Synthesis of multi-walled carbon nanotube/polyhedral oligomeric silsesquioxane nanohybrid by utilizing click chemistry
© Yadav et al; licensee Springer. 2011
Received: 2 September 2010
Accepted: 8 February 2011
Published: 8 February 2011
A new hybrid material consisting of a polyhedral oligomeric silsesquioxane (POSS) and carbon nanotube (CNT) was synthesized by a simple and versatile approach entailing click coupling between azide moiety-functionalized POSS and alkyne-functionalized multi-walled CNTs. This approach provides a simple and convenient route to efficiently functionalize a wide variety of nanoscale nanostructure materials on the surface of CNTs.
A hybrid nanomaterial can be broadly depicted as a multi-component system where two or more nanomaterials are unified to form a new nanomaterial fabricated with the aim of realizing attractive multi-functional properties. Hybrid nanomaterials of carbon nanotubes (CNTs) with metals, metal oxides, and biological compounds have been developed for various applications such as sensors, actuators, solar cells, biosensors, and light emitting devices [1, 2]. CNTs offer diverse optical, electrical, and mechanical properties [3, 4], making them attractive building blocks for realizing novel functionality via hybridization [5, 6].
Polyhedral oligomeric silsesquioxane (POSS), a type of inorganic nanostructured molecule [7–9], contains Si-O cores that have a special cage structure and good solubility. Surrounded by various organic groups, POSS is a strong candidate for further functionalization to develop nanohybrid materials [10–12]. The functionalization of CNTs has been one of the most intensively explored methods to produce CNT-based nanostructure materials. Various functionalization strategies for CNTs can be performed with non-covalent bonding, such as van der Waals and π-π interaction, as well as by covalent bonding, such as acid treatment, oxidation, esterification, amidation, radial coupling, anionic coupling, and click coupling [13, 14]. These functionalization methods are dependent on the type, distribution, and concentration of compounds, i.e., polymers, metals, or inorganic nanoparticles, on the surface of the CNTs . Since a landmark report by Sharpless and co-authors , Cu(I)-catalyzed [3+2] Huisgen cycloaddition reaction of azides and alkynes moieties, referred to as "click chemistry," has received a great deal of attention from researchers in fields ranging from organic synthesis to materials chemistry.
This article describes the synthesis of a CNT-POSS nanohybrid material using a click chemistry reaction. It is anticipated that this approach can be utilized to prepare nanohybrids with high interfacial bonding.
Multi-walled carbon nanotubes (MWNTs) used in this study were purchased from Iljin Nano Tech, Seoul, Korea. Their diameter and length ranges were approximately 10-20 nm and 20 μm, respectively. EP0402-epoxycyclohexyllsobutyl POSS (Hybrid Plastic Co. Hattiesburg, MS, USA), propargyl bromide, p-nitrophenol, terabutylammonium bromide, 3-methyl butyl nitrite, copper iodide, and 1,8-diazabicyclo[5, 4]undecene-7-ene were used without further purification.
Fourier transform-infrared (FT-IR) spectroscopic measurements were performed using a Jasco FT-IR 300E device. Elemental analysis was determined by Perkin-Elmer analyzer model 2400 CHN analyzer. 1H NMR and 13C NMR spectra were measured on a 400-MHz instrument by Bruker on CDCl3 solutions at room temperature. Raman spectroscopy (LabRam HR Ar-ion laser 514 nm, Jobin-Yvon, Longjumeau, France) was used to confirm the functionalization of MWNTs. X-ray photoelectron spectroscopy (XPS, ESCSA 2000) was used to analyze the surface composition of the nanotubes. Observation of the surface morphology and energy dispersive X-ray spectrum (EDX) measurement of the MWNT-POSS nanohybrid was carried out by transmission electron microscopy (TEM, JEM 2100F, JEOL). Thermogravimetric analysis (TGA) was carried out in a TA Q 50 system TGA.
