WO2009097669A1 - Procédé de synthèse de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques - Google Patents

Procédé de synthèse de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques Download PDF

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Publication number
WO2009097669A1
WO2009097669A1 PCT/BR2009/000013 BR2009000013W WO2009097669A1 WO 2009097669 A1 WO2009097669 A1 WO 2009097669A1 BR 2009000013 W BR2009000013 W BR 2009000013W WO 2009097669 A1 WO2009097669 A1 WO 2009097669A1
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WIPO (PCT)
Prior art keywords
carbon nanotubes
metal nanoparticles
nanoparticles
metal
nanotubes according
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PCT/BR2009/000013
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English (en)
Portuguese (pt)
Inventor
Luiz Orlando Ladeira
Rodrigo Gribel Lacerda
André Santarosa FERLAUTO
Eudes LORENÇON
Sergio De Oliveira
Edelma Eleto Da Silva
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Universidade Federal De Minas Gerais-Ufmg
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Publication of WO2009097669A1 publication Critical patent/WO2009097669A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive

Definitions

  • the present invention relates to a process of decorating the outer surfaces of carbon nanotubes with metallic nanoparticles resulting in hybrid nanostructured systems formed by carbon nanotubes and metallic nanoparticles.
  • nanotechnology In recent decades, scientific and technological advances such as the recent discovery of carbon nanotubes and fullerenes as well as the development of nanoscopic matter observation systems have allowed the rapid development of nanoscale science and technology, known as nanotechnology.
  • Carbon nanotubes are fibrillary and tubular structures consisting of carbon-carbon sp 2 hybridization bonds with a diameter ranging from 0.7 - 80 nm in diameter and length from 10 to 80,000 nm. Carbon nanotubes due to this large aspect ratio and their exceptional mechanical and electronic structural properties have become of great importance to science [Popov, Materials Science & Engineering R-Reports, 2004, 43, 61].
  • Carbon nanotubes can be synthesized in two forms, namely single-walled carbon nanotubes (NTCPS), formed by a single layer of carbon atoms, and multi-walled carbon nanotubes (NTCMP), consisting of several concentric carbon tubes. .
  • NCPS single-walled carbon nanotubes
  • NTCMP multi-walled carbon nanotubes
  • its properties such as chemical inertia, high aspect ratio and high specific area place this material in a strategic position for the development of nanotechnology mesoscopic systems in which interfacial interactions are preponderant.
  • Hybrid systems that combine carbon nanotubes and other nanostructures such as additional molecular bonds to their wall or miscellaneous nanoparticles allow the creation of new nanoscopic systems with definite function and diverse applications in the areas of new materials and their use in devices such as: hydrogen storage [Zuttel et al., International Journal of Hydrogen Energy, 2002, 27, 203] as catalytic supports [Dicks, Journal of Power Sources, 2006, 156, 128], in the creation of new electronic devices such as single electron transistors, molecular diodes, memory elements.
  • NTC / NPM carbon nanotubes with metal nanoparticles
  • NTC / NPM hybrid systems can be used for heterogeneous catalysis in various chemical, petrochemical and pharmaceutical industry procedures as well as energy applications such as electrodes and catalytic reforming of methanol in PEM (Proton Exchange Membrane) fuel cells [Liang et al., Carbon, 2005, 43, 3144], high performance batteries [Qiu et al., New Journal of Chemistry, 2004, 28, 1056], supercapacitors [Kim et al., Journal of Materials Chemistry, 2005, 15 , 4914], photovoltaic power generation [Camacho et al., Jom, 2007, 59, 39] and nanobiotechnology [Wang et al., Electrochemistry Communications, 2003, 5, 800].
  • PEM Proton Exchange Membrane
  • nanoparticles may be preformed and covalently connected to nanotubes through organic fragments. Chen and colleagues report that first oxidation of NTCPS occurs and subsequently reaction with aliphatic aminothiols that lead to the formation of thiol-terminated nanotubes, which act as connections for the deposition of Au (gold) nanoparticles. [Chen et al., Science, 1998, 282, 95].
  • carbon nanotubes can form polyelectrolyte salts that are soluble in polar organic solvents without the need for functionalization or sonification processes, thus forming a thermodynamically stable solution of isolated nanotubes.
  • Dissolution consists of chemically reducing nanotubes with alkali metals, leading to the formation of polyelectrolyte salts that can carry a charge every 10 carbon atoms.
  • the reducing metal when oxidized, acts as a counter ion compensating for the negative charges acquired by the tube.
  • nanotube reduction can be performed in a system containing a mixture of carbon nanotubes (NTC) and metallic sodium in tetrahydrofuran (THF) in the presence of organic molecules such as naphthalene, anthraquinone and fluorenone under inert atmosphere.
  • NTC carbon nanotubes
  • THF tetrahydrofuran
  • the donation of alkaline metal electrons to the nanotube is through the organic molecules, because they have the property of being directly reduced. by the metal, resulting in an anionic radical that cyclically yields electrons to the nanotube.
  • the nanotube is saturated with charges the organic molecules become permanently charged. This last step can be easily checked by varying the color of the solution that presents the characteristics of the absorption spectrum of the anionic radical.
  • the present invention has great advantages over the existing technological framework on the subject, since the method here
  • the proposed approach describes a rapid process of decoration of NTC with a wide range of binary and ternary metallic NP or alloys and nanoparticles are generated in situ by reducing their ions directly by the NTC, ensuring good adhesion. Also no initial steps of nanotube functionalization are required.
  • the present process proposes the use of carbon nanostructure itself as a reducing agent, whose electrochemical potential in thermodynamic equilibrium is equal to that of Na (sodium) in metallic form.
  • carbon nanostructures become very strong reducing agents thus serving to reduce numerous metal cations in addition to Au, Ag, Pt and Pd cations.
  • the reduction of metal ions will be induced directly on the surface of the NTC, with no free nanoparticles forming in solution.
  • Another advantage is that the new technique does not require any prior NTC functionalization process since the reduced form nanotubes are formed by well dispersed and isolated polyelectrolyte salts.
  • the present invention proposes a process using carbon nanotubes themselves in the form of polyelectrolyte salts as reducing agents of metal salt solutions for the formation of metal nanoparticles and alloys of metal nanoparticles on their outer surface.
