WO2003072247A1 - Catalyseur organometallique immobilise sur des nanoparticules magnetiques et procede de production associe - Google Patents

Catalyseur organometallique immobilise sur des nanoparticules magnetiques et procede de production associe Download PDF

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Publication number
WO2003072247A1
WO2003072247A1 PCT/KR2002/002369 KR0202369W WO03072247A1 WO 2003072247 A1 WO2003072247 A1 WO 2003072247A1 KR 0202369 W KR0202369 W KR 0202369W WO 03072247 A1 WO03072247 A1 WO 03072247A1
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catalyst
magnetic nanoparticle
magnetic
ionic
organometallic catalyst
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PCT/KR2002/002369
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English (en)
Inventor
Jin-Kyu Lee
Woo Lee
Tae-Jong Yoon
Yoon-Seuk Oh
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Far East Asia Corporation
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Priority to AU2002367727A priority Critical patent/AU2002367727A1/en
Publication of WO2003072247A1 publication Critical patent/WO2003072247A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2282—Unsaturated compounds used as ligands
    • B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/33—Electric or magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0209—Impregnation involving a reaction between the support and a fluid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • Organometallic catalyst immobilized on magnetic nanoparticle and process for the production thereof Organometallic catalyst immobilized on magnetic nanoparticle and process for the production thereof
  • the present invention relates to an ionic organometallic catalyst immobilized on magnetic nanoparticle and a process for the production thereof. More specifically, the present invention relates to a recyclable immobilized catalyst prepared by chemically bonding an ionic organometallic catalyst to the surface of a magnetic nanoparticle, thereby being homogeneously dispersed in solvent, having a very high catalytic activity, and being easily recovered by the magnetic property of the supporter after the catalytic reaction.
  • Homogeneous organometallic catalysts have been studied extensively for a long time, since they can show high catalytic activity under relatively mild reaction conditions compared to the conventional heterogeneous c atalysts that usually w orked under high temperature and high pressure conditions.
  • Homogeneous catalysts which can be mixed with reactants in the same phase, usually have high catalytic activities, and their chemical structures are well defined to make it possible to study the detailed catalytic reaction mechanisms.
  • they have some problems regarding practical applications. They are difficult to be separated from the products mixture, since they are also homogeneously dissolved in the products mixture and thermal isolation processes such as distillation usually result in the decomposition of the organometallic catalysts.
  • Rh-based catalysts have some limitations of being commercialized; they are very expensive and could cause severe environmental problems if they are discarded after only one use.
  • recyclable organometallic catalysts which can be easily separated from products after the catalytic reaction, have been actively developed. There have been known two major methods to make the homogeneous catalysts to be isolated and reused.
  • One method is to use a water-soluble organometallic catalyst, more specifically, to make the catalyst itself soluble in water by introducing an ionic functional group(s) into a ligand(s) binding to metal and carry out the catalytic reaction in the biphasic system, where the catalyst is present in aqueous phase and reactants are present in organic phase. After completing the reaction, therefore, the products in the organic phase can be easily separated and the catalyst in the aqueous phase can also be easily recovered for reuse.
  • Another way is to chemically attach an organometallic catalyst on the surface of micrometer-sized organic or inorganic supporters, which are stable in organic solvent or water.
  • the catalytic reaction is carried out heterogeneously and then, after completing the reaction, the catalyst is simply recovered by filtration for reuse.
  • the first method has the problem of preparing water-soluble organometallic catalysts, mostly due to the difficulty and limitation of synthesizing water-soluble organic ligands.
  • the second one of using the supported catalyst also has very serious drawback of significantly reducing catalytic activity due to the diffusion problem in the heterogeneous reaction system. As one can easily imagine, furthermore, if a small size supporter (smaller than micrometer size) is used in order to overcome the diffusion problem, the difficulty of separating and recovering the catalyst from the products mixture arises again just like in the case of homogeneous system.
