WO2005090233A2 - Reductive functionalization of carbon nanotubes - Google Patents
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- WO2005090233A2 WO2005090233A2 PCT/US2005/008303 US2005008303W WO2005090233A2 WO 2005090233 A2 WO2005090233 A2 WO 2005090233A2 US 2005008303 W US2005008303 W US 2005008303W WO 2005090233 A2 WO2005090233 A2 WO 2005090233A2
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- B82Y40/00—Manufacture or treatment of nanostructures
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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- 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
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/06—Multi-walled nanotubes
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- C01B2202/00—Structure or properties of carbon nanotubes
- C01B2202/20—Nanotubes characterized by their properties
- C01B2202/36—Diameter
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- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- 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
Definitions
- This invention relates generally to carbon nanotubes, and specifically to methods of derivatizing carbon nanotubes via reductive pathways.
- SWNTs have been studied extensively due to their unique mechanical, optical, electronic, and other properties. For example, the remarkable tensile strength of SWNTs has resulted in their use in reinforced fibers and polymer nanocomposites (Zhu et ah, Nano Lett. 2003, 3, 1107 and references therein). For other existing and potential applications of CNTs, see Baughman et al, Science, 2002, 297, 787-792. [0005] SWNTs normally self-assemble into aggregates or bundles in which up to several hundred tubes are held together by van der Waals forces. For many applications, including bio-medical ones, the separation of individual nanotubes from these bundles is essential.
- CNT "type,” as used herein, refers to such electronic types described by the (n,m) vector (i.e., metallic, semi-metallic, and semiconducting).
- CNT “species,” as used herein, refers to CNTs with discrete (n,m) values.
- CNT “composition,” as used herein, refers to make up of a CNT population in terms of nanotube type and species.
- the present invention is directed to novel processes (methods) for the functionalization (i.e., chemical derivatization) of carbon nanotubes and, by extension, to fullerenes and other carbon surfaces (i.e., inorganic carbon materials in general).
- processes involve reductive pathways.
- carbon nanotubes are reacted with alkali metal and organic halides in anhydrous liquid ammonia.
- polymers are grown in situ from carbon nanotube sidewalls by reacting carbon nanotubes with alkali metal and monomer species in anhydrous liquid ammonia.
- the present invention is directed to methods of functionalizing carbon materials, such methods comprising the steps of: (a) combining carbon material with liquid ammonia to form a mixture; (b) dissolving a quantity of alkali metal in the mixture to form a reductive mixture; and (c) adding an organic halide, comprising an organic portion and a halide portion, to the reductive mixture such that the organic portion of the organic halide adds to the carbon material to form derivatized carbon material.
- One or more of various quenching (to neutralize unreacted alkali metal), acidification (to neutralize unevaporated ammonia), filtering (to collect the derivatized carbon material), and washing (to remove unwanted species from the derivatized carbon material) steps can optionally be performed.
- carbon materials include, but are not limited to, carbon nanotubes, nanoscrolls, fullerenes, diamond, acetylenic carbon, carbon black, activated charcoal, graphitic carbon, and combinations thereof.
- the monomer is seen to undergo free radical polymerization.
- carbon materials include, but are not limited to, carbon nanotubes, nanoscrolls, fullerenes, diamond, acetylenic carbon, carbon black, activated charcoal, graphitic carbon, and combinations thereof.
- Variations on the above-described embodiments include the use of other solvents, like anhydrous amines, instead of, or in addition to, ammonia.
- the methods of the present invention are novel in that no similar methods for this type of sidewall functionalization exist. Furthermore, such methods fill a recognized need in the art for a gentle (i.e., not requiring ultrasonication) and scalable process for derivatizing the sidewalls of carbon nanotubes.
