WO2012123435A1 - Nanoparticules creuses monoparois de métaux nobles de type platine/argent et leur procédé de préparation - Google Patents

Nanoparticules creuses monoparois de métaux nobles de type platine/argent et leur procédé de préparation Download PDF

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WO2012123435A1
WO2012123435A1 PCT/EP2012/054319 EP2012054319W WO2012123435A1 WO 2012123435 A1 WO2012123435 A1 WO 2012123435A1 EP 2012054319 W EP2012054319 W EP 2012054319W WO 2012123435 A1 WO2012123435 A1 WO 2012123435A1
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nanoparticles
nanoparticle
single wall
noble metal
silver
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Víctor FRANCO PUNTES
Edgar Emir GONZÁLEZ
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Fundació Privada Institut Català De Nanotecnologia
Institució Catalana De Recerca I Estudis Avançats
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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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/52—Gold
    • 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
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • 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
    • B22F1/0547—Nanofibres or nanotubes
    • 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
    • B22F1/0553—Complex form nanoparticles, e.g. prism, pyramid, octahedron
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0466—Alloys based on noble metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/02—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/0087—Galenical forms not covered by A61K9/02 - A61K9/7023
    • A61K9/0092—Hollow drug-filled fibres, tubes of the core-shell type, coated fibres, coated rods, microtubules or nanotubes
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5107—Excipients; Inactive ingredients
    • A61K9/5115—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/48—Preparations in capsules, e.g. of gelatin, of chocolate
    • A61K9/50—Microcapsules having a gas, liquid or semi-solid filling; Solid microparticles or pellets surrounded by a distinct coating layer, e.g. coated microspheres, coated drug crystals
    • A61K9/51—Nanocapsules; Nanoparticles
    • A61K9/5192—Processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
    • B22F2301/255—Silver or gold
    • 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
    • B22F2304/00—Physical aspects of the powder
    • B22F2304/05—Submicron size particles
    • B22F2304/054—Particle size between 1 and 100 nm
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to the field of nanoparticles, more particularly to noble metal nanoparticles with well defined hollow interiors.
  • the invention relates to noble metal nanoparticles with a multiple wall and with a hollow interior, the process to obtain them as well to the use as catalyst. It also relates to Pt/Ag single wall hollow interior nanoparticles, the process to obtain them, as well as to their uses.
  • noble metal nanoparticles have been extensively studied owing to their interesting optical, electronic and catalytic properties.
  • the introduction of hollows into their interiors could offer some properties, such as resonant cavities, increased surfaces areas or reduced density.
  • Nanoparticles obtained by galvanic replacement reaction present an alloy of the metals all over the structure.
  • other approach to produce noble metal nanoparticles has been described by Xiaohu et al. "Au- Ag alloy nanoporous nanotubes" Nano Research, 2009, vol. 2, pag. 386-393. In this document, it is described the obtention of bimetallic nanoporous nanotubes by dispersion in water of silver nanoparticles containing
  • CAB cetyltrimethylammonium bromide
  • ascorbic acid under magnetic stirring and at 40°C, followed by the addition of a salt of Au.
  • CAB cetyltrimethylammonium bromide
  • the sample is mixed with nitric acid. Unfortunately, the pores distribution and size of the nanoparticles obtained are irregular and the particles show signs of fragmentation and structural damage, suggesting that by this method, nanoparticles with sufficient quality can not be obtained.
  • Nanoparticles of Pt/Ag have been produced by the method described in Gao et al. "Bimetallic Ag-Pt hollow nanoparticles: synthesis and tunable surface plasmon resonance", Scripta Materialia, 2007, Vol. 57, pag 687, but when the nanoparticles are formed, the platinum nucleates in form of islands which growth in the surface without the alloying. So, the nanoparticle is not a smooth alloy.
  • Chen et al. “Optical properties of Pd-Ag and Pt-Ag nanoboxes synthesized via galvanic replacement reactions", Nano Lett.
  • an aspect of the invention relates to a Pt/Ag single wall nanoparticle with a hollow interior, wherein the nanoparticle has at least two dimensions at the nanoscale, particularly the nanoparticle has all three dimensions at the nanoscale, where the nanoscale is the range about 1 nm to about 100 nm. Particularly, the nanoparticle has a size from 5 nm to 100 nm, more
  • This Pt/Ag nanoparticle is of a
  • Another aspect of the invention relates to a process for the preparation of Pt/Ag single wall nanoparticles as defined above at room temperature, the process comprising the steps of: a) adding benzyldodecyldimethylammonium chloride in a molar concentration from 3 x10 "2 M to 4 x10 "2 M in an aqueous medium comprising nanoparticles of silver, b) adding a salt of platinum in a molar concentration from 0,05 x 10 "2 to 4 x10 "2 M, particularly from 3 x 10 "2 to 4 x10 "2 M, and c) isolating the obtained nanoparticles.
