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Chemistry of Carbon Nanotubes for Everyone

Sharmistha Basu-Dutt,*, Marilyn L. Minus, Rahul Jain, Dhriti Nepal, and Satish Kumar

Department of Chemistry, University of West Georgia, Carrollton, Georgia 30118, United States Department of Mechanical and Industrial Engineering, Northeastern University, Boston, Massachusetts 02115, United States School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332-0295, United States ABSTRACT: Carbon nanotubes (CNTs) have the extraordinary potential to change our lives by improving existing products and enabling new ones. Current and future research and industrial workforce professionals are very likely to encounter some aspects of nanotechnology including CNT science and technology in their education or profession. The simple structure and interesting chemistry of CNTs make their inclusion in an undergraduate curriculum appropriate. An overview of the chemistry of CNTs is presented starting with a brief history followed by discussions on chemical structure, exceptional properties, potential applications, nature of technological challenges, and possible solutions that will expand the optimal utilization of these materials in the near future. This article is intended to be a starting point for developing a variety of CNT-based undergraduate projects. KEYWORDS: General Public, Upper-Division Undergraduate, Analytical Chemistry, Interdisciplinary/Multidisciplinary, Organic Chemistry, Physical Chemistry, Textbooks/Reference Books, Applications of Chemistry, Consumer Chemistry, Nanotechnology

ver the past decade, the term nano has found a prominent place in a variety of professional and popular media. There are many dierent opinions about where this new and fast evolving global cross-disciplinary undertaking will lead us, but many would agree that it has the extraordinary potential to change our lives by improving existing technologies to enable new product development. The ability to fabricate, characterize, and utilize material structures on the 1100 nm scale will profoundly inuence future research and developments in physics, chemistry, and biology; as well as revolutionize bio-, computer, mechanical, and electrical engineering; electronics and communications; medicine; transportation; and space exploration by making new materials, sensors, and devices. The eld of nanotechnology is very broad and understanding every aspect of it, for an individual, is impossible. Yet, the far-reaching nature of this eld makes it vital for everyone to understand some aspects that are most relevant to their professional and personal lives. According to the U.S. National Nanotechnology Initiative (NNI), nanoscience involves research to discover new behaviors and properties of materials with dimensions at the nanoscale, which ranges roughly from 1 to 100 nanometers and nanotechnology is the way discoveries made at the nanoscale are put to work.1 The nanoscale vision can be attributed to Nobel Laureate Richard Feynman who gave a lecture in 1959 entitled There is Plenty of Room at the BottomAn Invitation to Enter a New Field of Physics, and encouraged manufacturing of objects that can be maneuvered at the level of an individual atom.2 Problems encountered today in processing nanomaterials were well predicted by Professor Feynman. For example, he had stated, There is a problem that materials stick together by the molecular (Van der Waals) attractions. It would be like this: After

you have made a part and you unscrew the nut from a bolt, it isnt going to fall down because the gravity isnt appreciable; it would be even hard to get it o the bolt. In the light of this remark about nanoscale aggregation (sticking) phenomena, it is easy to understand the problems of dispersing nanomaterials into a given media. He also stated that, The problems of Chemistry and Biology can be greatly helped if our ability to see what we are doing, and to do things on an atomic level, is ultimately developed a development which I think cannot be avoided. The development of scanning tunneling and atomic force microscopes in 1980s has provided us with the initial ability for such studies, and since then, many other instrumental developments have aided nanoscale (atomic level) studies. In addition, the rst books on nanotechnology were written by Eric Drexler even though some of the views are perhaps controversial.3 Nanomaterials such as thin lms and engineered surfaces, where one of the dimensions (i.e., thickness) is on the order of the nanometer scale, have been used for decades in silicon integrated circuits, fuel cells, and catalysts. New research has now led to the development of two- and three-dimensional nanomaterials, where one or more dimensions are at the nanometer scale. Carbon and inorganic nanotubes and nanowires can therefore be considered as examples of two- or three-dimensional nanomaterials. Nanoparticles, dendrimers, and quantum dots with all three dimensions at the nanometer scale display many intriguing phenomena observable at this scale, but they are unobservable in the bulk material. For example, copper nanoparticles do not exhibit the same malleability and ductility as bulk copper,4 and even though
Published: October 27, 2011
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Copyright r 2011 American Chemical Society and Division of Chemical Education, Inc.