- FIGURE 1 pictorially illustrates embodiments where a SWNT bundle 100 is reduced in anhydrous liquid ammonia (NH ) by Li to yield reduced intercalated/exfoliated bundle 101, and wherein this intercalated/exfoliated bundle 101 is then reacted with an organic halide (RI) to yield functionalized SWNTs 102;
- NH hydrous liquid ammonia
- RI organic halide
- FIGURE 3 is a Raman spectrum (780 nm excitation) of raw SWNTs that have been butylated according to methods of the present invention
- FIGURE 5 is a Raman spectrum (780 nm excitation) of raw SWNTs that have been dodecylated according to methods of the present invention
- FIGURES 6(A) and (B) are Raman spectra (780 nm excitation) of pure (B) and dodecylated bucky pearls (A) samples;
- FIGURE 7 is an AFM image of the dodecylated purified SWNTs;
- FIGURE 8 is a section analysis of the AFM image shown in FIGURE 7;
- FIGURES 10(A) and (B) are high resolution transmission electron microscopy (HRTEM) images of dodecylated purified SWNTs showing individual nanotubes and extensive debundling;
- FIGURES 16(A) and (B) are SEM images, at different magnifications, of SWNTs-PMMA.
- Carbon nanotubes include, but are not limited to, single-wall carbon nanotubes (SWNTs), double-wall carbon nanotubes (DWNTs), multi-wall carbon nanotubes (MWNTs), small diameter carbon nanotubes, and combinations thereof. Small diameter carbon nanotubes are defined herein as carbon nanotubes having diameters of at most about 3 nm, regardless of the number of walls. All methods of making CNTs yield product with carbonaceous impurities. Additionally, most methods of making SWNTs, and many methods of making MWNTs, use metal catalysts that remain in the product as impurities.
- FIGURE 2 Scheme 1
- SWNTs are first intercalated/reduced with lithium (or other suitable alkali metal) in anhydrous liquid ammonia, an then reacted with an organic halide 1 to yield functionalized SWNTs 2a-f, wherein organic halides la-f are provided as examples.
- organic halides la-f are provided as examples. While not intending to be bound by theory, the debundling can be explained in terms of extensive intercalation by the lithium (or other alkali metal), leading to lithium ions dispersed between the negatively charged tubes, as shown in FIGURE 2.
- This Example serves to illustrate benzylation of carbon nanotubes by Li/NH 3 reduction in the presence of benzyl chloride, as shown by Eq. 2.
- This reaction was carried out in a manner similar to that described in EXAMPLE 1.
- a flame dried 100 mL 3 -neck round bottom flask was placed 20 mg of raw single-wall carbon nanotubes. Then, to this flask was condensed -60 mL of NH 3 , followed by the addition of Li metal in very small pieces ( ⁇ 462 mg total). After the complete addition of Li, -2.108 g (1.92 mL) of benzylchloride was added to the flask with a syringe. The ice bath below the flask was subsequently removed and the reaction was allowed to proceed overnight with slow evaporation of NH 3 .
- This Example serves to illustrate dodecylation of carbon nanotubes by Li/NH 3 reduction in the presence of /z-dodecyl iodide, as shown by Eq. 3.
- SWNTs (raw) + Li/NH 3 + CH 3 -(CH 2 )n-I ⁇ w-dodecylated SWNTs (Eq. 3)
- NH 3 gas 60 mL was condensed in it.
- Li metal in small portions (-462 mg total).
- the mixture turned deep blue in color.
- 4.933 g (4.107 mL) of 1-iodododecane was added.
- the ice bath was removed and the reaction was was allowed to proceed overnight with slow evaporation of NH 3 .
- the bucky paper (SWNT mat) thus obtained was used for subsequent Raman analysis which revealed a significant disorder peak as shown in FIGURE 5.
- SWNTs (raw) + Li/NH 3 + CH 3 -(CH 2 ) 7 -Br ⁇ n-octylated SWNTs (Eq. 4)
- This Example serves to illustrate tert-butylation of carbon nanotubes by Li/NH 3 reduction in the presence of t-butyl iodide, as shown by Eq. 5.
