WO2004043857A2 - Manipulation de nanotubes de carbone derivatises - Google Patents

Manipulation de nanotubes de carbone derivatises Download PDF

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Publication number
WO2004043857A2
WO2004043857A2 PCT/SE2003/001751 SE0301751W WO2004043857A2 WO 2004043857 A2 WO2004043857 A2 WO 2004043857A2 SE 0301751 W SE0301751 W SE 0301751W WO 2004043857 A2 WO2004043857 A2 WO 2004043857A2
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nanotube
nanotubes
molecule
type
bond
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PCT/SE2003/001751
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English (en)
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WO2004043857A3 (fr
Inventor
Kim Bolton
Arne ROSÉN
Simon Gustavsson
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Kim Bolton
Rosen Arne
Simon Gustavsson
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Application filed by Kim Bolton, Rosen Arne, Simon Gustavsson filed Critical Kim Bolton
Priority to AU2003284814A priority Critical patent/AU2003284814A1/en
Publication of WO2004043857A2 publication Critical patent/WO2004043857A2/fr
Publication of WO2004043857A3 publication Critical patent/WO2004043857A3/fr

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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
    • 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
    • C01B32/172—Sorting
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/44—Carbon
    • C09C1/48—Carbon black
    • C09C1/56—Treatment of carbon black ; Purification
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/13—Nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