Journal of Chemical Education Table 1. Enhancement of Surface-to-Volume Ratio (SVR) at the Nanoscale Compared to the Meterscale
Cube 1 m3 1 nm
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Surface Area/nm2 6 1018 (= 6 m2) 6

Volume/nm3 1 1027 (= 1 m3) 1

SVR/ (nm2/nm3) 6 109 nm2/nm3 6 nm /nm

2 3

SVR Enhancement 6/(6 109) = 109

Table 2. Carbon NanotubeRelated Publications, 19912008

Year 19912000 20012008 2001 2002 2003 2004 2005 2006 2007 2008 No. of publications 3000 34719 1395 2161 2741 3762 4597 5645 6680 7738

Table 3. Worldwide Distribution of Carbon Nanotube Publications, 19912008

Country United States China Japan Germany Korea France United Kingdom Russia Taiwan Italy No. of Publications 11,400 8,900 4,900 2,400 2,400 1,790 1,724 1,196 1,143 924 Country India Spain Canada Singapore Australia Switzerland Belgium Brazil Israel Poland No. of Publications 870 839 761 656 648 548 536 488 466 423

a bulk sample of gold is yellow, a solution of gold nanoparticles can appear to be a variety of colors depending on the size of the nanoparticles, including red for particles <100 nm.5 These drastic changes are due to an enormous enhancement in the surface area-to-volume ratio (Table 1) and quantum scale phenomena. In this regard, it is worth noting that Feynman had predicted that devices at the atomic level would involve new kinds of forces and new kinds of possibilities, new kinds of eects. The problems of manufacture and reproduction of materials will be quite dierent.2 Over 38,000 publications have resulted due to extensive research on carbon nanotubes (CNTs),6 with only 3000 of these written in 19912000 (Table 2). The top 20 countries publishing articles on nanotubes, based on the number of publications as of March 2009 on CNTs,6 are listed in Table 3. Using that number of publications as a good indicator of the research output, the United States, China, and Japan are among the leading countries in CNT research in the world. Real-life applications of these materials will not be very far behind. For this reason, current and future research and industrial workforce professionals are very likely to encounter some aspects of nanotechnology including CNT science and technology in their education and professions. An overview of the chemistry of CNTs is presented here with related topics, including chemical structure, properties, applications, and technical challenges. This article will also provide material for developing CNT-based undergraduate projects, which may allow expansion of the current limited literature in this Journal and The Chemical Educator.7

and Galpern, completed Huckel calculations (i.e., calculating molecular orbital energy levels) showing that graphene sheets can curl up to make hollow molecules with a relatively large band gap.10 The worldwide enthusiasm for carbon-based nanomaterials came after Sumio Iijima synthesized needles of carbon made of hollow tubes by the electric-arc technique in 1991.11 A breakthrough occurred two years later when single-wall carbon nanotubes were discovered simultaneously and independently by Sumio Iijima12 and Donald Bethune.13 These materials gained further attention after the Nobel Prize in Chemistry was awarded in 1996 for the discovery of fullerenes or C60.14

DISCOVERY OF CARBON NANOTUBES In the late 1950s, Roger Bacon at Union Carbide was studying carbon bers and observed images of straight and hollow nanowhiskers with carbon layers that were separated by the same spacing as the planar layers of graphite.8 In the 1970s, Morinobu Endo observed carbon bers, produced by the pyrolysis of benzene and ferrocene at 1000 C, with a hollow core and catalytic particles at the end as observed under a high-resolution transmission electron microscope (HR-TEM).9 Russian scientists, Bochvar

