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WO2007138345A1 - Procédé de production de nanoparticules métalliques stabilisées - Google Patents

Procédé de production de nanoparticules métalliques stabilisées Download PDF

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Publication number
WO2007138345A1
WO2007138345A1 PCT/GB2007/050281 GB2007050281W WO2007138345A1 WO 2007138345 A1 WO2007138345 A1 WO 2007138345A1 GB 2007050281 W GB2007050281 W GB 2007050281W WO 2007138345 A1 WO2007138345 A1 WO 2007138345A1
Authority
WO
WIPO (PCT)
Prior art keywords
metal
process according
solution
solvent
nanoparticles
Prior art date
Application number
PCT/GB2007/050281
Other languages
English (en)
Inventor
Peter Trenton Bishop
Alan Boardman
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Priority to EP07733702A priority Critical patent/EP2021520A1/fr
Publication of WO2007138345A1 publication Critical patent/WO2007138345A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B11/00—Obtaining noble metals
    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/054—Nanosized particles
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the present invention relates to a process for producing metal nanoparticles, the metal colloid solution obtained as an intermediate in said process and the high metal content stabilised metal nanoparticles obtained as the final product of said process.
  • Metal nanoparticles have many different applications in areas such as decoration, catalysis, optoelectronics and biotechnology. Various techniques are known for their formation including chemical reduction of metal salts and electrochemical methods. Metal salts previously used in the production of metal nanoparticles have included chloroauric acid (Aslam et al., J. Mat. Chern. , 2004, 14, 1795 and Osterloh et al., Chem. Mat, 2004, 16 (13) 276), silver acetate (Nakamoto et al., Kagaku Kogyo, 2004, 55(12) 943 and Osterloh et al., Chem. Mat, 2004, 16 (13) 276) and silver nitrate (Nakamoto et al., Shikizai Kyokaishi, 2005, 78(5) 221).
  • Stabilisers such as ligands, polymers and surfactants are often used in an effort to reduce nanoparticle agglomeration.
  • ligands to stabilise the surface of nanoparticles is gold nanoparticles stabilised with thiols, as formed by the House method (Brust et al., J. Chem. Soc. Commun., 1994, p. 801). More recently stabilised nanoparticles have been made using long chain alkylamines in place of thiols in various methods including a one-pot aqueous synthesis (Aslam et al., J.
  • the invention provides a process for making high metal content stabilised metal nanoparticles, which process comprising decomposing at least one metal acetylide in the presence of a first solvent under reducing conditions to yield a metal colloid solution and then recovering metal nanoparticles as a precipitate by either:
  • high metal content means that the metal content of the metal nanoparticles is greater than or equal to 65 wt%, for example 75 wt%.
  • the at least one metal acetylide is decomposed by carrying out the reaction at a temperature of from 70 0 C to 200 0 C.
  • the at least one metal acetylide can be decomposed using a chemical reductant, by cathodic reduction or an electrochemical reductant, or by exposure to electromagnetic radiation, e.g. UV or visible light.
  • the process described above uses at least one metal acetylide.
  • the at least one metal in the at least one metal acetylide can be selected from the platinum group metals and the coinage metals.
  • the platinum group metals comprise the metals ruthenium, rhodium, palladium, osmium, iridium and platinum
  • coinage metals comprise the metals silver, gold and copper.
  • the at least one metal acetylide used in the present invention will comprise one or more of silver, gold and copper.
  • the inventors have found that the copper compounds are air sensitive, therefore when the process involves the use of at least one copper acetylide the present invention should be carried out under an inert atmosphere. Reactions not involving the use of at least one copper acetylide may be carried out in air.
  • the at least one acetylide group in the at least one metal acetylide used in the process of the invention can be selected from the list consisting of 1-dodecyne, 1-decyne, 1-nonyne, 1-octyne, 3-methyl-octyn-3-ol, l-octyn-3-ol, 1-ethynyl cyclohexanol, 10-undecynoic acid, 1-ethynyl cyclohexyl acetate and dehydrolinalool.
  • the first solvent comprises a substantially non water-miscible solvent, for example one or more selected from the group consisting of xylene, Shellsol (a C9 aromatic hydrocarbon mixture available from Shell chemicals), toluene, mesitylene, triethylamme, dioxane, cyclohexanone, 4-methyl-2-pentanone, cyclohexanol, dimethylacetamide and dimethylformamide.
  • the first solvent is water, thereby offering an aqueous route to the production of aqueous metal colloids.
  • the second solvent may comprise a solvent with slight organic character, for example one or more selected from the group consisting of methanol, ethanol, iso-propanol and acetone.
  • the second solvent may comprise acetonitrile or a short-to-medium chain hydrocarbon solvent such as hexane.
