnetite, 자철석) 결정 구조의 형성에 중요한 역할을 한다. In particular, the alkylamine in the present invention plays an important role in the formation of Fe 3 O 4 (magnetite) crystal structure as a reactant in the preparation of iron oxide nanoparticles.
알킬아민은 탄소수 6 내지 20인 것일 수 있으며, 바람직하게는 헥실아민, 헵틸아민, 옥틸아민 등을 사용할 수 있으나, 반드시 이에 제한되는 것은 아니다. 탄소수가 20을 초과하는 알킬아민을 사용할 경우 상분리가 일어나서 아민이 물과 잘 혼합되지 않는 현상이 발생할 수 있다.The alkylamine may have 6 to 20 carbon atoms, and hexylamine, heptylamine, octylamine and the like may be preferably used, but the present invention is not limited thereto. When an alkylamine having more than 20 carbon atoms is used, phase separation may occur and the amine may not mix well with water.
본 발명의 나노입자의 제조방법에 있어서 반응 온도 및 금속염 농도에 따라서, 나노입자의 크기, 형태, 및 응집의 정도가 달라질 수 있다.In the method for producing nanoparticles of the present invention, the size, shape, and degree of aggregation of the nanoparticles may vary depending on the reaction temperature and the concentration of the metal salt.
즉, 나노입자의 자기조립은 높은 반응 온도에서 증가할 수 있다.That is, the self-assembly of nanoparticles can increase at high reaction temperatures.
반응온도가 낮을 경우 생성되는 나노입자의 크기가 균일하지 못하고 제조 효율이 떨어질 수 있으며, 온도가 높아질수록 대체로 크기가 균일해지며 반응속도가 빨라지지만 특정 온도 이상에서는 개선정도에 큰 차이가 없다. 이러한 점을 고려하여 반응 온도는 20 내지 95℃ 인 것이 바람직하나, 100℃ 미만이기만 하면 반드시 이에 제한되지 않는다.When the reaction temperature is low, the size of the generated nanoparticles is not uniform and the production efficiency may be decreased. As the temperature increases, the size becomes uniform and the reaction speed becomes faster. In consideration of this point, the reaction temperature is preferably 20 to 95 ° C, but not necessarily limited to 100 ° C or less.
본 발명에서 제조되는 산화금속 및 수산화금속 나노입자의 크기는 다른 조건을 유지하면서 금속염의 함량(농도)를 변화시킴으로써 조절될 수 있다.The size of the metal oxide and metal hydroxide nanoparticles produced in the present invention can be controlled by changing the content (concentration) of the metal salt while maintaining other conditions.
본 발명에서 반응액 중 금속염의 몰농도에 대한 폴리에틸렌이민의 단위체인 C2H5N을 기준으로 한 몰농도의 비는 0.2 내지 1.0 인 것이 바람직하며, 보다 바람직하게는 0.55 내지 0.65일 수 있다. 0.2 미만인 경우 환원력이 부족하여 적은 수의 핵이 생성되고, 캐핑력의 부족으로 인해 입자의 성장을 제어하지 못하여 입자간 결합이 발생할 수 있고, 응집현상 등의 문제가 발생할 수 있으며, 1.0 초과인 경우 입자의 성장을 방해하여 크기가 일정하지 않은 입자가 만들어 질 수 있고, 응집현상 등의 문제가 발생할 수 있다.In the present invention, the molar concentration ratio based on C 2 H 5 N, which is the unit of the polyethyleneimine with respect to the molar concentration of the metal salt in the reaction liquid, is preferably 0.2 to 1.0, more preferably 0.55 to 0.65. If it is less than 0.2, a small number of nuclei are formed due to a lack of reducing power, the particle growth can not be controlled due to the lack of the capping force, so that intergranular bonding may occur and problems such as agglomeration may occur. The particles may not be uniform in size due to obstruction of the growth of the particles, and problems such as aggregation may occur.