STRUCTURE AND PROPERTIES OF CARBON NANOTUBES Carbon nanotubes (CNTs) have unique structural features and properties. In addition to being very small, they have high structural perfection and exceptional electronic, mechanical, optical, thermal, and transport properties. They are hollow cylindrical molecules composed of carbon atoms only and are equivalent to a graphitic (graphene) sheet rolled into a seamless tube, capped or uncapped at the ends. When carbon atoms combine to form graphite, one s orbital and two p orbitals hybridize to form three sp2 orbitals at 120 to each other within a plane. A strong covalent in-plane bond binds the atoms in the plane and results in high stiness and high strength of the CNTs.15 The remaining p orbital, perpendicular to the plane of the bonds, contributes to interlayer interaction and forms weak, out-of-plane, and delocalized bonds.16 CNTs have nanometer-scale diameters and nano-, micro-, or even millimeter-scale lengths giving them very large aspect (length/diameter) ratios that are sometimes greater than 104. These give them characteristics similar to single molecules or quasi-one-dimensional crystals with translational periodicity along the tube axis. CNTs can be divided into two groups: the multi-wall carbon nanotube (MWNT) and the single-wall carbon nanotube (SWNT), shown in Figure 1. MWNT are made of concentric cylinders placed around a common central hollow core and have diameters between 5 and 100 nm and a 0.34 nm
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Figure 1. Schematic representation of (A) single-wall carbon nanotubes (SWNT), (B) multi-wall carbon nanotube (MWNT); color is used to distinguish the walls.

Figure 3. (A) Schematic of the roll-up of a graphene sheet to form a SWNT structure. (B) OO0 denes the chiral vector Ch = na1 + ma2 = (n,m). Translation vector, T, is along the nanotube axis and perpendicular to Ch. The shaded area represents the unrolled unit cell formed by T and Ch. The chiral angle, , is dened as the angle between Ch and the (n,0) zigzag direction. The (n,0) zigzag and (n,n) armchair SWNTs are indicated in blue and red markings, respectively. From ref 19. Copyright 2002 American Chemical Society.

the length of the (n,m) SWNT unit cell. Once (n,m) is specied, other structural properties, such as diameter (dt) and chiral angle (), can be determined, dt 31=2 =acc m2 mn n2 1=2
Figure 2. Molecular models of two closed carbon nanotubes formed by introducing pentagons (shaded black) in the hexagonal carbon network. Apex angles () of 38.9 and 19.2 are formed by adding four and ve pentagons, respectively. Reprinted with permission from ref 18. Copyright 2003 Annual Review.

1 2

tan1 31=2 m=2n m

spacing between the layers.17 SWNT consist of only one wrapped graphene sheet having diameters between 0.4 and 4 nm.17 Owing to van der Waals forces between SWNT, they have a tendency to self-assemble into bundles or ropes. There are a number of ways of rolling the graphene sheet to form open or closed types of CNTs. An open-ended tube results when a single layer of graphite is folded into a cylinder and the open edges match perfectly to form a seamless structure. A closed tube is formed by inserting pentagons on each end of the cylinder, shown in Figure 2.18 The resulting apex angle depends on the number of pentagons inserted, and it results in higher chemical reactivity due to increased strain at these positions. Properties of CNTs depend on symmetries that can be determined by their diameter and helicity. The helicity or chirality of a CNT is characterized by a chiral vector and angle. The length of the chiral vector equals the circumference of the tube, and the tube axis is perpendicular to the rollup vector. This is represented graphically in Figure 3.19 The structure of a SWNT is uniquely characterized by the roll-up vector, Ch = na1 + ma2  (n,m), where a1 and a2 are graphenes primitive vectors and n,m are integers. The translation vector, T, is directed along the SWNT axis and perpendicular to Ch; the magnitude of T corresponds to
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where acc is the nearest-neighbor carbon atom distance of 0.142 nm.20 In this way, depending on how the two-dimensional graphene sheet is rolled up, three types of nanotubes are possible: (i) armchair, (ii) zigzag, and (iii) chiral shown in Figure 4.18 Armchair nanotubes are formed when two CC bonds on opposite sides of each hexagon are perpendicular to the tubes axis making n = m and = 30. Zigzag nanotubes are formed when the two CC bonds are parallel to the tube axis making either n or m = 0 and = 0. All other conformations in which the CC bonds lie at an angle to the tube axis are known as chiral with between 0 and 30. Although chemical bonding between the carbon atoms is identical and no doping or impurities are present, the three types of SWNT exhibit unique electronic properties. In general, a (n,m) carbon nanotube will be metallic when n m = 3q, where q is an integer, and semiconducting when n m 6 3q. Armchair (n,n) SWNT are always metallic with overlapping valence and conduction band, zigzag (n,0) SWNT are semimetallic with zero energy band gap with some exceptions, and two-thirds of the chiral (n,m) SWNT are semiconductors with nite band gap between valence and conduction bands. The electronic properties of SWNT are caused by quantum connement of electrons normal to the nanotube axis. Electrons can only propagate along the nanotube axis and are conned by a monolayer thickness of the graphene sheet. This quasi one-dimensionality causes the electronic density of states (i.e., energy levels able to be occupied)
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Figure 6. Raman spectra of carbon nanotubes.