  • a metal colloid solution may be obtained as an intermediate in the process described above.
  • Such a solution may absorb UV light in the wavelength range of from 510 to 540 iim for gold containing solutions, from 395 to 425 nm for silver containing solutions and from 555 to 585 nm for copper containing solutions.
  • This intermediate metal colloid solution is that it can remain stable for a period of 3 months or more, e.g. 6 months in storage.
  • the intermediate metal colloid solution is concentrated, typically containing from 5% to 70% metal by weight. Both of these properties mean that the intermediate may readily be transported thereby enabling production of high metal content stabilised metal nanoparticles as and when needed, either at the same site or at a different site from where the metal colloid solution was produced.
  • nanoparticles can range in diameter from 2 to 10 nm, commonly from 2 to 6 nm.
  • Gold dodecyne is a stable compound that did not discolour after several months of storage in a refrigerator.
  • Silver dodecyne is a stable compound that did not discolour after several months of storage in a refrigerator, whilst showing good stability in light in comparison to many silver compounds.
  • This gold acetylide was prepared using the same method as Example 1 except that l-octyn-3-ol was used in place of dodecyne. Gold l-octyne-3-ol formed in high yield (90%) as a white coloured, light sensitive powder that remained stable after 2-3 days storage in the dark.
  • This gold acetylide was prepared using the same method as Example 1 except that 3-methyl-l-octyn-3-ol was used in place of dodecyne.
  • Gold 3-methyl-octyn-3-oI formed in high yield, predominantly in the form of an orange oil with approx. 10% yield of a lemon yellow coloured powder. Both the oil and the powder remained stable after 2-3 days storage in a refrigerator.
  • Example 7 The oil from Example 7 was mixed with 80 ml of triethylamine and 20 ml of xylene then heated over a water bath to dissolve the oil, which formed a clear orange solution. The solution quickly darkened to an opaque brown colour by 80 0 C, before forming a red colloid after heating to 100 0 C for approx. 50 mins. The solution was filtered on cooling and the contents poured into excess methanol (approx. 250 ml) to form a precipitate of black powder. The nanoparticles were washed with 2 x 25 ml of methanol before being air-dried to produce a free-flowing, non-tacky brown nanoparticulate powder.
  • Gold ethynyl cyclohexanol is a stable compound that did not discolour after 2-3 months of storage in the dark (even when not refrigerated).
  • Gold dodecyne -ethynyl cyclohexanol (50:50) is a stable compound that did not discolour after 2-3 months of storage in the dark and only discoloured slightly when stored in the light for a day.
  • This gold acetylide was prepared using the same method as Example 9a except that 1.8 g (0.010 moles) of 1-dodecyne and 4.1 g (0.030 moles) of 1 -ethynyl cyclohexanol were used.
  • the compound is brilliant yellow in colour and shows improved light stability in comparison to gold dodecyne and the 50:50 mixed compound prepared in Example 9a.
  • This gold acetylide was prepared using the same method as Example 9a except that 3.7 g (0.020 moles) of dehydrolinalool was used in place of the 1 -ethynyl cyclohexanol.
  • the compound is light tan in colour. The stability of this product has not yet been determined.
  • This gold acetylide was reacted using the same method as Example 12a except that gold dodecyne-ethynyl cyclohexanol (25:75) was used in place of the gold dodecyne-ethynyl cyclohexanol (50:50).
  • This gold acetylide was prepared using the same method as Example 1 except that 1-decyne was used in place of 1-dodecyne. Gold decyne formed in quantitative yield as a yellow coloured powder that remained stable after being stored for a week in the dark.
  • metal acetylides may be prepared and decomposed using electrosynthetic methods in addition to the chemical methods described above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Nanotechnology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Le procédé selon l'invention permet la fabrication de nanoparticules métalliques stabilisées à teneur élevée en métal et comprend la décomposition d'au moins un acétylure métallique en présence d'un premier solvant dans des conditions réductrices pour donner une solution de colloïdes métalliques puis la récupération des nanoparticules métalliques sous la forme d'un précipité, soit en évaporant le premier solvant, soit en ajoutant un second solvant au premier solvant. La solution de colloïdes métalliques pouvant être obtenue en tant qu'intermédiaire grâce à un tel procédé et les nanoparticules métalliques stabilisées à teneur élevée en métal pouvant être obtenues en tant que produit final d'un tel procédé sont également décrites.
PCT/GB2007/050281 2006-05-26 2007-05-22 Procédé de production de nanoparticules métalliques stabilisées WO2007138345A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP07733702A EP2021520A1 (fr) 2006-05-26 2007-05-22 Procédé de production de nanoparticules métalliques stabilisées