  • the present invention in general relates to carbon nanotubes and in particular to their selective manipulation and separation thereor by derivatization techniques, comprising for example ether linkages to polymers.
  • nanotubes Since their discovery in the early 1990's, nanotubes have been studied, especially for their special mechanical, thermal and electrical properties. They have a high strength and toughness while simultaneously being light; they are at least 100 times stronger than steel while having just 1/6 of its weight.
  • SWNTs Single walled nanotubes
  • Purification of nanotubes is achieved with the aid of filtration and centrifugation, but also chromatographic methods can be used to separate nanotubes from impurities that typically include nanoparticles, amorphous carbon, and tracers of catalysts, etc.
  • the twist of the carbon backbone of nanotubes i.e., the chirality, influences the nanotube's electrical conductivity.
  • the nanotube is a semiconductor while for the remaining chiralities it is a metal with very good conductivity.
  • nanotubes with this good electrical, conductivity, including that nanotubes serve as an electronical conductor or that they can be mixed in a composite material to increase the electrical conductivity of the material.
  • nanotubes serve as an electronical conductor or that they can be mixed in a composite material to increase the electrical conductivity of the material.
  • semiconducting nanotubes most of which are common with conceivable areas where semiconducting silicon material are used.
  • AFM Atomic force microscope
  • EP 1205 436 is presented a method for producing single walled carbon nanotubes with substantially the same structure, by depositing different layers of fullerenes and a catalyst on a substrate through a mask. When the resulting structure is thermolyzed in vacuum in the presence of a magnetic field, the produced layers are transformed into single walled carbon nanotubes with substantially the same structure. This method concerns the production of nanotubes by growing a nanotube crystal from the deposited fullerenes.
  • the method cannot be used to obtain sufficiently large amounts of nanotubes that have a particular or desired chirality from a mixture of nanotubes that have a variety of chiralities.
  • Basiuk wrote, concerning the reactivity of carboxyl groups on the ends of carbon nanotubes with 'armchair' and 'zigzag' chirality, (Basiuk, V.A., Nano Letters, 2(8), (2002), 835-839), that an increased solubility of nanotubes and an improved affinity of nanotubes to metal surfaces can be useful for the separation of different types of nanotubes, providing that there is a method to selectively derivatize them.
  • Basiuk claims that, if a long alcohol chain is used in the treatment the resulting ester-derivatized carbon nanotube of armchair type would dissolve in organic solvents substantially better than the non-derivatized nanotube of zigzag type, which in turn, is proposed to be able to open up an accessible route for separation. Every possible separation of nanotubes of armchair type from nanotubes of zigzag type, according to the method of Basiuk, requires therefore that there is a way to selectively derivatize nanotubes of armchair type.
  • the method of Basiuk moreover requires that the selectively derivatized nanotube has an increased solubility in organic solvents compared to the non-derivatized nanotube, where the selectively derivatized nanotube is of armchair type and the non-derivatized nanotube is of zigzag type.
  • An object of the present invention is to provide a method for selectively manipulating nanotubes based on their chirality.
  • Another object of the present invention is to provide a method for selectively manipulating carbon nanotubes.
  • An additional object of the present invention is to provide a method for selectively separating carbon nanotubes based on their chirality.
  • the above objects are achieved with a method for manipulating more than one type of nanotube, where a first type has a first chirality and a second type has a second chirality, where at least two types of nanotubes are bound to a least one molecule, where the bonding energy between a nanotube and a molecule depends at least partially on the chirality of the nanotube, where the breaking of a chemical bond between a nanotube and a molecule in one step only occurs between one type of nanotube and the corresponding molecule, so that at least the first type of nanotube can be manipulated.
  • a first advantage with the method according to the present invention is that it allows specific manipulation of nanotubes based on their chirality.
  • a second advantage is that the invention makes use of binding a molecule to the end of the nanotube, which gives the produced nanotube-molecule complex properties different from the nanotube itself, which, for example, gives an increased solubility in a solvent for the produced nanotube-molecule complex compared with the solubility of the nanotube with the same chirality in the same solvent.
  • the method for manipulating nanotubes according to claim 5, that the molecule to which the nanotube is bound via a functional group has an extended structure, comprising repetitive units, in the form of a polymer, has the advantage that it enhances the solubility of the nanotube-molecule complex in a solvent, compared with the functionalized nanotube itself with the same chirality, which provides simpler dosing and manipulation of nanotubes in general.
  • the realization of the above objectives is based on the fact that the energy of a chemical bond between two molecules in general depends on the properties of the associated molecules. In particular it is based on the fact that one component of this bond energy depends on the structure of at least one of the bound molecules.
  • Fig. 1 shows a diagram of the energies in kJ mol "1 of the chemical bond (— ) for nanotube-O— CH 3 , for a range nanotubes with (n,n) armchair and (k,0) zigzag structures as a function of the nanotube's diameter.
  • the bond energies for the nanotubes with armchair and zigzag structures are presented by squares and triangles, respectively.
  • the lines that join the data in both armchair and zigzag series are included merely to aid the eye in identifying different bond strength levels and lack physical/chemical significance.
  • Fig. 2a and 2b schematically present a method for separating nanotubes based on their chirality.
