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WO2008127396A2 - Synthèse de solution d'ensembles conjugués de nanotubes en carbone/nanoparticule contenant un métal - Google Patents

Synthèse de solution d'ensembles conjugués de nanotubes en carbone/nanoparticule contenant un métal Download PDF

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WO2008127396A2
WO2008127396A2 PCT/US2007/083414 US2007083414W WO2008127396A2 WO 2008127396 A2 WO2008127396 A2 WO 2008127396A2 US 2007083414 W US2007083414 W US 2007083414W WO 2008127396 A2 WO2008127396 A2 WO 2008127396A2
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metal
swnt
mcnp
nanoparticle
polymer
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WO2008127396A3 (fr
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Liwei Chen
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Ohio University
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Ohio University
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y10/00—Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
    • 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
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/168—After-treatment
    • C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/02—Single-walled nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/22—Electronic properties
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2202/00—Structure or properties of carbon nanotubes
    • C01B2202/20—Nanotubes characterized by their properties
    • C01B2202/28—Solid content in solvents
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/20—Carbon compounds, e.g. carbon nanotubes or fullerenes
    • H10K85/221—Carbon nanotubes

Definitions

  • Conjugated systems of nanomaterials are desired because they have the potential to exhibit collective properties drastically different from what would be expected from a simple combination of the individual components.
  • a coupling occurs between the plasmonic modes for the different types of metal nanoparticles at the nanoparticle interfaces that can lead to interesting physical phenomena such as an enhancement, by several orders of magnitude, of electromagnetic field strengths exhibited in the optical frequency range.
  • Carbon nanotubes have extraordinary mechanical, thermal, and electrical properties due to their unique all-carbon structure.
  • a single wall carbon nanotube (SWNT) can be conceptualized as a one-atom-thick layer of graphite called graphene wrapped into a seamless cylinder.
  • the particular properties and unique structures associated with SWNTs is a reason why there is the strong interest in synthesizing SWNT/Metal nanoparticle assemblies.
  • the coupling between the plasmonic modes of metal nanoparticles and the dipole moments or plasmons in single wall carbon nanotube may possibly be utilized for light harvesting.
  • Futhermore since carbon nanotubes have large surface areas and high electrical conductivities, they are ideal support substrates for depositing catalytic metal nanoparticles like Pt and Pd.
  • Metal nanoparticles have great potential for use in electrochemical cell and fuel cell applications.
  • Metal nanoparticles might also be attached to carbon nanotubes in a way that allows the carbon nanotubes to serve as a growth template for producing fused metal nanowires, which could then be used for hydrogen storage or in chemical and biological sensing applications.
  • SWNT-metal nanoparticle assemblies Attempts to produce individually dispersed SWNT-metal nanoparticle assemblies have been unsuccessful and literature reports of SWNT assemblies have been limited to assemblies made with metal nanoparticles using multi-walled CNT, or large bundles of SWNTs, or surface attached SWNTs.
  • SWNTs can be dispersed into aqueous solutions by chemically functionalizing the sidewalls of the individual SWNT to make them hydrophilic.
  • SWNTs may be dispersed into aqueous solutions using polymer surfactants to solubilize the SWNTs by incorporating them into micelle-type structures.
  • a natural polymer that has been used for this purpose is single stranded (ss) DNA. It is believed that DNA forms a micelle with the SWNTs by wrapping around the SWNTs such that the aromatic bases of the DNA strand are directed to the SWNT 's hydrophobic exterior surface, while the hydrophilic, charged DNA backbone is directed towards the aqueous solution.
  • SWNT/MCNP assembly methods for producing assemblies of single-walled carbon nanotubes (SWNT) and metal-containing nanoparticles (MCNP) in a medium, herein referred to as a SWNT/MCNP assembly.
  • the methods involve dispersing SWNTs in a medium in the presence of one or more polymer surfactants, adding metal ions to the SWNTs dispersed in the medium to form a solution, incubating the solution, and reacting the metal ions with an effective amount of a reagent to form a SWNT/MCNP assembly.
  • Methods are also provided herein for producing SWNT/MCNP assemblies in various types of media.
  • the medium is an aqueous solvent, or an organic solvent, or mixtures thereof.
  • the medium is a matrix, or a mixture of a matrix with an aqueous or organic solvent.
  • the matrix may be but is not limited to a polymer matrix or a sol-gel matrix.
  • the polymer surfactants may be chosen from materials that are naturally occurring polymers such as DNA, proteins, and peptides or may be chosen from synthetic polymers.
  • SWNT/MCNP assemblies prepared by the methods described herein.
  • the SWNT/MCNP assemblies may be prepared wherein the MCNPs are metal nanoparticles, though in other embodiments, the SWNT/MCNP assemblies may be prepared wherein the MCNPs are semiconductor nanoparticles or metal-oxide nanoparticles.
  • a SWNT/MCNP assembly comprising a SWNT, at least one polymer surfactant, and at least one MCNPs.