  • Nanoparticles have attracted much attention for the various applications due to their novel chemical, physical, electrical, magnetic, and optical properties. Especially, magnetic nanoparticles have been studied for a long time to generate a liquid phase magnet, and some commercial products have already been shown in the market. Since magnetic nanoparticles tended to co-aggregate by magnetic interaction between the nanoparticles, the magnetic nanoparticles which are stable in solvent have been extensively studied. The water-soluble magnetic nanoparticle has been successfully developed based on the principle that electrostatic repulsion between ionic charges on the incompletely bonded sites of metal surface is stronger than the magnetic attraction between the magnetic nanoparticles.
  • the magnetic nanoparticle dispersible in organic solvent was usually prepared by treating the surface of a magnetic nanoparticle with an organic acid having a long alkyl chain such as stearic acid and octadecanoic acid so that the carboxyl groups react with the surface of the magnetic nanoparticle to leave the hydrophobic long alkyl chains to the solution.
  • a new concept of immobilized catalyst to overcome the disadvantages of the conventional homogeneous and heterogeneous catalyst systems is provided by chemically attaching an ionic organometallic catalyst to the surface of a magnetic nanoparticle.
  • the ionic repulsion force between the ionic organometallic catalysts on the magnetic supporter particles keeps them to be dispersed in solvent without any excessive amount of ionic organometallic catalysts (surface capping agent).
  • the nanometer size supporter can have the catalytic activity, which is comparable to the homogeneous one, because the diffusion process is expected to be almost the same in the nanoparticle system.
  • the magnetic property of the supporter material makes the recovery of the catalyst simple and easy by applying an external magnetic field (magnetic decantation).
  • An object of the present invention is, therefore, to provide an ionic organometallic catalyst immobilized on magnetic nanoparticle, which is homogeneously dispersed in organic solvents, which can be simply and easily recycled by magnetic decantation method, and which maintains high catalytic activity.
  • Another object of the present invention is to provide a process for preparing an ionic organometallic catalyst immobilized on magnetic nanoparticle.
  • the immobilized catalyst of the present invention is prepared by chemically attaching an ionic organometallic catalyst to the surface of a magnetic nanoparticle.
  • the immobilized catalyst of the present invention can be dispersed in solvent, in particular organic solvent without any excessive amount of surface treating agent, since the ionic repulsion between the ionic organometallic catalysts overcomes the magnetic attraction between the magnetic nanoparticles.
  • the ionic organometallic catalyst of the present invention comprises any kind of o rganometalhc c atalyst h aving a n i onic s ubstituent o n t he o rganic 1 igand orb eing ionic as a whole due to the oxidation number of the metal, and ionic organic compounds themselves.
  • the ionic organometallic catalyst has to have at least one ligand having functional groups, preferably carboxyl group, to react with the surface of the magnetic nanoparticle.
  • the i onic o rganometallic c atalyst p referably comprises rhodium b ased catalyst, in particular [Rh(l,5-cyclooctadiene)(r ⁇ 6 -benzoic acid)BF 4 of formula (I).
  • the magnetic nanoparticle of the present invention consists of metal or metal oxide, preferably Fe, Co, Ni, ⁇ -Fe 3 O 4 , or ferrite containing Co, Ni, Zn or Mn, most preferably ferrite containing Co.
  • the magnetic nanoparticle preferably has the particle size of 1 to lOOnni.
  • the present ionic organometallic catalyst immobilized on magnetic nanoparticle can be dispersed in water or organic solvent according to the kind of the ionic organometallic catalyst.
  • [Rh(l,5-cyclooctadiene)(rL 6 -benzoic acid)BF 4 immobilized on magnetic nanoparticle can be dispersed in organic solvent such as acetone and methylene chloride.
  • the present ionic organometallic catalyst immobilized on magnetic nanoparticle can be simply prepared comprising the steps of:
  • the ionic organometallic catalyst can be prepared by introducing an organic ligand(s) having an ionic substituent(s), or by modifying a neutral organometallic catalyst.
  • an organic ligand(s) having an ionic substituent(s) or by modifying a neutral organometallic catalyst.
  • [ Rl ⁇ (l ,5-cyclooctadiene)( ⁇ 6 -benzoic a cid)BF 4 can b e p repared by subsequently reacting commercially available chloro(l,5-cyclooctadiene)rhodium(I) dimmer ([Rh(l,5-cyclooctadiene)Cl] 2 ) with AgBF 4 and benzoic acid.