Preparation of alkyne-functionalized MWNTs
For the click reaction, p-aminophenyl propargyl ether was first synthesized according to a procedure reported in the literature  to introduce alkyne-functionality on the CNTs. Initially, 60 mg of MWNTs and 3.0 g of p-aminophenyl propargyl ether were placed in a two-necked flask fitted with a reflux condenser and a magnetic stirrer bar under a N2 atmosphere. Then, 3.0 g 3-methyl butyl nitrite was slowly injected via a syringe, and the reaction mixture was stirred at 60°C for 5 h. The resulting product was washed three times with 100 ml of dimethylformamide (DMF), and dried under vacuum at 60°C for 80 h, and the product yield was 80%.
Azidation of POSS molecules
Synthesis of MWNT-POSS nanohybrid by click coupling
Coupling of an azide moiety-containing POSS and alkyne-functionalized MWNTs was carried out via Cu(I)-catalyzed click chemistry. Typically, 20 mg of alkyne-functionalized MWNTs was dispersed in 15 ml of DMF. The MWNTs solution was added to a two-necked flask containing a 400 mg (0.43 mmol) solution of POSS-N3 in 15 ml of DMF. The flask was equipped with a magnetic stirrer bar with a reflux condenser. 162 mg (0.85 mmol) of copper iodide and 6.4 g (42.5 mmol) of 1,8-diazabicyclo[5, 4]undecene-7-ene were charged to the above homogenous solution, which was then heated at 60°C with continuous stirring for 24 h under a nitrogen atmosphere. The product was precipitated into 200 ml of water followed by 100 ml of THF for three times to remove unreacted POSS molecules. The product was dried overnight under vacuum at room temperature, and the product yield was 75-80%.
Result and discussion
Elemental analysis data of POSS-N3
Atomic % and weight % of MWNT-POSS nanohybrid determined from EDX experimental data
In summary, the synthesis of a MWNT-POSS nanohybrid was accomplished via Cu(I)-catalyzed azide-alkyne cycloaddition between azide moiety-containing POSS and alkyne-functionalized MWNTs. Click coupling can provide a new strategy for the synthesis of CNT-based nanohybrids.
energy dispersive X-ray spectrum
Fourier transform infrared
multi-walled carbon nanotubes
polyhedral oligomeric silsesquioxane
transmission electron microscopy
X-ray photoelectron spectroscopy.
This study was supported by the Defense Acquisition Program Administration (DAPA) and the Agency for Defense Development (ADD), and Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education, Science and Technology (R11-2005-065).
- Yang Y, Qu L, Dai L, Kang T, Durstock M: Electrophoresis coating of titanium dioxide on aligned carbon nanotubes for controlled syntheses of photoelectronic nanomaterials. Adv Mater 2007, 19: 1239.View Article
- Park HS, Choi BG, Yang SH, Shin WH, Kang JK, Jung D, Hong WH: Ionic-liquid-assisted sonochemical synthesis of carbon nanotube-based nanohybrid control in the structures and interfacial characteristics. Small 2009, 5: 1754.View Article
- Iijima S: Helical microtubules of graphitic carbon. Nature 1991, 354: 56.View Article
- Srivastava SK, Vankar VD, Kumar V: Excellent field emission properties of short conical carbon nanotubes prepared by microwave plasma enhanced CVD process. Nanoscale Res Lett 2008, 3: 25.View Article
- Ajayan PM, Stephan O, Colliex C, Trauth D: Aligned carbon nanotube arrays formed by cutting a polymer resin nanotube composite. Science 1994, 265: 1212.View Article
- Moniruzzaman M, Winey KI: Polymer nanocomposites containing carbon nanotubes. Macromolecules 2006, 39: 5194.View Article
- Letant SE, Maiti A, Jones TV, Herberg JL, Maxwell RS, Saab AP: Polyhedral oligomeric silsesquioxane (POSS) stabilized Pd nanoparticles factors governing crystallite morphology and secondary aggregate structure. J Phys Chem C 2009, 113: 19424.View Article
- Madbouly SA, Otaigbe JU: Recent advances in synthesis, characterization and rheological properties of polyurethanes and POSS/polyurethane nanocomposites dispersions and films. Prog Polym Sci 2009, 34: 1283.View Article
- Kannan RY, Salacinski HJ, Groot JD, Clatworthy I, Bozec L, Horton M, Butler E, Seifalian AM: The antithrombogenic potential of a polyhedral oligomeric silsesquioxane (POSS) nanocomposites. Biomacromolecules 2006, 7: 215.View Article
- Cordes DB, Lickiss PD, Rataboul F: Recent developments in the chemistry of cubic polyhedral oligosilsesquioxanes. Chem Rev 2010, 110: 2081.View Article
- Ni C, Wu G, Zhu C, Yao B: The preparation and characterization of amphiphilic star block copolymer nano micelles using silsesquioxane as the core. J Phys Chem C 2010, 114: 13471.View Article
- Lickiss PD, Rataboula F: Fully condensed polyhedral oligosilsesquioxanes (POSS): from synthesis to application. Adv Organomet Chem 2008, 57: 1.