  • the MCNP in the SWNT/MCNP assembly may be metal nanoparticles, semiconductor nanoparticles or metal-oxide nanoparticles.
  • FIGURE 1 shows various carbon nanotube structures.
  • FIGURE 2 is a schematic representation of the synthetic polymeric surfactants described herein.
  • FIGURE 3 shows two representative embodiments of polymeric backbones of synthetic polymeric surfactants described herein.
  • FIGURE 4(A) is an AFM image of a SWNT complex ed with PSMA with free
  • FIGURE 4(B) is an AFM image of a SWNT/Pd metal nanoparticle assembly.
  • FIGURE 4(C) is an AFM image of a SWTMT/Pt metal nanoparticle assembly.
  • FIGURE 4(D) is an AFM image of a mixture containing Pd metal clusters
  • SWNTs complexed with PSMA The mixture was formed without incubation.
  • FIGURE 5(A) is an AFM image of S WNT/ Au metal nanoparticle assembly.
  • FIGURE 5(B) is an AFM image of S WNT/Cu metal nanoparticle assembly.
  • FIGURE 5(C) is an AFM image of SWNT/Fe metal nanoparticle assembly.
  • FIGURE 6(A) is a TEM image of a SWNT/Pd metal nanoparticle assembly.
  • FIGURE 6(B) is a TEM image of a S WNT/Pt metal nanoparticle assembly.
  • FIGURE 7 is an AFM image of Pt particles obtained reduction of Pt(terpy) 2+ in the absence of SWNTs complexed with PSMA.
  • the terms “disperse” and “dispersion” means to provide a homogeneous and stable mixture. In some embodiments, these dispersions remain stable to precipitation at room temperature for at least one month, but particular examples can have even greater stability and for such cases these conditions will be specified.
  • species that are chemically compatible are species that have similar molecular structures or at least one similar chemical property, (for example polarity, hydrophobicity or hydrophilicity) chemical structures or chemical properties in common.
  • RAFT radical reversible addition-fragmentation chain transfer
  • an agent such as a dithioester, dithiocarbamate, trithiocarbonate, and xanthate
  • RAFT polymerization produces polymers with low polydispersity and high functionality and is suitable for use with a variety of monomers and for producing complex architectures such as block, star, graft, comb, and brush (co)polymers.
  • the procedures, reaction conditions and techniques of RAFT polymerization are well known in the art.
  • SWNTs When SWNTs are made, many varieties of SWNTs may be simultaneously produced, each variety possibly having distinct properties. SWNTs can be produced that have metallic-type or semiconducting-type properties, and SWNTs can be produced that have different chiral vector conformations.
  • a graphene sheet wraps up to form a SWNT, it wraps in the direction of a chiral vector represented by a pair of indices (n, m).
  • the indices (n, m) are the chiral vector coordinates along the two axes of the plane constituting the 2- dimensional honeycomb lattice of a graphene sheet. Certain chiral vector values are associated with specific conformations.
  • SWNT conformational or electronic variety
  • the polymer surfactants may be selected from materials that are naturally occurring polymers such as DNA, proteins, peptides, and from synthetic polymers.
  • polymer surfactants are selected from naturally occurring materials such as DNA, protein, and peptides, they can be obtained from a variety of commercial sources, or alternatively, DNA, peptides and protein polymers can be custom made by various suppliers. These materials can be used directly, at the concentrations and in the solutions as they are supplied, or they can be further isolated, derivatized, or otherwise manipulated in order to tailor their solubility in a variety of aqueous solutions, pH ranges, and organic solvents using techniques that are well known in the art, which have been previously reported.
  • the synthetic polymers described herein have a backbone comprised of a plurality of repeat units, where each repeat unit is a structure derived from one or more monomers capable of undergoing polymerization to form the repeat unit structure.
  • the plurality of repeat units may be selected to have chemical compatibility with the media of choice.
  • a side chain moiety may be attached to one or more of the repeat units in the polymer backbone. In some embodiments, these side chain moieties are selected to have chemical compatibility with the SWNTs.
  • a spacer group may also be present attached in-between the side chain moiety and a repeat unit of the polymer backbone.
  • Synthetic polymers have a basic structure as represented by FIGURE 1.
  • polymer backbones are contemplated where at least one monomer used to produce the repeating unit is either styrene or vinyl ether.
  • Other polymer backbones are contemplated where at least two monomers are used to produce the repeat unit and wherein one of the monomers is either styrene or vinyl ether and the other monomer is selected from the group consisting of acrylic acid, acrylic anhydride, acrylamide, acrylate, methacrylate, methacrylamide, methyl -methacrylate, fumaric acid, fumaric anhydride, maleic acid, and maleic anhydride, and mixtures thereof.
  • Exemplary embodiments of polymer backbones may also include a styrene/maleic acid (anhydride) alternating polymers; vinyl ether/maleic acid (anhydride) alternating copolymers, in which vinyl ether is vinyl methyl, ethyl, propyl, isopropyl, or butyl ether and etc; other copolymers containing maleic acid (anhydride), fumaric acid, and fumaric esters in the backbone; acrylic polymers, which are either homo- or co-polymers made from pure or mixture of acrylic acid, acrylic anhydride, acrylates, acrylamides, methacrylates, and methacrylamides.