Figure 4. Molecular models of SWNT exhibiting dierent chiralities. Reprinted with permission from ref 18. Copyright 2003 Annual Review.

Figure 5. Absorbance (gray) and emission (black) spectra of SWNT dispersed in lysozyme. From ref 21. Copyright 2006 Wiley-VCH Verlag GmbH & Co. KGaA. Reproduced with permission.

of isolated SWNT to have a series of sharp peaks in the electronic spectra dependent mainly on tube structure and diameter. These sharp peaks found in one-dimensional materials (nonaggregated, individual SWNT) are called van Hove singularities (VHS) and provide remarkable information about their optical properties. In contrast, broad and weak absorbance indicates aggregation due to van der Waals interactions disturbing electronic structures. The absorbance and emission spectrum of highly dispersed and debundled SWNT in an aqueous solution of lysozyme21 are shown in Figure 5. The absorbance (gray) spectrum shows peaks in the near-IR and far-IR absorption regions (4001500 nm) corresponding to the rst (S11) and second (S22) interband transitions for semiconducting SWNT, as well as the rst transition (M11) for metallic SWNT. In addition, debundled semiconducting SWNT also display a near-IR uorescence corresponding to the S11 transition between 900 and 1400 nm as shown in the emission (black) spectrum. The interactions between adjacent SWNTs in bundles quench the luminescence.22
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Study of vibrational modes in CNTs has been useful for understanding their structural makeup. A CNT vibrational spectrum is interesting due to its intricate dependence on diameter, and Raman spectroscopy has been a useful tool to study these vibrational modes. Using the right frequency of the Raman laser, phonons can be excited in SWNT leading to interesting features (peaks) in the Raman spectra, due to resonance phenomena and sensitivity to the tube structure. The most prominent Ramanactive peaks in CNTs are shown in Figure 6. Peaks at the low frequency (<400 cm1) are called the radial breathing modes (RBM) and the high frequency (>1200 cm1) peaks correspond to the disorder (D) and graphite (G and G0 ) modes. Although the D, G, and G0 modes are also found in graphite, the RBM mode is a unique feature for some types of CNTs, particularly in all SWNT, some double-wall nanotubes (DWNT), but not observed in MWNT. The position of the RBM mode is located between 75 and 300 cm1 and shifts with the diameter of the tubes. Owing to resonance-enhanced Raman intensity, several laser wavelengths are needed to nd the entire diameter distribution in a sample of SWNT.23 Theoretical bulk SWNT density depends on its diameter but independent of chirality.24 Equation 3 was used to nd the total number of carbon (C) atoms in a tube of diameter (dt) and length (h). Knowing that the atomic weight of a C atom is 12.011 amu, eq 4 was used to calculate the molar mass of a SWNT (MWSWNT) with a 1 nm diameter and 10 m length and was estimated to be 1.44 107 g/mol. Density (FNT) is then calculated using the nanotube molecular weight and its associated volume (Vt) using eq 5. Using this equation, the density of a SWNT bundle with 1 nm diameter is estimated to be 1.552 g/cm3, Number of carbon atoms dt h MW SWNT dt h FNT MW SWNT NA Vt 32 0:838368 3 4 5