- Sahoo NG, Cho JW, Li L, Chan SH: Polymer nanocomposites based on functionalized carbon nanotubes. Prog Polym Sci 2010, 35: 837.View Article
- Jin J, Dong Z, He J, Li R, Ma J: Synthesis of novel porphyrin and its complexes covalently linked to multi-walled carbon nanotubes and study of their spectroscopy. Nanoscale Res Lett 2009, 4: 578.View Article
- Sainsbury T, Fitzmaurice D: Templated assembly of semiconductor and insulator nanoparticles at the surface of covalently modified multiwalled carbon nanotubes. Chem Mater 2004, 16: 3780.View Article
- Kolb HC, Finn MG, Sharpless KB: Click chemistry: diverse chemical function from a few good reactions. Angew Chem Int Ed 2001, 40: 2004.View Article
- Li H, Cheng F, Duft AM, Adronov A: Functionalization of single-walled carbon nanotubes with well-defined polystyrene by "click" coupling. J Am Chem Soc 2005, 127: 14518.View Article
- Leu CM, Chang YT, Wei KH: Synthesis and dielectric properties of polyimide tethered polyhedral oligomeric silsesquioxane (POSS) nanocomposites via POSS diamine. Macromolecules 2003, 36: 9122.View Article
- Kim CK, Kim BS, Sheikh FA, Lee US, Khil MS, Kim HY: Amphiphilic poly(vinyl alcohol) hybrids and electrospun nanofibers incorporating polyhedral oligosilsesquioxane. Macromolecules 2007, 40: 4823.View Article
- Sheikh FA, Barakat NAM, Kim BS, Aryal S, Khil MS, Kim HY: Self-assembled amphiphilic polyhedral oligosilsesquioxane (POSS) grafted poly(vinyl alcohol) (PVA) nanoparticles. Mater Sci Eng C 2009, 29: 869.View Article
- Ge Z, Wang D, Zhou Y, Liu H, Liu S: Synthesis of organic/inorganic hybrid quatrefoil shaped star cyclic polymer containing a polyhedral oligomeric silsesquioxane core. Macromolecules 2009, 42: 2903.View Article
- Sato-Berrú RY, Basiuk EV, Saniger JM: Application of principal component analysis to discriminate the Raman spectra of functionalized multiwalled carbon nanotubes. J Raman Spectrosc 2006, 37: 1302.View Article
- Yadav SK, Mahapatra SS, Cho JW, Lee JY: Functionalization of multiwalled carbon nanotubes with poly(styrene-b-(ethylene-co-butylene)-b-styrene) by click coupling. J Phys Chem C 2010, 114: 11395.View Article
- Yadav SK, Mahapatra SS, Cho JW, Park HC, Lee JY: Enhanced mechanical and dielectric properties of poly(vinylidene fluoride)/polyurethane/multi-walled carbon nanotube nanocomposites. Fibers Polym 2009, 10: 756.View Article
- Izuhara D, Swager TM: Electroactive block copolymer brushes on multiwalled carbon nanotubes. Macromolecules 2009, 42: 5416.View Article
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.