  • a preferred polymer backbone is an alternating copolymer of styrene and maleic acid (PSMA).
  • synthetic polymers described herein may have a cationic polymer backbone structure and may be capable of carrying a cationic charge.
  • the polymer backbone may contain amine or amide-type functionalities or mixtures thereof as part of the repeating unit.
  • amine or amide- type functionalized polymers include polymers having the repeat unit structures shown in FIGURE 2.
  • Synthetic polymers having a cationic polymer backbone structure may be water- soluble and may manifest a Lower Critical Solution Temperature (LCST).
  • LCST Lower Critical Solution Temperature
  • the LCST is the temperature at which a polymer dissolved in aqueous solution undergoes a phase transition, going from one phase (a homogeneous solution) to a two-phase system (a polymer rich phase and a water rich phase).
  • Polymers that change from a one to two phase system as the temperature increases are characterized as having inverse solubility and are called temperature sensitive polymers.
  • temperature sensitive polymers undergo solubilization quickly and exhibit highly dispersive properties in cold water but remain relatively inert in warmer water.
  • synthetic polymers having an LCST in the temperature range from about 25 to about 35 0 C.
  • Useful temperature sensitive polymers include polymers synthesized from n-alklyacrylamide-based monomers, as for example isoproplymethacrylamide, diethylacrylamide, proplyacrylamide, ethylproplyacrylamide, n- and tert-butlyacrylamide and ethoxyethylacrylamide.
  • Other useful temperature sensitive polymers include poly(lysine), poly(N-isopropylacrylamide), poly(N- (3-ethoxypropyl)acryl-amide), or derivatives thereof.
  • temperature sensitive polymers having a cationic polymer backbone structure that is based on monomers of the type described herein may not need to be further derivatized with side group moieties in order to be useful. However, the temperature sensitive polymers may be further converted if it is so desired by attaching any of the various side group moieties described herein onto the backbone structures of the temperature sensitive polymers using conventional chemical synthesis techniques.
  • Any suitable polymerization method may be used to make the backbone part of the synthetic polymers contemplated and claimed herein.
  • One useful method is radical reversible addition-fragmentation chain transfer (RAFT) polymerization.
  • Polymers having repeat units derived from at least two monomers capable of undergoing RAFT polymerization can be made when the two monomers undergo RAFT polymerization to form the repeat units.
  • RAFT polymerization synthesis is carried out to provide a copolymer having alternating styrene and maleic acid monomers in the backbone (PSMA).
  • SCHEME 1 shows the synthesis of a copolymer of styrene and maleic acid (PSMA) obtained by reacting styrene (PS) monomers with maleic acid (MA) monomers.
  • SCHEME 1 shows how PSMA may be further derivatized with side chain moieties to produce additional embodiments of polymer surfactants. Additional embodiments of polymer surfactants can be synthesized by subjecting PSMA to further functionalization with, for example, an amino-containing side chain moiety. Shown in SCHEME 1 is a particular embodiment where PSMA is derivatized with the side chain moiety amino-pyrene. Functionalization of PSMA in this manner involves a condensation reaction between the electrophilic maleic acid anhydride groups present on PSMA and the nucleophilic amine groups present on amino-pyrene.
  • SCHEME 1 exemplifies a particular embodiment of how the synthetic polymers herein contemplated may be derivatized to contain a side chain moiety.
  • side chain substitution may take place anywhere along the polymer backbone such that the side chain moiety is attached to a repeat unit located anywhere in the polymer chain, including for example at the end of a polymer chain. In embodiments where attachment of a side chain moiety occurs at this position, in the terminal position of the polymer chain, this constitutes an end-cap to the polymer chain.
  • Side chain moieties are optional, and one skilled in the art will recognize that the amount of side chain substitution required to disperse SWNT in a media may depend on the nature of the polymer backbone and the nature of the media.
  • the polymer backbone is PSMA and the media is water
  • the benzene-like structures (arising from the styrene monomers used in the polymer backbone) are sufficiently compatible with SWNTs that underivatized PSMA polymer alone is capable of dispersing SWNTs into an aqueous solution even though no SWNT-compatible side chains moieties are incorporated into the polymer structure.
  • Synthetic polymers are contemplated containing side chain moieties that may be derived from organic dyes.
  • Suitable organic dyes include structures such as porphyrins, porphyrin derivatives, metal porphyrin complexes, metal porphyrin derivative complexes, rhodamine dyes, fluorescein dyes, any other type of organic dyes, and combinations thereof.
  • Synthetic polymers are also contemplated containing side chain moieties that may be derived from aromatic hydrocarbons.