32 12:011 g mol1 0:838368

where NA is Avogadros number. The relationships between SWNT diameter and the density and tensile modulus are shown in Figure 7. A tube with a diameter of more than 2 nm has a density less than water, which suggests that materials made from such tubes can be made to oat on water, even when they are in a fully packed state. SWNT density as a function of diameter can also be calculated from the best-t equation given in Figure 7A. The theoretical specic tensile
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CNT Fiber and Fabrics. Recently, a New Hampshire-based company Nanocomp Technologies, Inc. has produced (3 ft by 6 ft and longer) CNT fabrics/sheets made directly from the nanotube reactor.31 CNT fabrics and sheets show breaking strengths of 500 MPa to 1.2 GPa. These values are comparable to aluminum (breaking strength 500 MPa) and carbon steel (breaking strength 1 GPa), but the CNT sheets are only a fraction of the mass of aluminum and steel sheets of equal size. These fabrics are currently being studied for body armor applications. CNT yarns are also produced that exhibit tensile strength and toughness greater than current commercially available highperformance fibers Kevlar and Twaron.3234 Several factors aect the electrical properties of polymer carbon nanotube composites. These include (i) type of CNT, (ii) length of CNT, (iii) dispersion of CNT, (iv) ber or lm processing method, (v) ber draw ratio or orientation of CNT, and (vi) type of polymer. By tailoring the aforementioned properties, one can get electrically conducting bers with wide range of conductivities for dierent applications. For example, in PAN/CNT composite bers, depending on the processing parameters used, the electrical conductivities values can be sucient for electrostatic dissipation (conductivity e 1 104 S/m, for example, casings for electronic equipment); electrostatic painting (1 104 S/m < conductivity < 1 101 S/m, for example, materials that allow for the application of paint by electrostatic deposition); or EMI shielding (1 101 S/m e conductivity < 1 104 S/m, for example, heat-resistant electrically conductive adhesive tape) applications. Similarly, polymer/CNT lms have also been fabricated with electrical conductivities on the order of 104 S/m (EMI shielding) and have been used as electrodes in electrochemical capacitor devices.3539
Gas Sensor Applications40,41 Electrical Applications for CNT Composites

Figure 7. Dependence of (A) density and (B) tensile modulus on diameter of SWNT.

modulus of graphite along the graphite plane is 469 N/Tex (ratio of tensile modulus of 1060 GPa and its specic density of 2.26 g/cm3).25 The tensile and specic tensile moduli of SWNT as a function of nanotube diameter are plotted in Figure 7B. Tensile modulus decreases with increasing SWNT diameter, whereas the specic tensile modulus does not change with nanotube diameter and its value is same as that for graphite.

DIVERSE APPLICATIONS OF CNTS The properties of CNTs make them suitable for a variety of applications including sensors, electrodes, eld emission materials, catalyst support, electronic devices, reinforcements in high-performance composites, nanoelectronic devices, and supercapacitors.
Structural Composite Applications

There are several reasons that make CNTs promising materials for gas sensor applications: (i) the nanoscale size allows sensors to be small, compact, lightweight; (ii) the unique electronic congurations that change when the CNTs are exposed to specic gases allowing sensors to be extremely sensitive so that extremely small levels of gases can be detected (gas concentration limits are less than 0.5 ppm); (iii) exibility of CNTs to be functionalized, thus, chemical groups can be grafted to the CNT surface to enable sensors to be tailored toward specic gases; and (iv) the use of CNTs in electronic applications, thus, combining CNT-based gas sensors with microelectromechanical (MEM) devices.
Visual Display Applications