  • the magnetic nanoparticle can be prepared by the slight modification of a known method such as coprecipitation [D. Zins, N. Cabuil, and R. Massart, J Mol. Liq., 1999, 83, 217].
  • the obtained ionic organometallic catalyst and magnetic nanoparticle are reacted in an appropriate solvent to bind the ionic organometallic catalyst to the surface of the magnetic nanoparticle, and then unreacted ionic organometallic catalyst on the surface of the magnetic nanoparticle is removed by washing with a suitable solvent to provide the ionic organometallic catalyst immobilized on magnetic nanoparticle.
  • the present ionic organometallic catalyst immobilized on magnetic nanoparticle can be used in various catalytic reactions according to the kind of the ionic organometallic catalyst.
  • the [Rh(l,5-cyclooctadiene)(r ⁇ 6 -benzoic acid)BF 4 immobilzed magnetic nanoparticle can be used in hydrofomiylation reaction.
  • the immobilzed catalyst of the present invention could be employed for the molecular recognition, D ⁇ A sequencing and heavy metal elimination, etc.
  • the present ionic organometallic catalyst immobilized on magnetic nanoparticle can be recovered by novel method of separating the magnetic particle (magnetic decantation).
  • the magnetic decantation is to apply external magnetic field to the reaction vessel either by permanent or electric magnets for a predetermined time after the catalytic reaction, to isolate magnetic particles containing catalysts from the products, and then to introduce another reaction mixture to the isolated magnetic particles for the consecutive usage.
  • Fig. 1 shows a X-ray powder diffractogram presenting the crystallographic characteristic of Co-ferrite magnetic nanoparticle.
  • Fig. 2 shows FT-IR spectra of (a) cationic Rh catalyst, (b) Co-ferrite magnetic nanoparticle, and (c) cationic Rh. catalyst immobilized on Co-ferrite magnetic nanoparticle.
  • Fig. 3 shows a High Resolution - TEM micrograph of cationic Rh catalyst immobilized on Co-ferrite magnetic nanoparticle.
  • the magnetic Co-ferrite nanoparticle was prepared by slightly modifying of the well-known coprecipitation method. Its chemical composition was confirmed as (CoFe 2 0 4 ) core (Feo . ⁇ O x /!e// by Inductive Coupled Plasma Atomic Emission Spectroscopy (ICP-AES; Shimazu/ICPS-lOOOrV), and its crystallographic characteristic was c onfirmed as s pinel s gagture b y X -ray p owder d iffraction ( XRD; P hillips 3710) (Fig. 1).
  • ICP-AES Inductive Coupled Plasma Atomic Emission Spectroscopy
  • Table 1 shows that the catalyst immobilized on polymer needed 20 hours for the completion of the hydroformylation reaction, while the catalyst immobilized on magnetic nanoparticle only needed 3 hours, which means that the immobilization system of the present invention can significantly enhance the catalytic activity of the immobilized catalyst.
  • the amount of Rh content in the reaction solution was less than 0.01 ppm, determined by ICP-AES, confirming that there is little loss of the Rh catalyst during the reaction and the actual catalytic species is not free Rh complex.
  • Rh catalyst immobilized on Co-ferrite magnetic nanoparticle used in Example 4 was easily recovered by the magnetic decantation method, and then the hydroformyalation reaction was carried out with the recovered catalyst using the same method as in Example 4.
  • the reaction time required for the completion of the reaction, regioselectivity of aldehyde products and reaction yield were analyzed by ! H NMR. The above procedures were repeated 4 times consecutively, and the results are summarized in Table 2.
  • Table 2 shows that the reactivity and regioselectivity of the present Rh catalyst immobilized on magnetic nanoparticle did not change, although it was reused several times. Furthermore, the amount of the Rh catalyst which might be detached from the magnetic nanoparticle during the catalytic reaction was determined by ICP-AES. As a result, it was observed that the amount of Rh in the reaction solution was less than 0.01 ppm, which confirms that there is little loss of the Rh catalyst during consecutive reuses.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne des catalyseurs organométalliques ioniques immobilisés sur des nanoparticules magnétiques ainsi qu'un procédé de production correspondant. Les catalyseurs organométalliques ioniques immobilisés sur des nanoparticules magnétiques sont préparés par l'établissement de liaison chimique entre les catalyseurs organométalliques ioniques et la surface des nanoparticules magnétiques, ces catalyseurs possédant ainsi une activité catalytique très élevée et pouvant être facilement récupérés et recyclés.
PCT/KR2002/002369 2002-02-28 2002-12-17 Catalyseur organometallique immobilise sur des nanoparticules magnetiques et procede de production associe WO2003072247A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2002367727A AU2002367727A1 (en) 2002-02-28 2002-12-17 Organometallic catalyst immobilized on magnetic nanoparticle and process for the production thereof