  • Suitable aromatic hydrocarbons include aromatic hydrocarbons, substituted aromatic hydrocarbons, and derivatives thereof selected from the group consisting of benzene, naphthalene, anthracene, tetracene, acenaphthylene, bezoanthracene, benzopyrene, benzofluoranthene, benzofluoranthene, benzophenanthrene, fluoranthene, fluorine, phenanthrene, acenapthene, pyrene, perylene any other polycyclic aromatic hydrocarbons (PAHs), and mixtures thereof.
  • PAHs polycyclic aromatic hydrocarbons
  • pyrene is a preferred side chain moiety.
  • the fused aromatic ring structure of pyrene is graphene-like and resembles the molecular structure of SWNTs, which indicates that pyrene may have chemical compatibility with SWNTs and may have a strong tendency to adsorb onto SWNTs.
  • pyrene may be used as the side chain moiety in the polymer structure, and that the resulting polymer formed may have the capacity to interact with and adhere to SWNTs.
  • maleic acid is used as one of the monomers constituting the polymer backbone, residual acid functionalities present on such a polymer may give the polymer water-solubility.
  • polymers synthesized and derivatized in the manner shown in SCHEME 1 to have pyrene side chain moieties may have sufficient SWNT compatibility and compatibility with water to mimic the surfactant behavior of ssDNA, in order to disperse SWNTs into aqueous solutions.
  • a spacer group may also be present and may be attached in-between a side chain moiety and a repeat unit of the polymer backbone.
  • Such spacer groups may have a short or an extended structure.
  • polymer compositions having either short spacer groups or no spacer groups may have side chain moieties that are too sterically hindered to exert any properties independent of the polymer backbone, and in these instances the net physical and chemical properties of the polymer may be dominated by the nature of the backbone structure.
  • the choice over polymer backbone is considered with the choice over both the side chain moiety and the spacer group, one skilled in the art will recognize how the properties of a given polymer system may be tuned to exhibit specifically desired properties.
  • spacer groups include but are not limited to the following structures and derivatives thereof: -(CH 2 ),-,-, where n is from 1-10; -[A(CH 2 ) m B] n -, where A and B are -N(H)- or -N(R)- (where R is an alkyl group) or -S- or -C(O)- or -C(O)O- or - CH(OH)- or -CH(R)- (where R is an alkyl group) and m is from 1-6 and n is from 1-16; and - [C 6 H 4 J n -, where n is from 1-2.
  • the longer or more extended the spacer group the more likely it will be that the side chain moiety that is attached to it will physically extend away from the polymer backbone.
  • SWNT/MCNP assemblies may be prepared wherein the MCNPs may be, for example, metal nanoparticles, semiconductor nanoparticles, metal-oxide nanoparticles, or any mixture thereof.
  • MCNPs are metal nanoparticles
  • these metal nanoparticles may exhibit a variety of quantum mechanical effects, and may have a variety of properties including but not limited to tunable electronic, magnetic, optical and catalytic properties.
  • the metal nanoparticles may be prepared using solution-based and colloidal-based synthesis techniques to reduce salts of the metal cations using a suitable metal ion reducing agent, according to any of the methods that are known to one of ordinary skill in the art, to produce zero-valence state metal nanoparticles.
  • Exemplary metal nanoparticles that may be made into SWNT/MCNP assemblies using the methods described herein include Fe, Ru, Rh, Pt, Pd, Cu, Ag, and Au metal nanoparticles.
  • Exemplary metal nanoparticles useful as catalysts for various reactions include but are not limited to Pt, Pd, Au, Cu, Ni, Ru, Rh, Fe metal nanoparticles.
  • MCNPs are semiconductor nanoparticles
  • these semiconductor nanoparticles may exhibit a variety of quantum mechanical effects, and may have a variety of properties including but not limited to tunable electronic, optical and catalytic properties.
  • the semiconductor nanoparticles may be prepared using solution-based and colloidal-based synthesis techniques to react salts of the group lib metal cations with any suitable group Via reagent containing at least one group Via element selected from the group S, Se, Te, or mixtures thereof, according to any of the methods that are known to one of ordinary skill in the art, to produce II- VI semiconductor nanoparticles.
  • Exemplary semiconductor nanoparticles that may be made into SWNT/MCNP assemblies using the methods described herein include ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, and HgTe semiconductor nanoparticles.
  • MCNPs are metal-oxide nanoparticles
  • these metal-oxide nanoparticles may exhibit a variety of quantum mechanical effects, and may have a variety of properties including but not limited to tunable electronic, optical and catalytic properties.
  • the metal -oxide nanoparticles may be prepared using solution-based and colloidal -based synthesis teclmiques to react non-oxide salts of the metal cations with any suitable metal-ion oxidizing agent, according to any of the methods that are known to one of ordinary skill in the art, to produce metal-oxide nanoparticles.
  • the metal-ion oxidizing agent should be an oxygen-based oxidizing agent.
  • Exemplary semiconductor nanoparticles that may be made into SWNT/MCNP assemblies using the methods described herein include TiO 2 , ZrO 2 , MnO 2 , FeO, Fe 2 O 3 , CuO, ZnO 2 , ZnO, SnO, SnO 2 , PbO, Pb 3 O 4 , and PbO 2 metal-oxide nanoparticles.