The extraordinary mechanical properties of CNTs make them ideal for structural composite applications. These materials have been combined with polymers to produce nanocomposites or fabricated directly into CNT bers and fabrics. Some examples of these materials include (i) poly(acrylonitrile) (PAN)/CNT-based carbon bers, (ii) CNT ber spun from CNT forests and aero gels, and (iii) CNT fabrics. PAN/CNT Nanocomposite-Based Carbon Fibers. CNTs have been used to reinforce conventional PAN-based carbon fibers. PAN-based carbon fibers are critical to the Department of Defenses structural materials needs. Fibers, made by gel spinning, lead to higher tensile strength and higher modulus than the conventional solution spun fibers.2630

The electron emission characteristics of CNTs make them good candidates for display applications, where companies such as Motorola have already developed a 5 in. nanoemissive display (NED).42 These CNT-based displays currently show 2030% power savings over current at panel displays.

CHEMICAL STRATEGIES TO SOLVE CNT-RELATED TECHNOLOGICAL CHALLENGES Control of the synthesis process is very important for the production of CNTs. Currently, the chemical vapor deposition (CVD) method is the most viable for commercial production of SWNT, although the arc-discharge and laser-ablation methods have also been used initially for CNT production. Both the arc-discharge and laser-ablation methods are currently limited to research (academic) use.4347 In the arc-discharge method
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Figure 8. Schematics of various carbon nanotube production methods including (A) electric arc discharge, (B) laser ablation, and (C) chemical vapor deposition.

(Figure 8), electric arc discharge is generated between two graphite electrodes under an inert atmosphere (helium or argon). The high temperature between the two rods during the process allows the sublimation of carbon. A direct current (dc) arc discharge is generated between the electrodes. The three components, argon, iron, and methane, are critical for the synthesis of SWNTs. A schematic for the laser-ablation method is shown in Figure 8B. The graphite target is vaporized by laser irradiation under owing inert atmosphere. The laser vaporization produces carbon species, which are swept by the owing gas from the high-temperature zone to a conical water-cooled copper collector. When a small amount of a transition metal such as Ni and Co has been added to the carbon target, SWNTs can form. SWNTs produced using the laser ablation method are remarkably uniform in diameter and form bundles of 520 nm diameter. These bundles exhibit a crystalline two-dimensional triangular lattice. Although the CVD method had been used to produce carbon lament and ber since the 1960s, it had not been applied to make carbon nanotubes until 1993 (Figure 8C). CVD production of SWNT involves the decomposition of a hydrocarbon over supported metal catalyst nanoparticles and as-grown SWNT is subsequently removed from the support.4850 For SWNT production using the high-pressure CO conversion (HiPCO) process, CO pressure is maintained between 30 and 50 atm and the temperature ranges from 900 to 1100 C.51 During the process, gas-phase CO ows over catalytic iron
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clusters Fe(CO)5. At this temperature and pressure, the ow of CO causes the thermal decomposition of Fe(CO)5, which leads to the formation of SWNT. This production method can yield a production rate of 450 mg/h of SWNT, and each batch has a purity level of 97%.52 All methods of CNT synthesis have limitations for yielding bulk materials with structural consistency (uniform diameter, chirality, defects, functional groups) and the presence of various types of impurities in the form of graphitic nanoparticles, amorphous carbon, fullerenes, polycyclic aromatic hydrocarbons, and residual catalyst material including particles containing transition metal and catalyst support. CNT structural features and purity are mostly characterized by electron microscopy (EM) including scanning EM (SEM) or transmission EM (TEM), thermo-gravimetric analysis (TGA), Raman spectroscopy, ultravioletvisiblenear-infrared (UVvis-NIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and X-ray diraction (XRD). The advantages and limitations of these methods53,54 are summarized in Table 4. Figure 9 shows HR-TEM images of an as-produced CNT sample containing residual catalyst metal particles with fewer impurities remaining after purication. Several methods of purication have been used to remove the impurities from commercial CNT samples. Purication techniques are classied into chemical or physical methods and detailed description of the methods are included in a review.53 Chemical methods employ selective oxidation where the carbonaceous impurities oxidize faster than the CNTs and the metallic impurities dissolve in acids. The high oxidation activity of the impurities is due to more dangling bonds and structural defects in the amorphous carbon and large curvature and pentagonal carbon rings in carbon nanoparticles.55,56 In general, chemical methods include gas-phase oxidation (with air, O2, Cl2, H2O, etc.), liquidphase oxidation (with acids such as HNO3, H2SO4, HCl; oxidants such as H2O2 and KMnO4), electrochemical oxidation, and functionalization.5764 Chemical methods of purication have the disadvantage of destroying the pristine structure of the CNT by opening ends, cutting the size, damaging the surface structure, and introducing reactive functional groups. In contrast, physical methods employ nondestructive and nonoxidizing techniques. Commonly used physical methods include ltration, chromatography, centrifugation, electrophoresis, and high-temperature annealing.6572 These methods employ dierences in morphology and physical properties, such as aspect ratio, solubility, gravity, and magnetism, between the CNT and impurities. Physical methods have the disadvantage of limited quantity of sample puried each time, poor eectiveness in removing impurities, and the need to be performed in solution requiring the samples to have good dispersibility that can be achieved by adding surfactants or sonication. Pristine SWNT have no surface functional groups and are extremely resistant to wetting. An additional problem with SWNT is their tendency to exist predominantly in an aggregated state that interferes with the optical and electrical properties. As mentioned earlier, the aggregation and bundling are due to van der Waals interactions that cause the tubes to form parallel bundles or ropes. In Figure 10, HR-TEM shows entangled SWNT bundles or ropes with an average diameter of 10 25 nm, which implies that each rope contains hundreds of individual SWNT and forms a highly dense, complex network.44 Dispersion of CNTs in a specic solvent depends strongly on the method used for their synthesis, the content of impurities, and the purication method.73 To make CNTs more easily
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Journal of Chemical Education Table 4. Summary of Commonly Used CNT Characterization Techniques
Technique EM TGA Advantages Allows direct observation of impurities, local structures, and CNT defects. Easy and straightforward method that provides precise content of metal impurities. Provides information about the thermal stability of a CNT and can be used to evaluate the quality of a CNT. Raman Spectroscopy Fast, convenient, and nondestructive method that provides detailed information on diameter, electronic structure, and purity of CNTs. Can be used to distinguish metallic and semiconducting as well as provides information about chirality of SWNT. UVVis-NIR Spectroscopy XPS XRD Rapid and convenient technique that provides conductivity features and content of SWNT. Provides information about functional groups on CNTs. Can be used to distinguish SWNT versus MWNT sample. Can also be used to calculate the number of graphitic layers in MWNT. Provides no information on the nature of metal impurity. A single Limitations Does not provide quantitative evaluation of CNT purity because a small volume of sample is analyzed.