  • the salt of platinum is not soluble in water.
  • the Pt/Ag single wall nanoparticles are homogeneous, namely are nanoparticles with a
  • nanoparticles obtainable by the process defined above also form part of the invention.
  • noble metal nanoparticles with multiple walls and with a hollow interior comprising two or three noble metals, the walls with a structure based on a layer of noble metals with a high concentration of one of the noble metals both in the exterior and interior face surfaces of the walls, and an alloy of two metals with specific features in the space between the two layers of the wall, advantageously are more stable than nanoparticles made of a simple metallic alloy all over the wall.
  • the reason lies on the high chemical stability of the metal which is in a high concentration in the external faces of the wall.
  • the highly concentrated in the faces noble metal is gold, as it is an inert metal, the nanoparticles are particularly suitable for their use in biological environments.
  • an aspect of the present invention relates to a noble metal nanoparticle with multiple walls and with a hollow interior, the nanoparticle comprising two or three noble metals, wherein each one of the walls comprises a layer of noble metals, with a concentration of one of the noble metals equal to or higher than 85%, both in the exterior and interior face surfaces of the walls, and an alloy of a first and a second noble metals in the space between the two layers of the wall, wherein the second noble metal has a higher reduction potential than the first noble metal, and the first and the second noble metals have different diffusion coefficients, and wherein the noble metal of the layer is made of the second noble metal or of a third noble metal.
  • Another aspect of the present invention relates to a process for the preparation of bimetallic nanoparticles at room temperature comprising the steps of: a) adding cetyltnmethylammonium bromide and ascorbic acid into an aqueous medium comprising nanoparticles of a first noble metal, b) adding a salt of a second noble metal in a molar concentration from 30 ⁇ to 100 ⁇ and with a flow rate from 20 ⁇ /min to 50 ⁇ /min, wherein the second noble metal has a higher reduction potential than the first noble metal, and wherein the first and the second noble metals have different diffusion coefficients, and c) isolating the obtained nanoparticles.
  • the bimetallic nanoparticles obtainable by the process defined above also form part of the invention.
  • Another aspect of the present invention relates to a process for the
  • trimetallic nanoparticles comprising carrying out the process for the preparation of bimetallic nanoparticles and further comprising adding before step c) a salt of a third noble metal in a molar concentration from 3.5x10 "3 M to 4x10 "3 M and with a flow rate from 200 ⁇ /min to 270 ⁇ /min.
  • a salt of a third noble metal in a molar concentration from 3.5x10 "3 M to 4x10 "3 M and with a flow rate from 200 ⁇ /min to 270 ⁇ /min.
  • Another aspect of the present invention relates to a process for the preparation of trimetallic nanoparticles having two or more cavities at room temperature comprising the steps of: a) adding cetyltrimethylammonium bromide or a mixture of cetyltrimethylammonium bromide and ascorbic acid into an aqueous medium comprising nanoparticles of a first noble metal, b) adding a salt of a second noble metal in a molar concentration from 3.5x10 " M to 4x10 "3 M,
  • the trimetallic nanoparticles having two or more cavities obtainable by the process defined above also forms part of the invention.
  • the trimetallic nanoparticles have the two or more cavities uniformly distributed.
  • Another aspect of the present invention refers to the use of any of the nanoparticles disclosed above as a catalyst.
  • nanoparticles can also be used as fuel cells, drug delivery carrier, sensor or plasmon resonators.
  • Another aspect of the present invention refers to the use of any of the nanoparticles disclosed above as a catalyst or drug delivery carrier.
  • the process of the invention ensures the formation of pores with control in the size and localization. This may be an important condition for its use as carrier and delivery system, on the other hand allows a fine modulation of the optical response. Accordingly, another aspect of the invention relates to a process for the preparation of bimetallic nanoparticles in the form of nanocages at room temperature the process comprising the steps of: a) adding
  • benzyldodecyldimethylammonium chloride in a molar concentration from 3 x 10 "2 M to 3.5 x 10 "2 M in an aqueous medium comprising nanoparticles of a first noble metal, b) adding a salt of a second noble metal in a molar concentration from 1 .4 x10 "4 M to 3 x10 "4 M and with a flow from 100- to 200 ⁇ /min, herein the second noble metal has a higher reduction potential than the first noble metal, and wherein the first and the second noble metals have different diffusion coefficients, and c) isolating the obtained nanoparticles.