  • Method for preparing SWNT/MCNP assemblies in a medium comprises dispersing SWNTs in a medium in the presence of at least one polymer surfactant; mixing metal ions with the SWNTs dispersed in the medium; incubating the mixture; and reacting the metal ions with an effective amount of a reagent to form a SWMT/MCNP assembly.
  • SCHEME 2 for forming SWNT/Metal nanoparticles in an aqueous medium.
  • the SWNTs are first dispersed with a polymer surfactant in an aqueous medium such as water.
  • the SWNTs become individually dispersed by forming SWNT-polymer surfactant complexes.
  • suitable metal ions are mixed with the SWNT-polymer surfactant complexes in the aqueous medium and this mixture is incubated for a sufficient time before the metal ions are chemically reduced with a metal-ion reducing agent to form metal nanoparticles coordinated and assembled along the outside of the SWNT.
  • Suitable SWNTs are any of the variety of SWNTs herein described.
  • Suitable polymer surfactants are selected from the group consisting of DNA, proteins, peptides, and synthetic polymers, where the synthetic polymers are any of the synthetic polymers herein described.
  • the step of dispersing SWNTs in the medium with at least one polymer surfactant may take some time to achieve a suitable dispersion of the SWNT in the medium.
  • the length of time it takes to disperse the SWNTs with the polymer surfactant will depend on several factors including but not limited to the nature of the polymer, the polymer backbone, the side chain moieties (if any are present), the nature of the media, the final concentration of SWNTs desired, and whether heat, stirring, sonication or other mechanical assistance is utilized to disperse the SWNTs.
  • One skilled in the art will understand how the length of time it takes to disperse SWNTs may be specific to the type of polymer surfactant used, how this will be affected by the aforementioned factors, and will further understand how reaction conditions may be modified without undue experimentation to suitably disperse the SWNTs.
  • SWNTs can be dispersed in aqueous medium in about 1 hour when mechanical assistance from sonication is utilized.
  • a polymer surfactant involves providing one or more naturally occurring polymers (such as DNA, proteins, peptides), or one or more synthetic or polymers, or a mixture of any of the synthetic polymers herein described.
  • a preferred embodiment of a synthetic polymer is an alternating copolymer of styrene and maleic acid (PSMA).
  • PSMA alternating copolymer of styrene and maleic acid
  • Suitable metal ions are selected from the group consisting of Ti, Zr, Mn, Fe,
  • the metal ions are provided in the form of a salt having solubility in the desired medium, as for example, in one embodiment where the medium is water and suitable metal salts are water- soluble and are dissolved in water to provide an aqueous solution of metal ions.
  • the metal ions can be provided at any suitable concentration appropriate for making the desired assemblies and for use with the methods described herein. Suitable concentrations may be determined by the concentration of SWNTs and the concentration of polymer surfactant used.
  • a suitable concentration of metal ions is where the molar ratio of metal ions to the carboxylic acid groups present on PSMA in the reaction mixture is generally less than 1: 100. Using this molar ratio of metal ions to the carboxylic acid groups ensures the majority of the metal ions are bound with SWNT-PSMA complexes after being incubated and that there is not a lot of excess and/or free metal ions remaining that would undergo uncontrolled growth to form metal nanoparticles unassociated with any SWNT- PSMA complexes.
  • Metal ions are mixed with the SWNT-polymer surfactant complexes and incubated for a period of time before a reagent is added. This incubation period allows the metal ions to associate with the SWNT-polymer surfactant complexes to help template or control the growth of the MCNT once the reagent is added. Controlling the growth of the MCNP facilitates formation of SWNT/MCNP assemblies.
  • FIGURES 4(A)-(D) Atomic force microscopy (AFM) is used to analyze samples of various reaction mixtures.
  • FIGURE 4(A) is a sample of SWNTs dispersed in an aqueous medium using PSMA as the polymer surfactant and the image shows the SWNT-PSMA complexes that form.
  • PSMA polymer surfactant
  • FIGURE 4(A) is a sample of SWNTs dispersed in an aqueous medium using PSMA as the polymer surfactant and the image shows the SWNT-PSMA complexes that form.
  • various metal ion salts are mixed in with these SWNT-PSMA complexes and given a period of time (approximately 12 hours) to incubate with the SWNT-PSMA complexes, adding a reducing agent to this mixture results in controlled production of metal nanoparticles.
  • Metal nanoparticles grow as discrete nodular-like structures interspaced along the length of individual SWNT-PSMA complexes and SWNT/Metal nanoparticle assemblies are produced.
  • FIGURE 4(B) images a SWNT/Pd nanoparticle assembly
  • FIGURE 4(C) images a SWNT/Pt nanoparticle assembly. Both these assemblies are produced using corresponding metal ion salts, PSMA as the polymeric surfactant to disperse SWNTs, and an incubation period before introducing a reducing agent and both images show the distinctive formation of nodular-like metal nanoparticles along the length of individual SWNT-PSMA complexes.