  • the present invention concerns a method for selectively manipulating nanotubes based on the nanotube's chirality.
  • Fig. 1 presents a diagram of the bond energies for the chemical bond between a nanotube and a methyl group, that is the nanotube— CH 3 bond, where the bond from the nanotube is from an oxygen atom, O, and the bond energy is presented as a function of the nanotube's diameter in Angstrom, A.
  • the diagram clearly shows that the bond energy between a methyl group and a nanotube of armchair type is approximately 40 kJ mol "1 larger than the bond energy between a methyl group and a nanotube of zigzag type, for nanotubes with the same or similar diameters.
  • This significant energy difference between the homologous series of nanotubes of armchair type and the homologous series of nanotubes of zigzag type forms the basis for the selective manipulation of nanotubes in the present invention.
  • the modeling study thus shows that the bond energy between the nanotube and the hydrocarbon specie has at least one component that depends on the nanotube's structure and that the corresponding bond energy is stronger for the nanotube of armchair type than the nanotube of zigzag type. Furthermore, the study shows that the nanotube's structure, in terms of its chirality, affects the bond's strength.
  • the differences in the bond energies between the complex that include nanotubes of armchair type and nanotubes of zigzag type which, for example, are shown in fig. 1, are neither limited to complexes in which nanotubes and hydrocarbon species are linked with -0-, that is an oxygen atom, nor to complexes in which the nanotube is linked to a CH 3 group, that is a methyl group.
  • the invention is applicable to chemical species that are linked with a chemical bond, for example a nanotube linked to a hydrocarbon specie, in a so-called complex.
  • a chemical bond for example a nanotube linked to a hydrocarbon specie
  • This difference in rates with which the complex between the hydrocarbon specie and nanotubes with different types of chiralities breaks, is used in the present invention and opens up many applications including selective manipulation of nanotubes, again with respect to their chirality, different types of control over and separation of nanotubes with different chiralities.
  • Fig. 2a and 2b shows one of many methods for selective manipulation of nanotubes with respect to their chirality, which is based on the difference in bond energies shown above.
  • step 202 Initially purified nanotubes in solution (step 202) is provided. Thereafter the nanotube is functionalized and this occurs preferably on the ends of the nanotube by supplying heat to the nanotube so that the C-O-C groups on the end of the nanotube breaks and free CO groups are obtained on the ends (step 204). These functional groups can subsequently be derivatized by letting a, against the functionalized nanotube reactive group of an alkyl chain molecule react with said functionalized nanotube so that the nanotube-molecule complex is formed (step 206), where the bond from the nanotube is from an oxygen atom, O.
  • the solution is heated to a temperature T (step 210), until its temperature T lies between T P and Ti (step 212). At this temperature the molecules that are bonded to the nanotube at places other than the nanotube end are released and the remaining molecules are only bonded to the ends of the nanotube. The released molecules are filtered off (step 214) and the solution is subsequently heated further to the temperature T (step 216).
  • T is equal to or higher than a first threshold temperature, Ti, but less than a second threshold temperature, T
  • step 222 it is determined whether neither the released nanotubes of type i, nor nanotubes of the type i+1, which still are present in nanotube-molecule complexes, are wanted (step 222). If neither of these nanotubes are wanted then the summation index is increased by one unit (step 224), after which the solution is heated again (step 216). If any of the free nanotubes of type i or i+1 is wanted, the already obtained free nanotubes (of type i) and the free corresponding molecules are separated from the remaining nanotube-molecule complex (step 226). The remaining nanotube-molecule complexes are collected (step 228) and the summation index is increased by one unit (step 224) and the temperature is increased (216).
  • step 230 The separated free nanotubes and the corresponding molecules from step 226 are collected (step 230) and the free molecules are subsequently filtered off (step 232) to obtain the free desired nanotubes of type i (step 234). If it is seen at step 220 that the solution does not contain any more desired nanotubes in complex, the free molecules are already filtered off (step 232), after which the desired nanotubes remain and is obtained (step 234).
  • the above method is preferably applied to solutions that initially contain more than one type of nanotube. It is also possible to stop it at an arbitrary step independent of whether the solution contains more desired nanotubes or not.
  • the invention can be varied in a number of different ways, for example:
  • the molecule to bond to the nanotubes in order to create soluble nanotube-molecule complexes can comprise many different species and groups.
  • the separation method described above thus includes the breaking of a chemical bond between at least one end of a nanotube and a molecule or a group that can be chosen from a wide variety of chemical species.
  • the separation step (step 232) that in the above method is achieved by filtration, can in a variation of the method according to the present invention be performed in many different ways.
  • One of them include electrophoretic methods to physically separate the molecules, where these electrophoretic methods include different types of electrophoresis.
  • electrophoretic variations it is preferable to use molecules or atoms, to be bond to the nanotubes, which molecules have an electric charge or that can be electrically charged in an electric field.
  • An example of such a group is a phosphate group.
  • Another way to perform the separation according to the invention is to use methods that include chromatographic separation methods.
  • An additional way to perform the separation described above is to allow the separation process to include centrifugation techniques.
  • the molecule in the molecule complex can comprise other hydrocarbon species, such as hydroxycarboxyllic acids.