  • the bimetallic nanoparticles in the form of nanocages obtainable by the process as defined above.
  • another aspect of the present invention relates to the use of Pt/Ag nanoparticles, in particular, in form of nanocages, nanoboxes or nanotubes, more particularly in form of nanocages, as defined above as a drug delivery carrier, as catalytic cathode in fuel cells or as a catalyst in oxidation reactions.
  • This aspect can also be formulated as a method of use of the mentioned nanoparticles as a drug delivery carrier, as catalytic cathode in fuel cells or as a catalyst in oxidation reactions.
  • This aspect can also be formulated as a method of use of the mentioned nanoparticles as catalytic cathodes in fuel cells. It can be prepared a colloidal solution of AuAg nanoparticles, in particular blue colour. For its preparation, Au nanocages are prepared. The gold nanocage may be prepared by the method explained in the Example 10 of this document. The gold nanoparticle may be prepared also by other methods known in the art. It is also prepared oxidized polyvinylpyrrolidone (PVP). For its preparation PVP is oxidized during two days in the presence of air. Other method known in the art for oxidizing the polyvinylpyrrolidone may also be used.
  • PVP polyvinylpyrrolidone
  • FIG. 1 shows a Transmission electron microscopy (TEM) image of double walled nanocubes Au/Ag.
  • FIG. 2 shows an Energy-dispersive X-ray spectroscopy (EDX) map of double walled nanocubes Au/Ag.
  • EDX Energy-dispersive X-ray spectroscopy
  • FIG 3 shows a schematic representation of double walled nanocubes with an open window.
  • FIG. 4 shows a TEM image for Pt-Ag nanoboxes.
  • FIG. 5 shows a TEM image of Au-Ag nanocages.
  • FIG. 6 show a schematic representation of a trimetallic Pd-Au-Ag triple walled nanocubes with five cavities
  • Pt/Ag single wall nanoparticles with a hollow interior of the invention are part of the invention.
  • the process is carried out at room temperature, and comprises the steps of: a) adding benzyldodecyldimethylammonium chloride until obtaining a molar concentration from 3 x 10 "2 M to 4 x 10 "2 M in an aqueous medium comprising nanoparticles of silver, b) adding a non-water soluble salt of platinum until obtaining a molar concentration from 0,05 x 10 "2 M to 4 x10 "2 M, particularly from 3 x 10 "2 M to 4 x 10 "2 M, in the aqueous medium, and isolating the obtained nanoparticles.
  • the salt of platinum is not soluble in water.
  • the salt of platinum is PtCI 2 .
  • PtCI 2 provides a high standard potential, favoring the inherent reactivity in addition to its insolubility in water, aspect that allows a kinetic control on reaction via a sustained release of Pt ions in the reacting mixture. It is known that PtCI 2 is soluble in HCI or ammonia, so, with the use of
  • amphyphilic/tensioactives/surfactant molecules as
  • BDAC benzyldodecyldimethylammonium chloride
  • the wall ot the Pt/Ag single wall nanoparticles with a hollow interior as defined above has a thickness from 3 to 10 nm, particularly of around 5 nm.
  • the nanoparticle of silver is a nanocube and, consequently, the obtained nanoparticle is a nanobox.
  • the nanoparticle of silver is a nanowire and the obtained nanoparticle is a nanotube.
  • the Pt/Ag single wall nanoparticles are homogeneous.
  • Pt/Ag single wall nanoparticles with a hollow interior in form of nanoboxes or in form of nanotubes obtainable by this process also form part of the invention.
  • Pt/Ag nanotubes show a great potential in their use as catalytic agents. Particularly, with Pt/Ag nanotubes it is not necessary having an additional substrate to form the catalytic cathode.
  • the salt of platinum is H 2 PtCI 6 .
  • H 2 PtCI 6 appear a formation of Pt-Ag nanocages with porous symmetrically distributed.
  • the isolation of the obtained nanoparticles can be carried out by conventional methods known to those skilled in the art, such as by filtration or
  • another aspect of the present invention relates to a noble metal nanoparticle with multiple walls and with a hollow interior, the nanoparticle comprising two or three noble metals, wherein each one of the walls comprises a layer of a noble metals with a concentration of one of the noble metals equal to or higher than 85% both in the exterior and interior face surfaces of the walls, and an alloy of a first and a second noble metals in the space between the two layers of the wall, wherein the second noble metal has a higher reduction potential than the first noble metal, and the first and the second noble metals have different diffusion coefficients, and wherein the noble metal of the layer is made of the second noble metal or of a third noble metal.
