WO2014117234A1 - Procédé d'obtention de nanotubes de carbone fonctionnalisés ntc-func à groupements thiols -sh - Google Patents

Procédé d'obtention de nanotubes de carbone fonctionnalisés ntc-func à groupements thiols -sh Download PDF

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Publication number
WO2014117234A1
WO2014117234A1 PCT/BR2013/000535 BR2013000535W WO2014117234A1 WO 2014117234 A1 WO2014117234 A1 WO 2014117234A1 BR 2013000535 W BR2013000535 W BR 2013000535W WO 2014117234 A1 WO2014117234 A1 WO 2014117234A1
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WIPO (PCT)
Prior art keywords
fact
cnts
ntc
carbon nanotubes
mass ratio
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PCT/BR2013/000535
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English (en)
Portuguese (pt)
Inventor
Oswaldo Luiz ALVES
Rafaella Oliveira DO NASCIMENTO
Diego Stéfani Teodoro MARTINEZ
Oscar Endrigo Dorneles RODRIGUES
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Universidade Estadual De Campinas - Unicamp
Universidade Federal De Santa Maria - Ufsm
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Publication of WO2014117234A1 publication Critical patent/WO2014117234A1/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
    • 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
    • C01B32/17—Purification
    • 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
    • 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

Definitions

  • the present invention relates to a process of obtaining functionalized single wall (SWCNT), double (DWCNT) or multiple (MWCNT) carbon nanotubes through the generation of carbanions and the application of elemental sulfur to obtain thiols groups (-SH ) on the surface of said nanotubes (SWCNT-SH, DWCNT-SH and MWCNT-SH).
  • SWCNT functionalized single wall
  • DWCNT double
  • MWCNT multiple
  • NTC-FUNC Functionalized nanotubes
  • NTC-FUNC have several applications that include, but are not limited to, serving as a reaction support for their connection with molecules and macromolecules (natural or synthetic origin) such as carbohydrates, polymers, amino acids, peptides, proteins, enzymes and antibodies; for the formation of multifunctional hybrid systems, applied to the transport of drugs and agrochemicals, for example.
  • nanoscience and nanotechnology have been presented as an important platform for innovation, encompassing the synthesis, characterization and application of nanoscale-sized materials / structures (n x10 * 9 m).
  • These nanostructures / nanomaterials are unique in that they have distinct physical and chemical properties from those observed in bulk materials due to their high surface area and consequent implications for different types of interaction [Yacaman, JM; Lorez, H .; Santiago, P .; Galvan, DH; Garzon, IL Appl. Phys. Lett., 8 (1996), 69; ackie, EB; Galvan, DH; Adem, E .; Talapatra, S .; Yang, G.L; Migone, AD Adv. Mater., 12 (2000), 495].
  • Carbon nanostructures are among the most studied today and present themselves as promising structures and with diverse applications, ranging from the use as engineering nanomaterials to sophisticated drug delivery systems, electronic and photonic devices.
  • Carbon nanotubes are characterized by being a cylindrically shaped graphite (graphene) sheet, with diameters of approximately 1 nm, or several sheets wrapped around each other forming concentric cylinders with a spacing of 0.34-0.36 nm. . This spacing is slightly higher than the interplanar distance of the graphite.
  • the driving force that causes the formation of NTCs is attributed to the instability of graphite in dimensions of few nanometers.
  • Nanotube functionalization techniques can be divided into three major groups: covalent, non-covalent and doping.
  • Doping carbon nanotubes is an option to make their application feasible. Such a technique can be divided into three classes; substitutional doping (flat doping), endohedral doping (encapsulation), and exohedral doping (interleaving).
  • substitutional doping consists of the creation of defects in the tubular structure of the NTCs and, to stabilize them, new atoms and / or functional groups are added to the NTCs.
  • Endohedral doping has as its principle the use of carbon nanotube capillarity, thus using them as encapsulating agents of molecules and / or nanostructures. [Terrones, M., Souza Filho, A.G., Rao, A.M., Doped Carbon Nanotubes: Synthesis, Characterization and Applications.
  • Exohedral doping follows the same principle as surface adsorption of NTCs; What differs from each other is that the adsorption is based on the ⁇ - ⁇ -type interactions between the carbon nanotubes and the molecules to be adsorbed; whereas exohedral doping is based on charge transfer between NTCs and an electron donating or receiving agent [Kazaoui, S., Minami, N., Jacquemin, R., Kataura, H., Achiba, Y., Phys . Rev. B, 60, p. 3339, 1999].
  • covalent functionalizations in carbon nanotubes can be done by generating functional groups along the wall of the NTCs that, in a second moment, can serve as a support for the formation of new groups, bonds and / or chain growth. polymeric. Functionalizations of NTCs generated by covalent bonds formed on their surface tend to occur in the curvature regions, since the BR2013 / 000535
  • NTCs Some covalent bonds directly modify the dispersibility of NTCs.
  • the NTCs become dispersible in water due to the hydrogen interactions generated between the water molecules and the oxygenated groups (eg carboxyl, carbonyl and hydroxyl) formed on the surface of the NTCs after such oxidative treatments.
  • the oxidative functionalization of NTCs is described by several authors. Ramanathan et al. described the oxidation of nanotubes by using a mixture of concentrated H 2 SO 4 and HNO 3 (3: 1) under sonication for approximately three hours to increase the penetration of the acid mixture into the nanotube bundle. [Ramanathan, T .; Fisher, FT; Ruoff, RS; Brinson, LC Chem. Maer., 17, (2005), 1290].
  • Lee et al reported in their invention to obtain carbon nanotubes functionalized with carboxylic acid groups with which reacted molecules with amino groups and thiols to obtain nanotubes with thiol functions, which were used to adsorb metallic particles and obtain an NTC. with conductive properties.