또한, 본 발명에서 반응액 중 금속염의 몰농도에 대한 알킬아민의 몰농도의 비는 1.0 내지 3.0 인 것이 바람직하며, 보다 바람직하게는 1.5 내지 2.5일 수 있다. 1.0 미만인 경우 환원력이 부족하여 입자의 성장이 안되어 크기와 모양이 일정하지 않을 수 있으며, 3.0 초과인 경우 과도한 환원력으로 인하여 입자의 성장이 고르게 적용되지 않아 입자의 크기, 형태가 균일하지 않는 문제가 발생할 수 있다.In the present invention, the ratio of the molar concentration of the alkylamine to the molar concentration of the metal salt in the reaction liquid is preferably 1.0 to 3.0, more preferably 1.5 to 2.5. If it is less than 1.0, the size and shape may not be constant due to lack of reducing power due to lack of reducing power. If it is more than 3.0, the particle growth is not applied uniformly due to excessive reducing power, .
본 발명의 반응은 종래에 비해 단시간 동안 진행될 수 있다. 바람직하게는 2 내지 12 시간 동안 진행될 수 있다. The reaction of the present invention can proceed for a shorter time than in the prior art. Preferably 2 to 12 hours.
본 발명의 반응은 상압에서도 진행될 수 있어, 제조비용이 절감될 수 있다.The reaction of the present invention can proceed at atmospheric pressure, and manufacturing cost can be reduced.
본 발명은 폴리에틸렌이민을 사용함으로써 제조되는 산화금속 나노입자의 크기를 10 내지 50 nm, 바람직하게는 20 내지 30 nm 로 제어할 수 있다.The present invention can control the size of the metal oxide nanoparticles produced by using polyethyleneimine to 10 to 50 nm, preferably 20 to 30 nm.
본 발명은 폴리에틸렌이민을 사용함으로써 제조되는 수산화니켈 나노입자의 크기를 바람직하게는 80 내지 100 nm 로 제어할 수 있다.The present invention can control the size of nickel hydroxide nanoparticles produced by using polyethyleneimine to preferably 80 to 100 nm.
본 발명은 폴리에틸렌이민을 사용함으로써 제조되는 수산화코발트 나노입자의 크기를 바람직하게는 250 내지 450 nm 로 제어할 수 있다.The present invention can control the size of the cobalt hydroxide nanoparticles produced by using polyethyleneimine to preferably 250 to 450 nm.
본 발명에 따라 제조한 산화금속 나노입자는 입자의 형태를 가지며, 수산화금속 나노입자는 판(plate) 형태를 가질 수 있다.The metal oxide nanoparticles prepared according to the present invention have a particle shape, and the metal hydroxide nanoparticles may have a plate shape.
바람직하게는 상기 산화금속 나노입자는 산화철(Fe3O4) 나노입자, 산화망간(Mn3O4) 나노입자 등 일 수 있다. 상기 산화철(Fe3O4)은 자철석(마그네타이트)일 수 있다.Preferably, the metal oxide nanoparticles may be iron oxide (Fe 3 O 4 ) nanoparticles, manganese oxide (Mn 3 O 4 ) nanoparticles, and the like. The iron oxide (Fe 3 O 4 ) may be magnetite (magnetite).
바람직하게는 상기 수산화금속 나노입자는 수산화니켈(Ni(OH)2) 나노입자, 수산화코발트(Co(OH)2) 나노입자 등 일 수 있다.Preferably, the metal hydroxide nanoparticles may be nickel hydroxide (Ni (OH) 2 ) nanoparticles, cobalt hydroxide (Co (OH) 2 ) nanoparticles, and the like.
본 발명에 따르면 기존 방법에 비해 상대적으로 저온에서도 물을 용매로 사용하여 단순하고 안전하고 친환경적이고 높은 생산효율로 산화금속 또는 수산화금속 나노입자를 제조할 수 있다. According to the present invention, metal oxide or metal hydroxide nanoparticles can be produced with simple, safe, environmentally friendly and high production efficiency by using water as a solvent even at a relatively low temperature as compared with the conventional method.
도 1은 본 발명의 실시예 1에 따라 과염소산철 일수화물(Fe(ClO4)2 ·xH2O) 및 헥실아민을 함유하는 수성 용액을 95 ℃에서 3시간 동안 가열하여 합성한 Fe3O4 나노입자의 (a) TEM 이미지이며, (b)는 HR-TEM 이미지 및 (c)는 XRD 패턴이다.