  • the layer of noble metals has a concentration of one of the noble metals equal to or higher than 90%, more preferably, metals equal to or higher than 95%, still more preferably equal to or higher than 97%, and even still more preferably equal to or higher than 99%.
  • nanoparticle refers to a particle with at least two dimensions at the nanoscale, particularly with all three dimensions at the nanoscale, where the nanoscale is the range about 1 nm to about 100 nm.
  • the “nanoparticle” refers to a particle with at least two dimensions at the nanoscale, this two dimensions being the cross-section of the nanoparticle.
  • the term "size” refers to a characteristic physical dimension.
  • the size of the nanoparticle corresponds to the diameter of the nanoparticle.
  • the size of the nanoparticle corresponds to the diameter of the cross-section of the
  • a size of a set of nanoparticles can refer to a mode of a distribution of sizes, such as a peak size of the distribution of sizes.
  • noble metal refers to metals that are resistant to corrosion and oxidation in moist air. Examples of noble metal are palladium, silver, platinum and gold.
  • multiple walls refers to at least a double wall, for example double wall, triple wall or quadruple wall.
  • hollow interior refers to the presence of one or more cavities in the interior of the nanoparticle, such as two, three, four or five cavities.
  • metal alloy refers to a homogeneous mixture of two or more metals, wherein each of the metals may be in different or equal amounts.
  • homogeneous as used herein is understood according to the common understanding of the term. Namely, in the context of composite metals, it relates to an alloy of metals which forms a solid solution, i.e., to a homogeneous mixture of two or more than two metals.
  • a “homogeneous Pt-Ag nanoparticle” is a nanoparticle with a single phase alloy between silver and platinum.
  • a “solid solution” is a solid-state solution of one or more solutes in a solvent. Such a mixture is considered a solution rather than a compound when the crystal structure of the solvent remains unchanged by addition of the solutes, and when the mixture remains in a single homogeneous phase.
  • the nanoparticle of the invention refers to a nanobox, nanotube or a nanocage.
  • the nanobox, nanotube or nanocage may have different morphologies depending on the sacrificial template, which can have different shapes such as cubes, spheres, wires, rods, prisms and so on.
  • the term "nanobox” as used herein, refers to nanoparticles with hollow interior and solid walls, or with one pore in one of the walls.
  • nanoparticles refers to nanoparticles with hollow interior and porous walls and/or porous corners.
  • nanotubes refers to cylindrical nanoparticles with porous walls or solid walls.
  • sacrificial template refers to nanoparticles that participate as reactant and are partially or totally consumed during the process.
  • the final product takes the same shape as the template, aspect that allows controlling the geometry of the hollow structure.
  • the first novel metal is silver.
  • the second and third noble metals are selected from the group consisting of gold, platinum, and palladium.
  • the nanoparticle is a bimetallic double walled nanoparticle and has an opening giving access to the hollow interior.
  • the nanoparticle is a Au/Ag double walled nanocube. This nanoparticle is shown in FIG. 1 .
  • FIG 2 shows the metalic distribution of the nanoparticle of FIG. 1 .
  • the nanoparticle is a Au/Ag double walled nanosphere.
  • the nanoparticle is a double walled nanotube.
  • opening giving access to the hollow interior refers to a hole that allows direct access to the interior of the nanoparticle.
  • a schematic representation of this access is shown in FIG. 3.
  • the nanoparticle is a trimetallic double wall nanoparticle nanoparticle and has an opening giving access to the hollow interior.
  • the nanoparticle is Pd/Au/Ag double walled nanocube.
  • the inventors have development trimetallic nanoparticles with interior cavities, symmetrically distributed in the nanoparticles.
  • the nanoparticle is a trimetallic nanoparticle having two or more cavities such as two, four or five central cavities.
  • the nanoparticle is a trimetallic nanoparticle having two or more cavities such as two, four or five central cavities.
  • nanoparticle is Pd/Au/Ag triple walled with five cavities. A schematic representation of this nanoparticle is shown in FIG. 6.
  • cavities refers to interior voids surrounded by only one wall of noble metals in the centre symmetrically distributed.
  • the term cavities does not include the gaps between the walls or the gaps around the cavities.