  • a donor material such as: Na (sodium), K (potassium) or Li (lithium) in unrestricted elemental form and dispersed or non-functionalized NTCPS or NTCPM carbon nanotubes in aprotic polar organic solvents.
  • This charge transfer is mediated by molecular compounds with high anionic radical formation capacity.
  • the process of decoration of nanostructured materials with metal nanoparticles occurs through the process of chemical reduction of the metal nanoparticle ions present in liquid medium in solid nanoparticles attached to the surface of the solid support, which are carbon nanostructures (NEC) such as: carbon nanotubes single or multiple walls, functionalized or not dispersed in liquid medium.
  • NEC carbon nanostructures
  • the proposed new process involves, in a first step, the electronic transfer of solid Na (sodium) to carbon nanotubes, dispersed in liquid medium through a polar aprotic solvent, such as tetrahydrofuran. Electron transfer by means of some organic compound with a large amount of conjugated double bonds, which have the ability to form anionic radicals such as naphthalene, benzophenone, anthraquinone or unconstrained conjugated organic polymers, used for conducting electrons of the alkali metal to the carbon nanotube (NTC) thus creates a CNT n " polyelectrolyte salt (negatively charged carbon nanotubes) under an inert atmosphere.
  • a polar aprotic solvent such as tetrahydrofuran.
  • Carbon nanotubes are dispersed in an anhydrous polar aprotic solvent such as tetrahydrofuran (THF), not restricted.
  • anhydrous polar aprotic solvent such as tetrahydrofuran (THF)
  • Carbon nanotubes may be single or multi-walled (NTCPSs or NTCMPs) functionalized or not with other molecular compounds, at varying mixing ratios depending on the type of NTC and other molecular groups attached or not to its outer wall.
  • naphthalene is an organic molecule capable of reacting with alkali metal to form an anionic species which has the alkali metal cation as a counterion.
  • naphthalene There are other substances that play the same role and can be used at this stage in place of naphthalene such as: anthraquinone or benzophenone, not restricted.
  • the amount of naphthalene present in the mixture is only limited by its solubility.
  • An amount of finely divided metallic sodium is added to the mixture from the previous step.
  • Metallic sodium can also be replaced by other alkaline metals such as lithium and unrestricted potassium.
  • the amount of sodium required is on the order of milligrams per gram of nanotube (0.1-1000 mg / g NTC). Using a larger quantity does not change the end result of the process.
  • solution A a well dispersed solution of carbon nanotubes in the form of polyelectrolytes is obtained.
  • the formation of polyelectrolytes is usually accompanied by a change in coloration of this solution due to the permanent formation of anionic radicals.
  • the formed anionic radicals interact with carbon nanotubes by solvation process, further increasing the colloidal dispersion of the NTC and avoiding their agglomeration. In this step this solution is called solution A.
  • a suitable amount of salt containing the metal ion of interest is dissolved in an unreacted polar anhydrous solvent such as THF, not restricted. This solution is prepared under ultrasonification or mechanical stirring until completely dissolved.
  • the precursor compounds of these elements are simultaneously dissolved in this non-reactive anhydrous polar solvent in the desired ratio for the formation of the corresponding alloy or for the formation of two or more types of metal nanoparticles. .
  • the most commonly used metal precursor compounds are chlorides, sulphates, oxalates and organometallic compounds of metals such as Fe, Ni, Co, Cu, Zn, Cd, Sn, Rh, Ru, Pd, HAuCU, H 2 PtCL 6l AgNO 3 , unrestricted, and their binary or ternary solutions.
  • the solution prepared in this step is called solution B.
  • Solution B is now slowly mixed with solution A without oxygen, i.e. in an inert atmosphere, by injection through the rubber stopper of the vial containing solution A under vigorous stirring. Because the reaction is very fast, long stirring times are unnecessary and do not alter the outcome of the final product. At this stage, the metal ions receive electrons from carbon nanotubes, thus being reduced into metal nanoparticles on the outer walls of the NTC. This final mixture is called solution C.
  • NTC decorated with metallic nanoparticles can be performed by ultrafiltration or ultra centrifugation processes.
  • NPMs metallic nanoparticles
  • vacuum assisted pore size 0.45 ⁇ m filters are used for separation of NTCs decorated with NPMs by filtration. In this way, after the passage of the mixture through the filter, the NTCs are retained in the filter and, by successive passages of ethanol through the filtration membrane, the NTCs are purified by eliminating solvent residues and other undesirable components.
  • NPM decorated NTC Another more efficient and faster way of purifying NPM decorated NTC is through ultra centrifugation processes.
  • Solution C is centrifuged at 5000rpm for 5 minutes, which causes NPM-decorated NTCs to precipitate and concentrate to the bottom of the centrifuge vessel.
  • the suspension is then discarded and ethanol is added to the centrifuge vessel.
  • the NTCs are then resuspended and centrifuged again at 5000rpm for 5 minutes. This process is repeated 3 to 5 times and finally the NTC are resuspended in ethanol and transferred to Petri dishes and oven dried at 100 ° C for 4 to 12 hours.
  • Example 1 Deposition of Au (gold) nanoparticles on the surface of single walled carbon nanotubes.
  • the sodium contained in the mixture is removed and the supernatant is filtered through a porous membrane filter (pores 0.45 ⁇ m in diameter), washed four times with ethanol and vacuum dried for 2 hours at 100 ° C to obtain nanotubes. carbon with gold nanoparticles on its surface.
  • Example 2 Deposition of Cu (copper) nanoparticles on the surface of single walled carbon nanotubes.
  • the sodium contained in the mixture is removed and the supernatant is filtered through a porous membrane filter (0.45 ⁇ m pore diameter), washed four times. with ethanol and vacuum dried for 2 hours at 100 ° C to obtain carbon nanotubes with copper nanoparticles on their surface.
  • Example 3 Deposition of Rh (rhodium) nanoparticles on the surface of single walled carbon nanotubes.
  • the sodium contained in the mixture is removed and the supernatant is filtered through a porous membrane filter (0.45 ⁇ m pore diameter), washed four times. with ethanol and vacuum dried for 2 hours at 100 ° C to obtain carbon nanotubes with rhodium nanoparticles on their surface.
  • Example 4 Deposition of Au (gold) nanoparticles on the surface of multiwall carbon nanotubes.
  • the sodium contained in the mixture is removed and the supernatant is filtered through a porous membrane filter (pores 0.45 ⁇ m in diameter), washed four times with ethanol and vacuum dried for 2 hours at 100 ° C to obtain multi-walled carbon nanotubes with gold nanoparticles on their surface.
  • a porous membrane filter pores 0.45 ⁇ m in diameter