  • Lee et al developed a carbon nanotube-based biosensor for enzymatic fixation using a strong activity electrocatalyst.
  • the biosensor proposed by the inventors is composed of a liquid-ionic mixture of chitosan and carbon nanotubes on which gold nanoparticles have been deposited.
  • the carbon nanotubes applied in this invention were functionalized with terminal thiol group organic molecules for interaction with the gold nanoparticles [Saraf, RF; Wickramasinghe, HK; 09 / 972,958, 2003; Hwan, JD; Tae, JH; Hun, KB; Hyeon, k.
  • the present invention relates to a process for obtaining thiol group functionalized single (SWCNT), double (DWCNT) or multiple (MWCNT) carbon nanotubes, wherein said functionalization basically comprises the following main steps:
  • NTCs carbon nanotubes
  • HCl hydrochloric acid
  • step (b) the reaction of the purified NTCs obtained in step (b) with lithium aluminum hydride (LiAIH 4 ) is promoted to carbonic formation on the surface of said NTCs;
  • NTC-S sulfide groups
  • NTC-SH functionalized NTCs containing thiol groups on their surface
  • step (h) washing the NTCs obtained in step (h) with tetrahydrofuran (THF) and distilled water is promoted; j) the clean, partially salt-free, elemental sulfur-free NTC-SH formed during reaction with the hydride; and
  • step (j) promote the dialysis of the NTC-SH obtained in step (j) to remove any remaining soluble salt residues in the nanotubes after washing with water.
  • the NTC / HCI mass ratio should be chosen from 1: 10 to 10: 1, preferably 5: 1.
  • the HCl concentration should be in the range 1 to 12 M, preferably 5 M.
  • the stirring is performed at a temperature between 60 to 110 ° C and may last from 6 to 10 hours.
  • the dispersion of the purified NTCs obtained in step (b) comprises a chosen NTC / THF mass ratio in the range 1: 3.10 3 to 1: 1.10 4 , preferably 1: 5.5.10 3 .
  • the system Prior to the addition of LiAIH 4 , the system remains under ultrasound for 30 to 120 minutes, preferably 45 minutes.
  • the system After the addition of LiAIH 4 , the system remains under an ultrasonic bath for a period of time ranging from 3 to 5 hours and at a temperature ranging from 20 to 70 ° C.
  • LiAIH 4 is added to the dispersion of NTC in dry THF at the LiAIH 4 / NTC in THF mass ratio chosen in the range 3: 1 to 6: 1, preferably 3.5: 1.
  • Elemental sulfur is added to the NTCs obtained in step (d) at an NTC / S mass ratio chosen from 1: 3 to 1: 8, preferably 1: 4.
  • step (k) Concentrated HCl is added to the NTCs obtained in step (f) at a chosen HCI / NTC mass ratio in the range 10: 1 to 20: 1, preferably 15.5: 1.
  • the dialysis of step (k) is performed against water until the water conductivity of said dialysis remains constant over a range of 5 pS to 1 pS, preferably 2 pS.
  • - Provides a product comprising 15 to 60 mass% of NTC, 40 to 85 mass% of SH and a water dispersion of around 5 mg / mL, and is free of metal residues, reaction residues and undesirable carbon chain bonds / adsorption on its surface.
  • the pre-treatment steps of the NTC sample with hydrochloric acid allowed the reduction of metallic residues associated with carbon nanotubes. The presence of such residues decreases the quality of the NTC sample.
  • lithium aluminum hydride in place of butyl lithium reduces the bonding / adsorption of undesirable carbon chains on the surface of MWCNT.
  • the steps subsequent to thiols formation remove the reaction residues and improve the sample quality of the functionalized carbon nanotube.
  • Figure 1 shows the schematic representation of the formation of carbonanions on the surface of carbon nanotubes with subsequent obtaining of organic halides. Adapted from Liang et al.
  • Figure 2 shows the MWCNT functionalization flowchart for obtaining thiol groups.
  • Figure 3 shows a schematic representation of the functional group formed on the outermost wall of the multiwall carbon nanotube.
  • Figure 4 shows the infrared spectrum of the MWCNT-SH.
  • Figure 5 shows the result of thermogravimetric analysis of the MWCNT-SH sample.
  • Figure 6 presents the 13 C analysis of the MWCNT-SH sample.
  • the present invention relates to a process of obtaining functionalized carbon nanotubes, wherein said functionalizations are performed by a reaction to form carbonanions on the surface of carbon nanotubes, whether single-walled (SWCNT) or double-walled (DWCNT). or multi-walled (MWCNT) using LiAIH 4 and further reaction with elemental sulfur to obtain thiols groups.
  • SWCNT single-walled
  • DWCNT double-walled
  • MWCNT multi-walled
  • the carbon nanotubes used in the present invention must, but are not limited to those obtained commercially from CNT Co. Ltd., provided they are single, double or multi-walled, obtained by different carbon nanotube synthesis techniques such as chemical deposition from the vapor phase (CVD), electric arc discharge, plasma ablation (continuous or pulsed), among others. Importantly, if the NTCs are immobilized on a polymeric matrix or not, it must be removed to perform the appropriate functionalization steps.
  • multi-wall carbon nanotubes were used, and to obtain this sample they were subjected to a (non-oxidative) purification pretreatment in which at least 1.0 g of MWCNT raw material was subjected to purification treatment to remove metallic residue.
  • MWCNT multi-wall carbon nanotubes
  • Such MWCNT were treated in a standard reflux and stirring system with 5M HCl solution for at least 6 hours at a maximum temperature of 110 ° C.
  • the conventional reflux and stirring system may be replaced by a Soxhlet system provided that the NTCs are in perforated Teflon capsules for acid passage.
  • the nanotubes were filtered and washed with distilled water to pH> 6.0. Finally, the nanotubes were dried in a vacuum line.
  • the first and second events occur between 94.5 ° C and 289 ° C and correspond to a 41% mass loss that can be associated with a degree of functionalization * of 75.08 moles of SH groups in the MWCNT-SH sample. .
  • the third event at 502.7 ° C refers to sample decomposition.
  • INOVA 500 with a frequency of 125.7 MHz using a 10 second relaxation time, and the number of accumulations ranging from 128 to 108880.
  • a direct probe the 5 mm Broad Band Switchable BBSW optimized for X-channel detection, was used.
  • the MWCNT-SH sample was dispersed in D 20 using ultrasound bath.