도 2는 본 발명의 실시예 2에 따라 염화망간 육수화물(MnCl2 ·4H2O) 및 헥실아민을 함유하는 수성 용액을 90 ℃에서 3시간 동안 가열하여 합성한 Mn3O4 나노입자의 (a) TEM 이미지, (b) XRD 패턴이다.
도 3의 (a)는 본 발명의 실시예 3에 따라 제조한 Fe3O4 나노입자의 TEM 이미지이며, (b)는 본 발명의 실시예 4에 따라 제조한 Fe3O4 나노입자의 TEM 이미지이며, (c)는 본 발명의 실시예 5에 따라 제조한 Fe3O4 나노입자의 TEM 이미지이며, (d)는 본 발명의 실시예 6에 따라 제조한 Fe3O4 나노입자의 TEM 이미지이다.
도 4는 본 발명의 실시예 7에 따라 제조한 Fe3O4 나노입자의 (a) TEM이미지. (b) SEM 이미지 및 (c) XRD 패턴이다.
도 5는 본 발명의 실시예 8에 따라 제조한 Fe3O4 나노입자의 (a) SEM이미지, (b) 및 (c)TEM 이미지, (d) ED 패턴, (e)XRD 패턴이다.
도 6은 본 발명의 실시예 9에 따라 제조한 Fe3O4 나노입자의 (a) 내지 (c) TEM이미지, (d) 및 (e) EDS mapping, (f) EDS 원소비율이다.
도 7은 본 발명에 따른 Fe3O4 나노입자의 반응 시간 별 pH의 변화를 나타낸 것이다.
도 8은 본 발명에 따른 Fe3O4 나노입자의 XRD 분석결과이다.
도 9는 본 발명의 실시예 1에 따라 제조한 Fe3O4 에 대한 X-레이 광전자 분광기(XPS) 분석결과이다.1 is a perchlorate, iron monohydrate according to Example 1 of the invention (Fe (ClO 4) 2 · xH 2 O) and a Fe composite by an aqueous solution containing hexylamine heated at 95 ℃ for 3 hours 3 O 4 (A) TEM image of nanoparticles, (b) HR-TEM image and (c) XRD pattern.
Figure 2 is a manganese chloride hexahydrate (MnCl 2 · 4H 2 O), and hexyl and the aqueous solution containing the amine synthesized by heating at 90 ℃ for 3 hours, Mn 3 O 4 nanoparticles according to the second embodiment of the present invention ( a) TEM image, and (b) XRD pattern.
3 (a) is a TEM image of Fe 3 O 4 nanoparticles prepared according to Example 3 of the present invention, and FIG. 3 (b) is a TEM image of Fe 3 O 4 nanoparticles prepared according to Example 4 of the present invention (C) is a TEM image of Fe 3 O 4 nanoparticles prepared according to Example 5 of the present invention, and (d) is a TEM image of Fe 3 O 4 nanoparticles prepared according to Example 6 of the present invention Image.
4 is a TEM image of Fe 3 O 4 nanoparticles prepared according to Example 7 of the present invention. (b) an SEM image and (c) an XRD pattern.
5 is a SEM image (a), (b) and (c) TEM image, (d) ED pattern, and (e) XRD pattern of Fe 3 O 4 nanoparticles prepared according to Example 8 of the present invention.
6 is a TEM image, (d) and (e) EDS mapping of the Fe 3 O 4 nanoparticles prepared according to Example 9 of the present invention, and (f) EDS element ratio.
FIG. 7 shows changes in pH of the Fe 3 O 4 nanoparticles according to the present invention at different reaction times.
8 shows the XRD analysis results of the Fe 3 O 4 nanoparticles according to the present invention.
FIG. 9 shows X-ray photoelectron spectroscopy (XPS) analysis results for Fe 3 O 4 prepared according to Example 1 of the present invention.
이하, 하기 실시예 및 실험예에 의하여 본 발명을 보다 상세하게 설명하고자 한다. 단, 하기 실시예 및 실험예는 본 발명을 예시하기 위한 것으로 하기 실시예 및 실험예 만으로 본 발명의 범위가 한정되는 것은 아니다.Hereinafter, the present invention will be described in more detail with reference to the following examples and experimental examples. However, the following Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited by the following Examples and Experimental Examples.
