EP2021520A1 - Process for producing stabilised metal nanoparticles - Google Patents
Process for producing stabilised metal nanoparticlesInfo
- Publication number
- EP2021520A1 EP2021520A1 EP07733702A EP07733702A EP2021520A1 EP 2021520 A1 EP2021520 A1 EP 2021520A1 EP 07733702 A EP07733702 A EP 07733702A EP 07733702 A EP07733702 A EP 07733702A EP 2021520 A1 EP2021520 A1 EP 2021520A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- process according
- solution
- solvent
- nanoparticles
- Prior art date
- Legal status (The legal status 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 status listed.)
- Withdrawn
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
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- 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.
Abstract
Description
Claims
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 |
PCT/GB2007/050281 WO2007138345A1 (en) | 2006-05-26 | 2007-05-22 | Process for producing stabilised metal nanoparticles |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2021520A1 true EP2021520A1 (en) | 2009-02-11 |
Family
ID=36687734
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07733702A Withdrawn EP2021520A1 (en) | 2006-05-26 | 2007-05-22 | Process for producing stabilised metal nanoparticles |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2021520A1 (en) |
GB (1) | GB0610409D0 (en) |
WO (1) | WO2007138345A1 (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103193826B (en) * | 2013-04-15 | 2016-01-06 | 中国科学院化学研究所 | Nanocluster and preparation method thereof and application |
WO2017057188A1 (en) * | 2015-09-29 | 2017-04-06 | トッパン・フォームズ株式会社 | Silver ink composition, process for producing same, and layered product |
JP6762092B2 (en) * | 2015-12-25 | 2020-09-30 | トッパン・フォームズ株式会社 | Silver ink composition |
EP3933056A1 (en) * | 2020-06-29 | 2022-01-05 | Remonds PMR B.V. | Process for recovering noble metals from a colloidal composition |
CN115609001B (en) * | 2022-07-15 | 2023-10-10 | 西北工业大学 | Method for preparing functionalized gold nanoparticles by using alkyne compounds |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE69819693T2 (en) * | 1997-09-30 | 2004-09-23 | Daiken Chemical Co. Ltd., Osaka | METAL ACETYLIDE COMPOUND AND METHOD FOR PRODUCING THE SAME |
DE19754304A1 (en) * | 1997-12-08 | 1999-06-10 | Hoechst Ag | Polybetaine-stabilized platinum nanoparticles, process for their preparation and use for electrocatalysts in fuel cells |
US6262129B1 (en) * | 1998-07-31 | 2001-07-17 | International Business Machines Corporation | Method for producing nanoparticles of transition metals |
JP2001154215A (en) * | 1999-11-30 | 2001-06-08 | Fuji Photo Film Co Ltd | Conductive film and its producing method |
US7348365B2 (en) * | 2001-04-30 | 2008-03-25 | Postech Foundation | Colloid solution of metal nanoparticles, metal-polymer nanocomposites and methods for preparation thereof |
KR100867281B1 (en) * | 2001-10-12 | 2008-11-06 | 재단법인서울대학교산학협력재단 | Synthesis of Monodisperse and Highly-Crystalline Nanoparticles of Metals, Alloys, Metal Oxides, and Multi-metallic Oxides without a Size-selection Process |
JP2005054240A (en) * | 2003-08-05 | 2005-03-03 | Fuji Photo Film Co Ltd | Electroconductive film, and its production method |
JP2005281781A (en) * | 2004-03-30 | 2005-10-13 | Kenji Sumiyama | Method for producing copper nanoparticle |
US7335245B2 (en) * | 2004-04-22 | 2008-02-26 | Honda Motor Co., Ltd. | Metal and alloy nanoparticles and synthesis methods thereof |
-
2006
- 2006-05-26 GB GBGB0610409.5A patent/GB0610409D0/en not_active Ceased
-
2007
- 2007-05-22 WO PCT/GB2007/050281 patent/WO2007138345A1/en active Application Filing
- 2007-05-22 EP EP07733702A patent/EP2021520A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO2007138345A1 * |
Also Published As
Publication number | Publication date |
---|---|
GB0610409D0 (en) | 2006-07-05 |
WO2007138345A1 (en) | 2007-12-06 |
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Legal Events
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Owner name: JOHNSON MATTHEY PUBLIC LIMITED COMPANY |
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Effective date: 20111129 |