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KR10-2002-0010837 2002-02-28
KR10-2002-0010837A KR100512451B1 (ko) 2002-02-28 2002-02-28 자성체 나노입자에 지지된 재사용가능한 유기금속촉매 및 그 제조방법

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006025627A1 (fr) * 2004-09-03 2006-03-09 Yonsei University Nanoparticules hydrosolubles stabilisees a l'aide de ligands de groupes multifonctionnels et procede de preparation associe
WO2006070964A1 (fr) * 2004-12-29 2006-07-06 Postech Foundation Synthèse de catalyseurs à base de métaux de transition supportés
WO2007142269A1 (fr) * 2006-06-07 2007-12-13 National University Corporation Chiba University Matériau composite hybride organique-inorganique et procédé de production associé
US8043702B2 (en) 2008-08-25 2011-10-25 Seoul National University Research & Development Business Foundation (Snu R&Db Foundation) Magnetic nanoparticles surface-modified with dithiocarbamate
US8157986B2 (en) 2008-08-27 2012-04-17 Seoul National University Research & Development Business Foundation Magnetic nanoparticle complex
US20130040292A1 (en) * 2005-09-16 2013-02-14 Instituto Nacional De Tecnica Aeroespacial Nanoparticle biosensor, method of preparing same and uses thereof
CN107866202A (zh) * 2017-11-15 2018-04-03 苏州纳贝通环境科技有限公司 一种纳米复合微胶囊水处理剂的制备方法
CN110117368A (zh) * 2019-06-10 2019-08-13 青岛大学 具有空腔结构的摇铃型磁性纳米复合材料及其制备方法

Families Citing this family (5)

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KR100572673B1 (ko) * 2003-10-06 2006-04-19 이진규 지용성 페로플루이드, 그의 제조방법 및 용도
KR100926128B1 (ko) * 2007-06-19 2009-11-11 포항공과대학교 산학협력단 자성체 나노촉매 및 이의 제조 방법
KR101976289B1 (ko) 2017-12-11 2019-05-07 경희대학교 산학협력단 다기능 입자 및 이를 이용한 미세유체 반응 시스템
CN111841638B (zh) * 2019-04-30 2022-05-13 杭州师范大学 一种可见光催化剂及其催化转化co2合成苯并氮杂环的应用
CN112892574A (zh) * 2021-01-25 2021-06-04 华南理工大学 适用于电芬顿的多元异质结核壳催化剂及其制备方法与应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734765A1 (fr) * 1995-03-28 1996-10-02 Mitsui Toatsu Chemicals, Inc. Catalyseur Raney modifié et méthode pour le préparer
WO1998032885A1 (fr) * 1997-01-24 1998-07-30 Hydro-Quebec Materiaux nanocristallins lixivies, leur fabrication et leurs usages dans le secteur energetique
US5939220A (en) * 1996-10-25 1999-08-17 Johnson Matthey Public Limited Company Catalyst
US6239065B1 (en) * 1998-12-22 2001-05-29 Hydro-Quebec Process for the preparation of a supported catalyst