<재료><Material>
과염소산철 일수화물(Fe(ClO4)2 ·H2O), 염화망간 사수화물(MnCl2 ·4H2O), 헥실아민, 옥틸아민, 도데실아민, 및 BPEI (MW= 25,000 및 750, 000, 50 wt% 수 중 용액) 을 Aldrich사로부터 구입하여 추가적인 정제없이 사용하였다. 선형 PEI (LPEI, MW= 25,000) 를 Polysciences사로부터 구입하였다. 물은 이온 교환으로 정제하였다 (탈이온수).Perchlorate iron monohydrate (Fe (ClO 4) 2 · H 2 O), manganese chloride tetrahydrate (MnCl 2 · 4H 2 O) , hexylamine, octylamine, dodecylamine, and BPEI (MW = 25,000 and 750, 000 , 50 wt% water solution) was purchased from Aldrich and used without further purification. Linear PEI (LPEI, MW = 25,000) was purchased from Polysciences. The water was purified by ion exchange (deionized water).
<실시예 1>≪ Example 1 >
0.5 g 의 BPEI(MW= 750, 000, 50 wt% 수 중 용액) 및 0.202 g 의 헥실아민을 100 mL 의 탈이온수에 용해한 후 자기교반하며 95 °C까지 승온하였다. 1 mL의 10 mM Fe(ClO4)2 ·H2O 용액을 첨가한 후 3 시간 동안 동일 온도에서 가열하였다. 가열 과정 중에, 용액의 색이 청록색에서 흑색으로 변했다. 최종 생성물을 반복 원심분리에 의해 수집하고 탈이온수 및 아세톤의 혼합물로 세척하여 잔류 시약을 제거하였다. 얻어진 Fe3O4 나노입자를 후속 특징분석을 위해 물에 재분산시켰다. 0.5 g of BPEI (MW = 750, 000, 50 wt% water solution) and 0.202 g of hexylamine were dissolved in 100 mL of deionized water, and the mixture was heated to 95 ° C with magnetic stirring. In 1 mL 10 mM Fe (ClO 4 ) 2 · H 2 O was added the solution was heated for 3 hours at the same temperature. During the heating process, the color of the solution changed from cyan to black. The final product was collected by repeated centrifugation and washed with a mixture of deionized water and acetone to remove residual reagent. The resulting Fe 3 O 4 nanoparticles were redispersed in water for subsequent characterization.
<실시예 2>≪ Example 2 >
Fe(ClO4)2 ·H2O 대신 1 mL의 10 mM MnCl2 ·4H2O를 반응용액에 첨가한 것을 제외하고는 실시예 1과 동일한 방법으로 Mn3O4 나노입자를 제조하였다. Fe (ClO 4) 2 · 10 mM in H 2 O instead of MnCl 2 · 1 mL were prepared and the Mn 3 O 4 nanoparticles in the same manner as in Example 1 except that the addition of the 4H 2 O in the reaction solution.
<실시예 3>≪ Example 3 >
헥실아민 대신 옥틸아민을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 Fe3O4 나노입자를 제조하였다.Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1, except that octylamine was used instead of hexylamine.
<실시예 4><Example 4>
헥실아민 대신 도데실아민을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 Fe3O4 나노입자를 제조하였다.Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1, except that dodecylamine was used instead of hexylamine.
<실시예 5>≪ Example 5 >
BPEI(MW= 25, 000, 50 wt% 수 중 용액)를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 Fe3O4 나노입자를 제조하였다.Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1 except that BPEI (MW = 25, 000, 50 wt% solution in water) was used.
<실시예 6>≪ Example 6 >
LPEI를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 Fe3O4 나노입자를 제조하였다.Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1 except that LPEI was used.
<실시예 7>≪ Example 7 >
0.30 g 의 PEI(MW= 750, 000, 50 wt% 수 중 용액) 및 0.101 g 의 헥실아민(10mM)을 100 mL 의 탈이온수에 용해한 후 자기교반하며 95 °C까지 승온하였다. Nickel(Ⅱ) acetate tetrahydrate 0.294g(10mM) 을 3mL 탈이온수에 첨가한 후 3 시간 동안 동일 온도에서 가열하였다. 최종 생성물을 반복 원심분리에 의해 수집하고 탈이온수로 세척하여 잔류 시약을 제거하여 Ni(OH)2 나노입자를 제조하였다. 0.30 g of PEI (MW = 750, 000, 50 wt% solution in water) and 0.101 g of hexylamine (10 mM) were dissolved in 100 mL of deionized water and heated to 95 ° C with magnetic stirring. 0.294 g (10 mM) of Nickel (II) acetate tetrahydrate was added to 3 mL of deionized water and heated at the same temperature for 3 hours. The final product was collected by repeated centrifugation and washed with deionized water to remove residual reagents to produce Ni (OH) 2 nanoparticles.