Abstract

La présente invention concerne un procédé d'obtention de nanotubes de carbone à parois simples (SWCNT), doubles (DWCNT) ou multiples (MWCNT) fonctionnalisés par production de carbanions et application de soufre élémentaire pour l'obtention de groupes thiols (-SH) sur la surface desdits nanotubes (SWCNT-SH, DWCNT-SH, MWCNT-SH). Les nanotubes fonctionnalisés (NTC-FUNC) présentent diverses applications incluant, non limitativement, la fourniture d'un apport réactionnel pour leur liaison à des molécules et des macromolécules, d'origine naturelle ou synthétique, telles que : des hydrates de carbone, des polymères, des acides aminés, des peptides, des protéines, des enzymes et des anticorps; pour la formation de systèmes hybrides multifonctionnels destinés au transport de médicaments et de produits agrochimiques, par exemple.
PCT/BR2013/000535 2013-01-31 2013-12-03 Procédé d'obtention de nanotubes de carbone fonctionnalisés ntc-func à groupements thiols -sh WO2014117234A1 (fr)

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BRBR1020130024120 2013-01-31
BR102013002412-0A BR102013002412B1 (pt) 2013-01-31 2013-01-31 Processo de obtenção de nanotubos de carbono de paredes simples, duplas ou múltiplas funcionalizados com grupamento tiol, nanotubos assim obtidos e uso dos nanotubos

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CN116022775B (zh) * 2022-12-29 2024-02-09 蜂巢能源科技(上饶)有限公司 一种碳纳米管提纯方法及应用

Citations (1)

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WO2008048227A2 (fr) * 2005-08-11 2008-04-24 Kansas State University Research Foundation Nanotubes de carbone synthétique

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008048227A2 (fr) * 2005-08-11 2008-04-24 Kansas State University Research Foundation Nanotubes de carbone synthétique

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ADAMS, L.; ET AL.: "Preparation and characterization of sulfonic acid- functionalized single-walled carbon nanotubes.", PHYSICA E-LOW- DIMENSIONAL SYSTEMS & NANOSTRUCTURES, vol. 41, no. 4, February 2009 (2009-02-01), pages 723 - 728 *
CONTURBIA, G; ET AL.: "Single-Wall Carbon Nanotubes Chemically Modified with Cysteamine and Their Application in Polymer Solar Cells: Influence of the Chemical Modification on Device Performance.", JOURNAL OF NANOSÇIENCE AND NANOTECHNOLOGY, vol. 9, no. 10, October 2009 (2009-10-01), pages 5850 - 5859 *

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