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2953996B2 (ja) * 1995-05-31 1999-09-27 日本電気株式会社 金属被覆カーボンナノチューブおよびその製造方法
KR19980048888A (ko) * 1996-12-18 1998-09-15 김종진 자성금속분말의 표면처리 방법
JP2001031695A (ja) * 1999-07-21 2001-02-06 Keiogijuku 多層サンドイッチ錯体及びその製造方法
KR100438408B1 (ko) * 2001-08-16 2004-07-02 한국과학기술원 금속간의 치환 반응을 이용한 코어-쉘 구조 및 혼합된합금 구조의 금속 나노 입자의 제조 방법과 그 응용

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0734765A1 (fr) * 1995-03-28 1996-10-02 Mitsui Toatsu Chemicals, Inc. Catalyseur Raney modifié et méthode pour le préparer
US5939220A (en) * 1996-10-25 1999-08-17 Johnson Matthey Public Limited Company Catalyst
WO1998032885A1 (fr) * 1997-01-24 1998-07-30 Hydro-Quebec Materiaux nanocristallins lixivies, leur fabrication et leurs usages dans le secteur energetique
US6239065B1 (en) * 1998-12-22 2001-05-29 Hydro-Quebec Process for the preparation of a supported catalyst

Cited By (14)

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Publication number Priority date Publication date Assignee Title
US8801955B2 (en) 2004-09-03 2014-08-12 Industry-Academic Cooperation Foundation, Yonsei University Water-soluble nanoparticles stabilized with multi-functional group ligands and method of preparation thereof
WO2006025627A1 (fr) * 2004-09-03 2006-03-09 Yonsei University Nanoparticules hydrosolubles stabilisees a l'aide de ligands de groupes multifonctionnels et procede de preparation associe
WO2006070964A1 (fr) * 2004-12-29 2006-07-06 Postech Foundation Synthèse de catalyseurs à base de métaux de transition supportés
KR100859748B1 (ko) 2004-12-29 2008-09-24 학교법인 포항공과대학교 불균일계 전이금속 촉매의 제조방법
US20130040292A1 (en) * 2005-09-16 2013-02-14 Instituto Nacional De Tecnica Aeroespacial Nanoparticle biosensor, method of preparing same and uses thereof
US8623636B2 (en) * 2005-09-16 2014-01-07 Consejo Superior De Investigaciones Cientificas Nanoparticle biosensor, method of preparing same and uses thereof
JP5477617B2 (ja) * 2006-06-07 2014-04-23 国立大学法人 千葉大学 有機−無機ハイブリッド複合材料及びその製造方法
WO2007142269A1 (fr) * 2006-06-07 2007-12-13 National University Corporation Chiba University Matériau composite hybride organique-inorganique et procédé de production associé
US8043702B2 (en) 2008-08-25 2011-10-25 Seoul National University Research & Development Business Foundation (Snu R&Db Foundation) Magnetic nanoparticles surface-modified with dithiocarbamate
US8366916B2 (en) 2008-08-27 2013-02-05 Seoul National University Research & Development Business Foundation (“SNU R&DB Foundation”) Magnetic nanoparticle complex
US8157986B2 (en) 2008-08-27 2012-04-17 Seoul National University Research & Development Business Foundation Magnetic nanoparticle complex
CN107866202A (zh) * 2017-11-15 2018-04-03 苏州纳贝通环境科技有限公司 一种纳米复合微胶囊水处理剂的制备方法
CN110117368A (zh) * 2019-06-10 2019-08-13 青岛大学 具有空腔结构的摇铃型磁性纳米复合材料及其制备方法
CN110117368B (zh) * 2019-06-10 2021-12-28 青岛大学 具有空腔结构的摇铃型磁性纳米复合材料及其制备方法

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