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB0610409.5A GB0610409D0 (en) 2006-05-26 2006-05-26 Process for producing metal nanoparticles
GB0610409.5 2006-05-26

Publications (1)

Publication Number Publication Date
WO2007138345A1 true WO2007138345A1 (fr) 2007-12-06

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PCT/GB2007/050281 WO2007138345A1 (fr) 2006-05-26 2007-05-22 Procédé de production de nanoparticules métalliques stabilisées

Country Status (3)

Country Link
EP (1) EP2021520A1 (fr)
GB (1) GB0610409D0 (fr)
WO (1) WO2007138345A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193826A (zh) * 2013-04-15 2013-07-10 中国科学院化学研究所 纳米团簇及其制备方法与应用
WO2017057188A1 (fr) * 2015-09-29 2017-04-06 トッパン・フォームズ株式会社 Composition d'encre argentée, son procédé de production, et produit feuilleté
JP2017115090A (ja) * 2015-12-25 2017-06-29 トッパン・フォームズ株式会社 銀インク組成物
EP3933056A1 (fr) * 2020-06-29 2022-01-05 Remonds PMR B.V. Procédé de récupération de métaux nobles à partir d'une composition colloïdale
CN115609001A (zh) * 2022-07-15 2023-01-17 西北工业大学 一种以炔类化合物制备功能化金纳米颗粒的方法

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969006A1 (fr) * 1997-09-30 2000-01-05 Daiken Chemical Co. Ltd. Compose d'acetylure de metal et procede de production
EP0977212A2 (fr) * 1998-07-31 2000-02-02 International Business Machines Corporation Méthode de fabrication de nanoparticules en métaux de transition
JP2001154215A (ja) * 1999-11-30 2001-06-08 Fuji Photo Film Co Ltd 導電性フィルムおよびその作製方法
US6391818B1 (en) * 1997-12-08 2002-05-21 Celanese Ventures Gmbh Polybetaine stabilized platinum nanoparticles, method for the production thereof and utilization for fuel-cell catalysts
WO2002087749A1 (fr) * 2001-04-30 2002-11-07 Postech Foundation Solution colloidale de nanoparticules metalliques, nanocomposites metal-polymere et procedes de preparation associes
WO2003031323A1 (fr) * 2001-10-12 2003-04-17 Korea Nano Technology Co., Ltd. Synthese de nanoparticules monodispersees et tres cristallines de metaux, d'alliages, d'oxydes metalliques et d'oxydes multi-metalliques sans faire intervenir un procede de selection de la taille
US20050040535A1 (en) * 2003-08-05 2005-02-24 Fuji Photo Film Co., Ltd. Conductive film and method for preparing the same
JP2005281781A (ja) * 2004-03-30 2005-10-13 Kenji Sumiyama 銅ナノ粒子の製造方法
WO2005118184A2 (fr) * 2004-04-22 2005-12-15 Honda Motor Co., Ltd. Nanoparticules a base de metal et a base d'alliages et leurs methodes de synthese

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0969006A1 (fr) * 1997-09-30 2000-01-05 Daiken Chemical Co. Ltd. Compose d'acetylure de metal et procede de production
US6391818B1 (en) * 1997-12-08 2002-05-21 Celanese Ventures Gmbh Polybetaine stabilized platinum nanoparticles, method for the production thereof and utilization for fuel-cell catalysts
EP0977212A2 (fr) * 1998-07-31 2000-02-02 International Business Machines Corporation Méthode de fabrication de nanoparticules en métaux de transition
JP2001154215A (ja) * 1999-11-30 2001-06-08 Fuji Photo Film Co Ltd 導電性フィルムおよびその作製方法
WO2002087749A1 (fr) * 2001-04-30 2002-11-07 Postech Foundation Solution colloidale de nanoparticules metalliques, nanocomposites metal-polymere et procedes de preparation associes
WO2003031323A1 (fr) * 2001-10-12 2003-04-17 Korea Nano Technology Co., Ltd. Synthese de nanoparticules monodispersees et tres cristallines de metaux, d'alliages, d'oxydes metalliques et d'oxydes multi-metalliques sans faire intervenir un procede de selection de la taille
US20050040535A1 (en) * 2003-08-05 2005-02-24 Fuji Photo Film Co., Ltd. Conductive film and method for preparing the same
JP2005281781A (ja) * 2004-03-30 2005-10-13 Kenji Sumiyama 銅ナノ粒子の製造方法
WO2005118184A2 (fr) * 2004-04-22 2005-12-15 Honda Motor Co., Ltd. Nanoparticules a base de metal et a base d'alliages et leurs methodes de synthese

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 200172, Derwent World Patents Index; AN 2001-619888, XP002450724 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103193826A (zh) * 2013-04-15 2013-07-10 中国科学院化学研究所 纳米团簇及其制备方法与应用
CN103193826B (zh) * 2013-04-15 2016-01-06 中国科学院化学研究所 纳米团簇及其制备方法与应用
WO2017057188A1 (fr) * 2015-09-29 2017-04-06 トッパン・フォームズ株式会社 Composition d'encre argentée, son procédé de production, et produit feuilleté
JPWO2017057188A1 (ja) * 2015-09-29 2018-07-12 トッパン・フォームズ株式会社 銀インク組成物、その製造方法及び積層体
JP2017115090A (ja) * 2015-12-25 2017-06-29 トッパン・フォームズ株式会社 銀インク組成物
EP3933056A1 (fr) * 2020-06-29 2022-01-05 Remonds PMR B.V. Procédé de récupération de métaux nobles à partir d'une composition colloïdale
CN115609001A (zh) * 2022-07-15 2023-01-17 西北工业大学 一种以炔类化合物制备功能化金纳米颗粒的方法
CN115609001B (zh) * 2022-07-15 2023-10-10 西北工业大学 一种以炔类化合物制备功能化金纳米颗粒的方法

Also Published As

Publication number Publication date
EP2021520A1 (fr) 2009-02-11
GB0610409D0 (en) 2006-07-05

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