  • PSMA metal ion salts
  • FIGURE 4(D) is sampled from an attempt to produce SWNT/Pt nanoparticle assemblies using identical reaction conditions as used to produce the assemblies shown in FIGURE 4(B) but without allowing any incubation time to pass before introducing the reducing agent.
  • the image provided in FIGURE 4(D) shows that the distinctive formation of nodular-like metal nanoparticles along the length of individual SWNT-PSMA complexes does not occur. Rather, a mixture of SWNT-PSMA complexes and various-sized clusters of Pd metal are obtained.
  • suitable incubation times may depend upon several factors including but not limited to the nature of the metal ion, the nature, concentration and solubility of the metal ion salt used, the nature of the polymer, the polymer backbone, the side chain moieties (if any are present), the nature of the media, the final concentration of SWNT/MCNP assemblies desired, and whether heat, stirring, sonication or other mechanical assistance is utilized during incubation.
  • One skilled in the art will understand how a sufficient time for incubation may be specific to both the types of metal ions and types of polymer surfactants used, how results will be affected by these factors and will understand how periods of time for incubation may be modified without undue experimentation to achieve suitable results.
  • Embodiments are contemplated of methods for dispersing SWNTs using a polymer surfactant to fo ⁇ n SWNT-polymer surfactant complexes that may further bind metal ions and act as a template to control the growth of metal nanoparticles, in order to produce metal nanoparticles bound to a SWNT-polymer surfactant complex.
  • a polymer surfactant to fo ⁇ n SWNT-polymer surfactant complexes that may further bind metal ions and act as a template to control the growth of metal nanoparticles, in order to produce metal nanoparticles bound to a SWNT-polymer surfactant complex.
  • PSMA when PSMA is used as the polymer surfactant, carbonyl groups present in PSMA can act as capping groups for metal nanoparticles formed in order to prevent the metal nanoparticles from aggregating with each other.
  • SWMTYMCNP assembly involves adding enough reagent as may be required in order to have a reaction between the metal ions present in the medium and the added reagent to produce the requisite MCNPs needed to form SWNT/MCNP assemblies.
  • the reagent should be provided in a form that is soluble or miscible with the desired medium, as for example, in one embodiment where the medium is water and suitable reagents are water-soluble and are dissolved in water to provide an aqueous solution of the reagent.
  • the reagent is reacted with metal ions in the medium long enough to react with (i.e.: to reduce, to form a product or precipitate with, or to oxidize) metals ions that are bound to the SWNT-polymer surfactant complexes, in order to produce the desired SWNT/MCNP assemblies. How long this is depends on several factors including but not limited to the type of MCNPs that are produced, the concentration of metal-ions present, the final concentration of SWNT/MCNP assemblies desired, and whether heat, stirring, sonication or other thermal or mechanical energy is utilized to aid in reacting the reagent with the metal ions.
  • Reagents can be a metal-ion reducing agent, a group Via reagent, or a metal- ion oxidizing agent.
  • Substances that are metal-ion reducing agents have the ability to reduce the metal ions present and are said to be reductive and are known as reducing agents, reductants, or reducers. Put another way, the reductant transfers electrons to the metal ions and is thus oxidized itself, and because it "donates" electrons it is called an electron donor.
  • Substances that are group Via reagents have the ability to form a product or precipitate with any group lib metal ions that are present.
  • Substances that are metal-ion oxidizing agents have the ability to oxidize the metal ions present and are said to be oxidative and are known as oxidizing agents, oxidants or oxidizers. Put another way, the oxidant removes electrons from the metal ions and is thus reduced itself, and because it "accepts" electrons it is called an electron acceptor.
  • a material that is a metal-ion reducing agent should primarily react with metal ions present to reduce these cationically charged metal ions to a valence state of zero. Although side reactions with other reagents in the medium, such as SWNTs or polymer surfactants, or reactions with the medium itself may occur, these are kept to a minimum and do not generate substantial amounts of any byproduct. Thus, SWNT/Metal nanoparticle assemblies produced can be used as-is or they can be isolated from the mixtures using standard purification and isolation techniques known in the chemical arts.
  • Common reducing agents include alkali metal hydrides; lithium aluminum hydride (LiAlH 4 ), hydrogen gas, sodium borohydride (NaBH 4 ); sulfite compounds; hydrazine; diisobutylaluminum hydride (DIBAH); and oxalic acid (C 2 H 2 O 4 ).
  • a preferred metal-ion reducing agent is NaBH 4 , which is a suitable metal-ion reducing agent for most metals.
  • NaBH 4 is a suitable metal-ion reducing agent for most metals.
  • those skilled in the art will recognize that other reducing agents may be used for other particular reactions.
  • a group Via reagent should contain a group Via element selected from the group S, Se, Te, or mixtures and should be suitable for reacting with salts of the group lib metal cations to produce II-VI semiconductor nanoparticles.