<실시예 8>≪ Example 8 >
0.30 g 의 PEI(MW= 750, 000, 50 wt% 수 중 용액) 및 0.101 g 의 헥실아민(10mM)을 100 mL 의 탈이온수에 용해한 후 자기교반하며 95 °C까지 승온하였다. Cobalt(Ⅱ) acetate 0.177g(10mM) 을 5mL 탈이온수에 첨가한 후 3 시간 동안 동일 온도에서 가열하였다. 최종 생성물을 반복 원심분리에 의해 수집하고 탈이온수로 세척하여 잔류 시약을 제거하여 Co(OH)2 나노입자를 제조하였다. 0.30 g of PEI (MW = 750, 000, 50 wt% solution in water) and 0.101 g of hexylamine (10 mM) were dissolved in 100 mL of deionized water and heated to 95 ° C with magnetic stirring. 0.177 g (10 mM) of Cobalt (Ⅱ) acetate was added to 5 mL of deionized water and heated at the same temperature for 3 hours. The final product was collected by repeated centrifugation and washed with deionized water to remove residual reagents to produce Co (OH) 2 nanoparticles.
<실시예 9>≪ Example 9 >
0.50 g 의 PEG(MN= 20, 000) 및 0.129 g 의 옥틸아민(10mM)을 100 mL 의 탈이온수에 용해한 후 자기교반하며 90 °C까지 승온하였다. Nickel(Ⅱ) acetate tetrahydrate 0.294g(10mM), Manganese(Ⅱ) chloride tetrahydrate 0.99g(5mM)을 5mL 탈이온수에 첨가한 후 10 시간 동안 동일 온도에서 가열하였다. 최종 생성물을 반복 원심분리에 의해 수집하고 탈이온수로 세척하여 잔류 시약을 제거하였다. 0.50 g of PEG (MN = 20,000) and 0.129 g of octylamine (10 mM) were dissolved in 100 mL of deionized water, and the mixture was heated to 90 DEG C with magnetic stirring. 0.294 g (10 mM) of nickel (Ⅱ) acetate tetrahydrate and 0.99 g (5 mM) of Manganese (Ⅱ) chloride tetrahydrate were added to 5 mL of deionized water and heated at the same temperature for 10 hours. The final product was collected by repeated centrifugation and washed with deionized water to remove residual reagent.
<비교예 1>≪ Comparative Example 1 &
BPEI 를 사용하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 Fe3O4 나노입자를 제조하였다. 그 결과 150 nm 정도의 큰 사이즈를 갖는 Fe3O4 입자가 생성되었다(도 3a 및 3b 참조).Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1 except that BPEI was not used. As a result, Fe 3 O 4 particles having a large size of about 150 nm were produced (see FIGS. 3A and 3B).
<비교예 2>≪ Comparative Example 2 &
헥실 아민을 사용하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로하게 Fe3O4 나노입자를 제조하였다. 그 결과 12 내지 40 nm 크기의 나노입자가 생성되었다. 생성물의 XRD 패턴은 Fe3O4 및 α-Fe2O3 를 포함하는 결정 구조의 혼합물의 존재를 나타낸다(도 3c 및 d). Fe 3 O 4 nanoparticles were prepared in the same manner as in Example 1, except that hexylamine was not used. As a result, nanoparticles of 12 to 40 nm in size were produced. The XRD pattern of the product shows the presence of a mixture of crystal structures containing Fe 3 O 4 and α-Fe 2 O 3 (FIGS. 3c and d).
상기 실시예 및 비교예로부터 본 발명에서 폴리에틸렌이민은 나노 사이즈 입자의 형성을 위해 주요한 캐핑제 역할을 하고, 헥실아민은 Fe3O4 결정 구조의 형성에 중요한 역할을 함을 알 수 있다. It can be seen from the above Examples and Comparative Examples that the polyethyleneimine serves as a main capping agent for the formation of nano-sized particles and hexylamine plays an important role in the formation of the Fe 3 O 4 crystal structure.