  • the connecting link, X can contain other link groups such as -NH-, -S-, -Si-, -CO-, -OCO- or -COO-.
  • the nanotube is preferably functionalized at the ends with -COOH groups. These -COOH groups can subsequently be derivatized by bonding with an alcohol molecule, so that the ester bond, i.e., -COO- bond, is obtained between the nanotube and the rest of the alcohol molecule.
  • This invention also includes manipulation of nanotube-molecule complexes where said molecule has an extension that is similar to a chain, in at least one direction.
  • the molecule can even contain a number of repetitive units and form an oligomer or a polymer.
  • the formed nanotube-molecule complexes can even include a molecule that is an organic specie, an inorganic specie or a metalloorganic specie.
  • the molecule can be chosen from a vast number of different types of species.
  • the molecule is preferably chosen in a way so that the formed nanotube-molecule complex has properties that the nanotube itself does not have, where the nanotube may or may not be functionalized.
  • the preparation of complexes between nanotubes and chemical species, possibly via a link or bonding group, can be performed in many different ways.
  • the nanotube ends can, for example, be functionalized.
  • the chemical species that will be bonded to the nanotube can, as an alternative, also be functionalized.
  • the important aspect with functionalisation of the nanotube and/or the chemical species for bonding, is to facilitate forming of a chemical bond between the nanotube and the molecule, possibly via a link.
  • a variation of the method for selective separation of nanotubes with respect to their chirality, according to the present invention a separation column which contains polymer packing is used. A solution that contains the functionalized nanotubes with different chiralities is added to the column. The functionalized nanotubes thereby bind to the polymer packing. To selectively release and manipulate the added nanotubes, different amounts of energy in some form can be supplied.
  • chemical methods can be used for selectively cleaving of nanotubes, which method includes the use of molecules that have specific reactivities.
  • An example of such a method is to a column that contains attached nanotubes of at least two types of chiralities, add a first reactive solution, by which preferably substantially only the bond between the attached polymers and the nanotubes of zig-zag type is cleaved, with the result that only these nanotubes are released and can be obtained.
  • a second reactive solution at least the bond between the polymer packing and the nanotubes with armchair structure is cleaved, which leads to that these nanotubes are obtained.
  • the functionalisation method contains a coupling of fullerenes to polymers during reflux boiling.
  • reflux boiling By using reflux boiling during the binding of molecules or hydrocarbon species to nanotubes with different chiralities, the nanotube that has the strongest bond to the molecule or hydrocarbon specie will form the most stable complex between the nanotube and the corresponding molecule.
  • By applying a deficit of such molecules to which the nanotubes can bond only complexes of nanotubes having the strongest bond to the molecule will be formed.
  • Sudeep and coworkers By applying the above method of Sudeep and coworkers to a mixture of armchair and zigzag nanotubes, the added molecule or hydrocarbon specie will bond to the armchair nanotube.
  • Sudeep and coworkers also shows that the polymer forms clusters with gold nanoparticles, and that such clusters can easily be separated from nanotubes that do not form these complexes with polymers.
  • the complexes that are created between nanotubes of armchair type and a molecule or a hydrocarbon specie, should therefore be able to form clusters with nanoparticles of gold, with which the nanotubes of armchair type easily will be separable from nanotubes of zigzag type that preferably will not form complexes with molecules or hydrocarbon species, when deficit amounts of those, during reflux boiling.
  • the method for separation of nanotubes with respect to their chirality, according to Figs. 2a and 2b can be varied and modified in many ways.
  • An example of a variation of said method is to use thermostatic control of the temperature, T, to the interval T, ⁇ T ⁇ T i+1 to reclaim nanotubes of type i, in such a way that the summation index i is not increased at the counting stage, step 224, which leads to that the temperature T already fulfils the demand to be positioned within the interval T, ⁇ T ⁇ T i+i , that is, that the temperature does not need to be increased further at the heating stage, step 216.
  • Nanotube-polymer complexes that may remain comprise nanotubes of type i, and are through this given a further possibility to be selectively decomposed to be separated from the nanotube-polymer complexes, containing nanotubes of a type other than type i, step 226.
  • the method according to this variation can be used to increase the yield of a certain type of nanotube from a mixture of nanotube- polymer complexes comprising different types of nanotubes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne de manière générale des nanotubes de carbone, et en particulier la manipulation et la séparation sélectives de ceux-ci par des techniques de dérivatisation comprenant, par exemple, des liaisons éther avec des polymères. Lors de la production de nanotubes de carbone, des nanotubes de diverses chiralités sont généralement formés. Les propriétés du nanotube dépendent de sa chiralité. Une manière d'affiner les propriétés de la matière des nanotubes consiste à affiner ceux-ci par rapport à leur chiralité. Il est dès lors souhaitable de pouvoir manipuler sélectivement les nanotubes de carbone par rapport à leur chiralité. Le procédé de l'invention consiste à dérivatiser les extrémités du nanotube de carbone avec une molécule, ce qui confère de nouvelles propriétés au complexe produit, par rapport au nanotube lui-même ; et à rompre ensuite de manière sélective une liaison entre le nanotube et la molécule, associée à la chiralité de la molécule (étape 216). Comme la résistance de la liaison entre le nanotube et la molécule liée dépend de la chiralité, l'invention comporte de nombreuses applications, y compris la manipulation sélective de nanotubes.
PCT/SE2003/001751 2002-11-13 2003-11-12 Manipulation de nanotubes de carbone derivatises WO2004043857A2 (fr)