  • the group Via reagent may also be an oxidizing agent, the group Via reagent should primarily react with any cationically charged group lib metal ions present to form a product or precipitate with any group lib metal ions that are present.
  • the group Via reagent forms a product with or precipitates with any group lib metal ions because a preferential exchange occurs of the group Via element for the negatively charged counter ions present in the group lib metal-ion salt, in order to produce a II-VI semiconductor material.
  • side reactions with other reagents in the medium such as SWNTs or polymer surfactants, or reactions with the medium itself may occur, these are kept to a minimum and do not generate substantial amounts of any byproduct.
  • SWNT/Semiconductor nanoparticle assemblies produced can be used as-is or they can be isolated from the mixtures using standard purification and isolation techniques known in the chemical arts.
  • Common group Via reagents include ammonium sulfide, hydrogen sulfide, the alkali-hydrogen sulfide salts, and alkali-sulfide salts; hydrogen selenide, the alkali-hydrogen selenide salts, and alkali-selenide salts; hydrogen teluride, the alkali-hydrogen teluride salts, and alkali-teluride salts.
  • a preferred group Via reagent for making ZnS, CdS, or HgS semiconductor nanoparticles is ammonium sulfide. However, those skilled in the art will recognize that other group Via reagent may be used for other particular reactions.
  • a material that is a metal-ion oxidizing agent should primarily react with metal ions present to either oxidize the cationic metal ions or preferentially replace the negatively charged counter ions present in the metal-ion salt with an oxide species to produce a metal-oxide.
  • side reactions with other reagents in the medium such as SWNTs or polymer surfactants, or reactions with the medium itself may occur, these are kept to a minimum and do not generate substantial amounts of any byproduct.
  • SWNT/Metal- oxide nanoparticle assemblies produced can be used as-is or they can be isolated from the mixtures using standard purification and isolation techniques known in the chemical arts.
  • the metal-ion oxidizing agent should be an oxygen-based oxidizing agent.
  • Common oxidizing agents include hypochlorite and other hypohalite compounds such as Bleach; chlorite, chlorate, perchlorate, and other analogous halogen compounds; permanganate salts; hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide; chromate/dichromate compounds; peroxide compounds such as H 2 O 2 ; persulfuric acid; ozone, oxygen gas, osmium tetroxide (OsO 4 ); nitric acid; and nitrous oxide (N 2 O).
  • hypochlorite and other hypohalite compounds such as Bleach
  • chlorite, chlorate, perchlorate, and other analogous halogen compounds such as permanganate salts
  • hexavalent chromium compounds such as chromic and dichromic acids and chromium trioxide
  • Methods are contemplated herein for producing SWNT/MCNP assemblies in aqueous solutions. Methods are also contemplated herein for producing SWNT/MCNP assemblies in other medium.
  • this medium is water-based, or it is an organic solvent, or mixtures thereof.
  • the medium may be a solid or semi-solid matrix (such as a gel), or it may be a mixture of a matrix with an aqueous solution or organic solvent.
  • the matrix may be for example, but is not limited to a polymer matrix or a sol-gel matrix.
  • Useful polymer matrices and sol-gel matrices are any of the polymer matrices and sol-gel matrices previously known and one skilled in the art will understand how these matrices can be produced. [0060] Since the methods described herein are suitable for producing SWNT/MCNP assemblies in medium that include water, water-based solutions, organic solvents, polymer matrices, sol-gel matrices, and mixtures thereof; polymers that are useful for carrying out these method in the different medium may have side chain moieties that interact with the SWNTs, to aid in dispersion of the SWNTs, while at the same time having a backbone that is soluble or compatible with the chosen medium that the SWNT/MCNP assemblies are to be produced in.
  • Monomers that may be useful for polymer backbones when the medium used is water include any of the various water-soluble structures herein described, and this provides for polymer surfactants having water-solubility.
  • the medium is a non-aqueous based system such as an organic solvent, or a polymer matrix, or a sol-gel matrix
  • one skilled in the art will understand how to choose specific monomers to produce a polymer backbone that has suitable chemical compatibility with and solubility within the non-aqueous based system, or polymer matrix, or sol-gel matrix used.
  • SWNT/MCNP assemblies described herein are useful for producing SWNT/MCNP assemblies that then may be used in a variety of functions and applications.
  • these SWNT/MCNP assemblies and methods may be used to purify various types of SWNTs from raw products.
  • these SWNT/MCNP assemblies and methods may also be used or may play a role in the preparation of SWNT/MCNP-based electrochemical electrodes or SWNT/MCNP-based films or membranes, in making SWNT/MCNP assemblies that are then further used in solar energy conversion (in the form of photovoltaic cells or photoelectrochemical solar cells) or in solar fuel production or in solar hydrogen production.
  • SWNT/MCNP assemblies and methods may also be used or may play a role in making SWNT/MCNP assemblies that are then used to prepare optoelectronic devices including light emitting diodes, light-emitting transistors, photo-detecting diodes, and transistors.