<실험예 1> TEM 및 SEM 분석≪ Experimental Example 1 > TEM and SEM analysis
200 kV에서 운전한 JEM-2100F 현미경을 사용하여 실시예 1에서 얻어진 Fe3O4 나노입자에 대한 TEM 및 고해상도 TEM (HRTEM) 이미지를 얻었다. TEM and high-resolution TEM (HRTEM) images of the Fe 3 O 4 nanoparticles obtained in Example 1 were obtained using a JEM-2100F microscope operated at 200 kV.
도 1a는 상기 Fe3O4 나노입자의 특징적인 SEM 이미지로서, Fe3O4 나노입자가 수상에서 성공적으로 합성되었음을 알 수 있다. FIG. 1A is a characteristic SEM image of the Fe 3 O 4 nanoparticles, and Fe 3 O 4 It can be seen that the nanoparticles were successfully synthesized in the water phase.
200 kV에서 운전한 JEM-2100F 현미경을 사용하여 실시예 2에서 얻어진 Mn3O4 에 대하여 SEM 이미지를 얻었다.SEM images of Mn 3 O 4 obtained in Example 2 were obtained using a JEM-2100F microscope operated at 200 kV.
<실험예 2> XRD 분석<Experimental Example 2> XRD analysis
Rigaku D-MAX/A diffractometer(35 kV 및 35 mA)를 사용하여 실시예 1에서 얻어진 Fe3O4 나노입자에 대한 분말 X-레이 회절(XRD) 패턴을 얻었다. A powder X-ray diffraction (XRD) pattern for the Fe 3 O 4 nanoparticles obtained in Example 1 was obtained using a Rigaku D-MAX / A diffractometer (35 kV and 35 mA).
분말 XRD 결과 30.1°, 35.5°, 43.1°, 57.1°, 및 62.7° 피크에서 회절 피크를 나타냈는데, 이는 각각 면심입방 Fe3O4 (마그네타이트)의 (220), (311), (400), (511), 및 (440) 면으로 할당될 수 있다(도 1c, Fd3m, a = 8.375 Å, Joint Committee on Powder Diffraction Standards [JCPDS] file no. 88-0315).Powder XRD results 30.1 °, 35.5 °, 43.1 ° , 57.1 °, and 62.7 ° naetneunde show a diffraction peak at a peak, which respectively face-centered cubic Fe 3 O (220) 4 (magnetite), 311, 400, (FIG. 1C, Fd3m , a = 8.375 A, Joint Committee on Powder Diffraction Standards [JCPDS] file No. 88-0315).
실시예 2에서 얻어진 Mn3O4 나노입자에 대해서도 XRD 분석을 실시하였다. 얻어진 패턴은 4각형 Mn3O4 (하우스마나이트) 구조를 시사한다(도 2b 참조, a = 5.765 Å 이고 c = 9.442 Å, JCPDS file no. 80-0382).XRD analysis was also performed on the Mn 3 O 4 nanoparticles obtained in Example 2. The pattern obtained suggests a tetragonal Mn 3 O 4 (hermannite) structure (cf. FIG. 2b, a = 5.765 Å and c = 9.442 Å, JCPDS file No. 80-0382).
<실험예 3> XPS 분석≪ Experimental Example 3 > XPS analysis
Thermo Scientific K-Alpha spectrometer를 사용하여 실시예 1에서 얻어진 Fe3O4에 대한 X-레이 광전자 분광기(XPS) 데이터를 얻었다. X-ray photoelectron spectroscopy (XPS) data for Fe 3 O 4 obtained in Example 1 was obtained using a Thermo Scientific K-Alpha spectrometer.