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Application Number Priority Date Filing Date Title
AU2003284814A AU2003284814A1 (en) 2002-11-13 2003-11-12 Manipulation of derivatized carbon nanotubes

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SE0203377A SE0203377L (sv) 2002-11-13 2002-11-13 Hantering av derivatiserade kolnanorör
SE0203377-7 2002-11-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010089395A2 (fr) 2009-02-06 2010-08-12 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé et kit de séparation de nanotubes de carbone métalliques et semi-conducteurs
CN101538031B (zh) * 2008-03-19 2012-05-23 清华大学 碳纳米管针尖及其制备方法
WO2016044698A1 (fr) * 2014-09-19 2016-03-24 Massachusetts Institute Of Technology Capteurs ratiométriques et multiplexés à partir de nanotubes de carbone de chiralité unique
US10614966B2 (en) 2014-08-11 2020-04-07 Arizona Board Of Regents On Behalf Of The University Of Arizona Aligned graphene-carbon nanotube porous carbon composite

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1998009913A1 (fr) * 1996-09-06 1998-03-12 University Of Massachusetts Liaison covalente reversible de fullerenes a des supports insolubles

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Publication number Priority date Publication date Assignee Title
WO1998009913A1 (fr) * 1996-09-06 1998-03-12 University Of Massachusetts Liaison covalente reversible de fullerenes a des supports insolubles

Non-Patent Citations (4)

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Title
SIMON GUSTAVSSON ET AL: "Theoretical analysis of ether-group derivatization at carbon nanotube ends" NANO LETTERS, vol. 3, no. 2, 2003, pages 265-268, XP002279688 *
T. YILDIRIM ET AL: "Exohydrogenated single-wall carbon nanotubes" PHYSICAL REVIEW B, vol. 64, 2001, pages 3-7, XP002279690 ISSN: 0163-1829 *
VLADIMIR A. BASIUK ET AL: "Direct amidation of terminal carboxylic groups of armchair and zigzag single-walled carbon nanotubes: a theoretical study" NANO LETTERS, vol. 1, no. 11, 2001, pages 657-661, XP002279691 *
VLADIMIR A. BASIUK: "Reactivity of carboxylic groups on armchair and zigzag carbon nanotube tips: a theoretical study of esterification with methanol" NANO LETTERS, vol. 2, no. 8, 2002, pages 835-839, XP002279689 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101538031B (zh) * 2008-03-19 2012-05-23 清华大学 碳纳米管针尖及其制备方法
WO2010089395A2 (fr) 2009-02-06 2010-08-12 Commissariat A L'energie Atomique Et Aux Energies Alternatives Procédé et kit de séparation de nanotubes de carbone métalliques et semi-conducteurs
US9206040B2 (en) 2009-02-06 2015-12-08 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method and kit for separating metal and semiconductor carbon nanotubes
US10614966B2 (en) 2014-08-11 2020-04-07 Arizona Board Of Regents On Behalf Of The University Of Arizona Aligned graphene-carbon nanotube porous carbon composite
WO2016044698A1 (fr) * 2014-09-19 2016-03-24 Massachusetts Institute Of Technology Capteurs ratiométriques et multiplexés à partir de nanotubes de carbone de chiralité unique
US11002741B2 (en) 2014-09-19 2021-05-11 Massachusetts Institute Of Technology Ratiometric and multiplexed sensors from single chirality carbon nanotubes

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AU2003284814A1 (en) 2004-06-03
SE0203377D0 (sv) 2002-11-13
SE0203377L (sv) 2004-05-14
AU2003284814A8 (en) 2004-06-03
WO2004043857A3 (fr) 2005-01-27

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