  • PSMA is synthesized as shown in SCHEME 1. 2.08 g (0.02 mol) of styrene
  • PS and MA maleic anhydride
  • PSMA alternating polystyrene-maleic acid copolymer
  • the molecular weight of the PSMA is measured using standard Gel Permeation Chromatography (GPC) techniques to be 8,400 daltons with a molecular weight distribution of (M w /M n ⁇ 1.2). This molecular weight distribution is much narrower than that obtained when simple radical copolymerization procedures are used.
  • the dispersability of SWNTs in an aqueous medium using PSMA as a polymer surfactant is compared to a control, which is the dispersability of SWNTs in an aqueous medium using (single strand) ssDNA d(GT) 2 o.
  • the dispersability of the SWNTs as a function of the polymer surfactant is expressed as the mass ratio of SWNT:polymer surfactant that is obtained, where the higher the ratio is the better the polymer surfactant is capable of dispersing SWNTs.
  • the dispersability of SWNTs in an aqueous medium using ssDNA d(GT) 20 was previously determined to be less than 0.4: 1.
  • SWNT/MCNP assemblies are synthesized where the MCNP produced are metal nanoparticles.
  • SWNTs are first individually dispersed in an aqueous medium in the presence of polymer surfactant to make SWNT-polymer surfactant complexes.
  • Metal ions are then mixed with the SWNT-polymer surfactant complexes and this mixture is incubated for a period of time before introducing a metal-ion reducing agent to chemically reduce the metal ions to produce metal nanoparticles. Once the metal-ion reducing agent is added, metal nanoparticles are formed as nodules associated with and located along the SWNT-polymer surfactant complexes.
  • the supernatant is then dialyzed using cellulose ester membrane with 1 million Dalton molecular weight cut-off (Spectrum Labs Inc., Collinso Dominguez, CA) to eliminate the free PSMA.
  • 10 ⁇ l of a 0.5 niM Pt(terpy)Cl 2 aqueous solution is added to 100 ⁇ l of the SWNT-PSMA mixture and this is incubated at room temperature for more than 12 h. After this time, 3 ⁇ l of a 6 mg/mL NaBH 4 aqueous solution is added and SWNT/MCNP assemblies are obtained.
  • FIGURES 4(B) and 4(C) are AFM images of SWNT assemblies containing Pd and Pt metal nanoparticles.
  • FIGURES 5(A)-(C) are AFM images of SWNT assemblies containing Au, Cu and Fe metal nanoparticles. The suspensions of the SWNT/Metal nanoparticle assemblies are stable in the aqueous medium at room temperature for weeks without precipitation or aggregation.
  • FIGURE 4 shows images of spin-cast samples on freshly cleaved mica obtained with MFP 3D AFM (Asylum Research, Santa Barbara, CA) in ambient. Comparing FIGURES 4(B) and 4(C) with the SWNT-PSMA complexes in FIGURE 4(A), it is clear that metal nanoparticles of about 3-6 nm in diameter form as nodules along the SWNT-PSMA complexes after chemical reduction. The spacing between these particles is about 25-100 nm. TEM micrographs similarly confirm these results.
  • FIGURE 6(A) is a TEM image of the same SWNTYPd nanoparticle assembly shown in FIGURE 4(B), while FIGURE 6(B) is a TEM image of the same SWNTVPt nanoparticle assembly shown in FIGURE 4(C)
  • the AFM image provided in FIGURE 4(D) shows that large clusters of particles are fo ⁇ ned when attempts to produce SWNT/Metal nanoparticle assemblies in this way are made, that is when no time is provided for the metal ions to incubate with the SWNT-PMSA complexes.
  • the result of these control experiments indicates that providing a time for incubation, aids in controlling the growth and association of metal nanoparticles so that SWNT/Metal nanoparticle assemblies may be prepared.

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Abstract

L'invention propose des ensembles de nanotubes monoparoi/nanoparticule contenant un métal (SWNT/MCNP) et des procédés de préparation des ensembles SWNT/MCNP dans divers milieux. La MCNP peut être une nanoparticule de métal, une nanoparticule de semi-conducteur ou une nanoparticule d'oxyde de métal. Les procédés proposés ici comportent l'utilisation d'au moins un agent tensioactif polymère pour disperser des SWNT dans un milieu tel que de l'eau, des solvants organiques, des matrices polymères et des matrices sol-gel. Les SWNT dispersées sont mélangées à des ions de métal et incubées, puis lesdites SWNT sont mises à réagir avec divers réactifs pour produire des ensembles SWNT/MCNP. Les agents tensioactifs polymères appropriés sont des matières présentes à l'état naturel telles que l'ADN, les protéines, les peptides et les polymères synthétiques. Un agent tensioactif polymère synthétique préféré est un copolymère alterné de styrène et d'acide maléique (PSMA).
PCT/US2007/083414 2006-11-02 2007-11-02 Synthèse de solution d'ensembles conjugués de nanotubes en carbone/nanoparticule contenant un métal Ceased WO2008127396A2 (fr)

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