Fe XPS 2p 코어 레벨 스펙트럼은 2p 피크의 두 세트를 포함하였다(도 9). 한 세트는 709.3 및 722.7 eV에서 Fe 2p3 /2 및 Fe 2p1 /2 피크로 각각 구성되는데, 이는 Fe3O4에 해당한다. α-Fe2O3 이나 γ-Fe2O3는 다른 719.2 eV 에서 Fe 피크를 포함하는데, 피크가 없는 것으로 보아 생성물이 Fe3O4 임을 시사한다. 생성물의 전형적인 TEM 이미지는 20 내지 30 nm의 크기를 갖는 8면체 나노입자가 생성되었음을 나타낸다(도 1).The Fe XPS 2p core level spectra included two sets of 2p peaks (FIG. 9). One set there is respectively configured in the 709.3 and 722.7 eV in Fe 2p 3/2 and Fe 2p 1/2 peak, which corresponds to Fe 3 O 4. α-Fe 2 O 3 and γ-Fe 2 O 3 contain Fe peaks at the other 719.2 eV, suggesting that the product is Fe 3 O 4 in the absence of peaks. A typical TEM image of the product shows that octahedral nanoparticles having a size of 20 to 30 nm have been generated (FIG. 1).
Claims (9)
상기 금속염은 철염, 망간염, 니켈염, 코발트염 또는 이들의 혼합물인 것을 특징으로 하는 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the metal salt is an iron salt, a manganese salt, a nickel salt, a cobalt salt or a mixture thereof.
상기 알킬아민은 탄소수 6 내지 20인 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the alkylamine has 6 to 20 carbon atoms.
상기 알킬아민은 헥실아민인 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the alkylamine is hexylamine. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 단계의 반응 온도는 20 내지 95℃ 인 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the reaction temperature in the step is 20 to 95 占 폚.
상기 단계는 금속염의 몰농도에 대한 폴리에틸렌이민의 단위체인 C2H5N을 기준으로 한 몰농도의 비가 0.2 내지 1.0인 반응액에서 수행되는 것인, 산화금속 또는 수산화금속 나노입자의 제조방법. The method according to claim 1,
Wherein the step is carried out in a reaction solution having a molar concentration ratio based on C 2 H 5 N, the unit of polyethyleneimine relative to the molar concentration of the metal salt, of from 0.2 to 1.0.
상기 단계는 금속염의 몰농도에 대한 알킬아민의 몰농도의 비가 1.0 내지 3.0인 반응액에서 수행되는 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein said step is carried out in a reaction solution having a molar concentration of alkylamine to molar concentration of metal salt of 1.0 to 3.0.
상기 산화금속 나노입자는 산화철(Fe3O4) 나노입자 또는 산화망간(Mn3O4) 나노입자인 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the metal oxide nanoparticles are iron oxide (Fe 3 O 4 ) nanoparticles or manganese oxide (Mn 3 O 4 ) nanoparticles.
상기 수산화금속 나노입자는 수산화니켈(Ni(OH)2) 나노입자 또는 수산화코발트(Co(OH)2) 나노입자인 것인, 산화금속 또는 수산화금속 나노입자의 제조방법.The method according to claim 1,
Wherein the metal hydroxide nanoparticles are nickel hydroxide (Ni (OH) 2 ) nanoparticles or cobalt hydroxide (Co (OH) 2 ) nanoparticles.
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| WO2019177205A1 (en) * | 2018-03-15 | 2019-09-19 | 경희대학교 산학협력단 | Anisotropic 2d silver nano plates and method for manufacturing same |
| CN114136853A (en) * | 2021-11-25 | 2022-03-04 | 西安交通大学 | Sensor and method for detecting concentration of active metal oxide in air |
| US12060282B2 (en) | 2017-11-10 | 2024-08-13 | Lg Energy Solution, Ltd. | Method for preparation of plate-type manganese dioxide nanoparticles |
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| KR101423563B1 (en) * | 2013-05-20 | 2014-08-01 | 경희대학교 산학협력단 | Sythesis of metal and metal oxide nanocrystals and nanoplate using polyethylenimine as a reducing agent and stabilizer |
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| US12060282B2 (en) | 2017-11-10 | 2024-08-13 | Lg Energy Solution, Ltd. | Method for preparation of plate-type manganese dioxide nanoparticles |
| WO2019177205A1 (en) * | 2018-03-15 | 2019-09-19 | 경희대학교 산학협력단 | Anisotropic 2d silver nano plates and method for manufacturing same |
| CN114136853A (en) * | 2021-11-25 | 2022-03-04 | 西安交通大学 | Sensor and method for detecting concentration of active metal oxide in air |
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| KR101946145B1 (en) | 2019-02-11 |
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