  • the bimetallic nanoparticles as defined above may be prepared by a process carried out at room temperature comprising the steps of: a) adding
  • cetyltrimethylammonium bromide and ascorbic acid into an aqueous medium comprising nanoparticles of a first noble metal, b) adding a salt of a second noble metal in a molar concentration from 30 ⁇ to 100 ⁇ and with a flow rate from 20 ⁇ /min to 50 ⁇ /min, wherein the second noble metal has a higher reduction potential than the first noble metal, and wherein the first and the second noble metals have different diffusion coefficients, c) isolating the obtained nanoparticles.
  • room temperature refers to a temperature between 20°C to 30°C, for example 25°C.
  • Hydrochloric acid may be optionally added in step a.
  • the trimetallic nanoparticles as defined above may be prepared by a process comprising carrying out the process of the second aspect of the present invention and further comprising adding before step c) a salt of a third noble metal in a molar concentration from 3.5x10 "3 M to 4x10 "3 M and with a flow rate from 200 ⁇ /min to 270 ⁇ /min.
  • the third noble metal has a lower reduction potential than the second noble metal, thereby a nanocage is obtained. In another particular embodiment, the third noble metal has a higher reduction potential than the second noble metal, thereby a nanobox is obtained.
  • Example 8 Production of trimetallic Pd-Au-Ag triple walled nanocubes with five cavities

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Abstract

L'invention porte sur des nanoparticules de métaux nobles et sur leur procédé de préparation. L'invention porte en particulier sur des nanoparticules monoparois de Pt/Ag homogènes ayant un intérieur creux, ainsi que sur le procédé pour leur préparation et sur les utilisations des nanoparticules comme vecteur d'administration de médicament, cathode catalytique dans des piles à combustible ou catalyseur dans des réactions d'oxydation.
PCT/EP2012/054319 2011-03-14 2012-03-13 Nanoparticules creuses monoparois de métaux nobles de type platine/argent et leur procédé de préparation WO2012123435A1 (fr)

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WO2017072701A1 (fr) * 2015-10-27 2017-05-04 Fondazione Istituto Italiano Di Tecnologia Procédé de préparation de nanoparticules creuses d'oxyde métallique
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CN111850528A (zh) * 2020-07-10 2020-10-30 南京大学 一种纳米银线表面抗氧化抗硫化保护方法
US20230294076A1 (en) * 2022-03-16 2023-09-21 Honda Motor Co., Ltd. Synthesis of bimetallic structures for use as catalysts

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410007B2 (en) 2012-09-27 2016-08-09 Rhodia Operations Process for making silver nanostructures and copolymer useful in such process
US9776173B2 (en) 2013-06-07 2017-10-03 Lg Chem, Ltd. Hollow metal nanoparticles
EP2990138A4 (fr) * 2013-06-07 2017-01-11 LG Chem, Ltd. Nanoparticules métalliques creuses
JP2016530676A (ja) * 2013-11-01 2016-09-29 エルジー・ケム・リミテッド 燃料電池およびその製造方法
US9614227B2 (en) 2013-11-01 2017-04-04 Lg Chem, Ltd. Fuel cell and method of manufacturing same
EP2998269A4 (fr) * 2013-11-01 2016-12-07 Lg Chemical Ltd Pile à combustible et son procédé de fabrication
US10814313B2 (en) 2015-10-27 2020-10-27 Fondazione lstituto Italiano Di Tecnologia Method for the preparation of metal oxide hollow nanoparticles
WO2017072701A1 (fr) * 2015-10-27 2017-05-04 Fondazione Istituto Italiano Di Tecnologia Procédé de préparation de nanoparticules creuses d'oxyde métallique
CN111554946A (zh) * 2020-04-23 2020-08-18 广东道氏云杉氢能科技有限公司 具有高HOR催化活性的Pt合金及其制备方法和应用
CN111554946B (zh) * 2020-04-23 2022-05-17 广东泰极动力科技有限公司 具有高HOR催化活性的Pt合金及其制备方法和应用
CN111850528A (zh) * 2020-07-10 2020-10-30 南京大学 一种纳米银线表面抗氧化抗硫化保护方法
US20230294076A1 (en) * 2022-03-16 2023-09-21 Honda Motor Co., Ltd. Synthesis of bimetallic structures for use as catalysts
US11766660B1 (en) * 2022-03-16 2023-09-26 Honda Motor Co., Ltd. Synthesis of bimetallic structures for use as catalysts
US20230381745A1 (en) * 2022-03-16 2023-11-30 Honda Motor Co., Ltd. Synthesis of bimetallic structures for use as catalysts
US12030035B2 (en) * 2022-03-16 2024-07-09 Honda Motor Co., Ltd. Synthesis of bimetallic structures for use as catalysts

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