Abstract

La présente invention concerne un procédé de décoration des surfaces extérieures de nanotubes de carbone avec des nanoparticules métalliques, d'où l'obtention de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques.
PCT/BR2009/000013 2008-01-15 2009-01-15 Procédé de synthèse de systèmes nanostructurés hybrides constitués par des nanotubes de carbone et des nanoparticules métalliques WO2009097669A1 (fr)

Applications Claiming Priority (2)

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BRPI0800605-9 2008-01-15
BRPI0800605A BRPI0800605B1 (pt) 2008-01-15 2008-01-15 processo de síntese de sistemas nanoestruturados híbridos: nanotubos de carbono-nanopartículas metálicas

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012143658A1 (fr) 2011-04-19 2012-10-26 Snecma Propulsion Solide Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse
RU2475445C2 (ru) * 2010-12-20 2013-02-20 Государственное образовательное учреждение высшего профессионального образования "Тамбовский государственный университет имени Г.Р. Державина" Способ получения объемного наноструктурированного материала

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346136B1 (en) * 2000-03-31 2002-02-12 Ping Chen Process for forming metal nanoparticles and fibers
US6875274B2 (en) * 2003-01-13 2005-04-05 The Research Foundation Of State University Of New York Carbon nanotube-nanocrystal heterostructures and methods of making the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6346136B1 (en) * 2000-03-31 2002-02-12 Ping Chen Process for forming metal nanoparticles and fibers
US6875274B2 (en) * 2003-01-13 2005-04-05 The Research Foundation Of State University Of New York Carbon nanotube-nanocrystal heterostructures and methods of making the same

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHOI HEE CHEUL ET AL.: "Spontaneous Reduction of Metal Ions on the Sidewalls of Carbon Nanotubes", J.AM.CHEM.SOC., vol. 124, 2002, pages 9058 - 9059 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2475445C2 (ru) * 2010-12-20 2013-02-20 Государственное образовательное учреждение высшего профессионального образования "Тамбовский государственный университет имени Г.Р. Державина" Способ получения объемного наноструктурированного материала
WO2012143658A1 (fr) 2011-04-19 2012-10-26 Snecma Propulsion Solide Procede de preparation d'un element monolithique de catalyse comprenant un support fibreux et ledit element monolithique de catalyse

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BRPI0800605B1 (pt) 2018-09-04

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