- SWNTs (raw) + Li/NH 3 + (CH 3 ) 3 C-I ⁇ ⁇ -butylated SWNTs (Eq. 5)
- the reaction was worked up by first quenching the reaction mixture with 10 mL of methanol followed by the addition of 20 mL of H 2 O and then acidification with 10% HC1. Repeated washing of the material with ethanol over 0.2 ⁇ m PTFE membrane filter gave bucky paper, which was used for further analysis.
- This Example serves to illustrate dodecylation of purified carbon nanotubes by Li/NH 3 reduction in the presence of n-dodecyl iodide, as shown by Eq. 6.
- SWNTs (purified) + Li/NH 3 + CH 3 -(CH 2 ) ⁇ I ⁇ ⁇ -dodecylated SWNTs (Eq. 6]
- FIGURE 6 is an atomic force microscopy (AFM) image of the dodecylated SWNTs produced in this example, and FIGURE 8 is the corresponding section analysis. Both FIGURES 7 and 8 reveal substantial debundling of the SWNTs (from their roped state) and a plethora of individual SWNTs — indicative of significant derivatization.
- AFM atomic force microscopy
- FIGURE 9 is an FTIR spectrum of dodecylated SWNTs
- FIGURES 10(A) and (B) are high resolution transmission electron microscopy (HRTEM) images of dodecylated SWNTs showing individual nanotubes and extensive debundling.
- HRTEM transmission electron microscopy
- FIGURE 11 depicts a GC-MS chromatogram of mass peaks (temperature profile: 2 minute hold at 50°C, ramp 10°C/minute to 280°C, 5 minute hold at 280°C) representing byproducts in the preparation of w-dodecylated SWNTs (Example 6) where:
- /z-C ⁇ 2 H , «-C 12 H 24 and /.-C 24 H 5 o are formed as major by-products when n- dodecyl iodide is used as the alkylating reagent.
- n-C ⁇ 2 H 26 and «-C 12 H 24 would arise from disproportionation of the dodecyl radical whereas «-C 24 H 5 o is formed by dimerization of dodecyl radicals.
- TGA thermal gravimetric analysis
- TGA thermogravimetric analyses
- MS mass spectrometer
- n-Dodecylated SWNTs were pyrolyzed in an argon atmosphere to a temperature of 800°C.
- TGA thermogravimetric analysis
- FT-IR Fourier transform- infrared
- the sample was held at 80°C for 30 minutes, ramped 10°C min "1 to 800°C, then isothermally held for 10 minutes at 800°C.
- the gaseous species released from the sample during the pyrolysis were fed into the FT-IR specfrophotometer, and their concentration variations during the pyrolysis process were monitored with time and/or temperature.
- n-dodecylated SWNTs produced using different alkali metals show quite different profiles in the TGA-FTIR.
- Reactions using lithium show two major peaks during the pyrolysis process: a major peak at around 160-300°C, and a small peak at around 480°C.
- Using sodium produces a quite different profile: one small peak at around 180-280°C and a major peak that appears at 380- 530°C.
- Trace C two peaks of similar intensity are shown at two different temperature regions.
- This example serves to illustrate polymerization of methyl methacrylate which is initiated by lithiated SWNTs, as depicted by Eq. 7.
- SWNTs (purified) + Li/N ⁇ 3 + CH 2 C(CH 3 )COOCH 3 ⁇ SWNTs-PMMA (Eq-7)
- Methyl methacrylate was washed twice with 5% NaOH, twice with water, then dried over anhydrous MgSO 4 , CaH 2 and then vacuum distilled.
- a sealed flame-dried 100 mL three-neck round-bottom flask containing 20 mg of purified single-wall carbon nanotubes was degassed and refilled with argon three times.
- Approximately 70 mL of NH 3 was then condensed into the flask followed by the addition of small pieces of lithium metal (-10 mg total) until a slightly blue color remained.
- Approximately 3.500 g (3.7 mL) of methyl methacrylate was then added to the flask with a syringe.
- the ice bath was then removed and the reaction was allowed to proceed overnight with the slow evaporation of NH 3 .
- the reaction was worked up by first quenching the reaction mixture with 10 mL of methanol followed by the addition of 20 mL of H O. After acidification with 10% HC1, the nanotubes were extracted into hexanes and washed several times with water. The hexane layer was then filtered through a 0.2 ⁇ m PTFE membrane filter, washed with ethanol, chloroform and then dried in a vacuum oven (80°C) overnight.
- FIGURES 14(A) and (B) are Raman spectra (780 nm excitation) of pristine SWNTs (A) and SWNTs-PMMA (B). This Raman analysis provides evidence that the polymerization of methyl methacrylate has been achieved at/to the sidewall of the SWNTs.
- the transmission electron microscopy (TEM) image of the SWNTs-PMMA (FIGURE 15) shows part of the nanotubes were covered with polymers.
- FIGURES 16(A) and (B) show scanning electron microscope (SEM) images of the SWNTs-PMMA, wherein (B) is at a higher magnification than (A).
Abstract
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JP2007503081A JP2007530400A (en) | 2004-03-12 | 2005-03-11 | Reductive functionalization of carbon nanotubes |
CA002559508A CA2559508A1 (en) | 2004-03-12 | 2005-03-11 | Reductive functionalization of carbon nanotubes |
US10/592,463 US7758841B2 (en) | 2004-03-12 | 2005-03-11 | Reductive functionalization of carbon nanotubes |
EP05749552A EP1732847A2 (en) | 2004-03-12 | 2005-03-11 | Reductive functionalization of carbon nanotubes |
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US60/611,045 | 2004-09-17 |
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KR (1) | KR20070001224A (en) |
CN (1) | CN101287678A (en) |
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WO2007051071A2 (en) * | 2005-10-28 | 2007-05-03 | William Marsh Rice University | Two-step method of functionalizing carbon allotropes and pegylated carbon allotropes made by such methods |
WO2007098578A1 (en) * | 2006-03-01 | 2007-09-07 | National Research Council Of Canada | Chemical functionalization of carbon nanotubes |
WO2008097343A2 (en) * | 2006-08-08 | 2008-08-14 | William Marsh Rice University | Functionalized graphene materials and method of production thereof |
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- 2005-03-11 JP JP2007503081A patent/JP2007530400A/en active Pending
- 2005-03-11 WO PCT/US2005/008303 patent/WO2005090233A2/en active Application Filing
- 2005-03-11 RU RU2006136018/15A patent/RU2006136018A/en not_active Application Discontinuation
- 2005-03-11 EP EP05749552A patent/EP1732847A2/en not_active Withdrawn
- 2005-03-11 KR KR1020067021116A patent/KR20070001224A/en not_active Application Discontinuation
- 2005-03-11 CA CA002559508A patent/CA2559508A1/en not_active Abandoned
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Cited By (21)
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WO2007051071A2 (en) * | 2005-10-28 | 2007-05-03 | William Marsh Rice University | Two-step method of functionalizing carbon allotropes and pegylated carbon allotropes made by such methods |
WO2007051071A3 (en) * | 2005-10-28 | 2007-06-14 | Univ Rice William M | Two-step method of functionalizing carbon allotropes and pegylated carbon allotropes made by such methods |
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EP1989143A1 (en) * | 2006-03-01 | 2008-11-12 | National Research Council of Canada | Chemical functionalization of carbon nanotubes |
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RU2006136018A (en) | 2008-04-20 |
JP2007530400A (en) | 2007-11-01 |
KR20070001224A (en) | 2007-01-03 |
EP1732847A2 (en) | 2006-12-20 |
US7758841B2 (en) | 2010-07-20 |
CN101287678A (en) | 2008-10-15 |
US20070196262A1 (en) | 2007-08-23 |
CA2559508A1 (en) | 2005-09-29 |
WO2005090233A3 (en) | 2008-03-20 |
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