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Destructive technique. Dicult to assign individual oxidation events to specic carbonaceous species such as amorphous carbon, graphitic carbon, and fullerenes.

laser cannot probe the entire sample because Raman scattering is observed only when probing laser is in resonance with an electronic transition in the SWNT.

Absolute purity of SWNT cannot be obtained due to unavailability of 100% pure SWNT standards or accurate extinction coecients. Does not provide information about electronic structure and diameter distribution. Does not provide the diameter distribution of CNTs in a sample.

Figure 9. Transmission electron microscope (TEM) image of HiPCO SWNT, (A) unpuried with 35 wt % metal catalyst impurities and (B) purication with 2.4 wt % metal catalyst impurities.

dispersible in liquids, physical or chemical methods have been used to attach certain molecules, or functional groups, to their smooth sidewalls without signicantly changing their desirable properties. Physical functionalization involves amphiphilic molecules (surfactants), polymers, and biomolecules, noncovalently associating with the sides of the nanotubes disrupting the hydrophobic interface with water and the interactions within the aggregated tubes.74 This method has the distinct advantage of preventing disruption of the tubes sp2 structure and conjugation while preserving its electronic properties. Chemical functionalization involves a variety of chemicals that covalently react at the end-caps, defect-sites, and sidewalls.75 As CNT manufacturing and processing problems are solved, new challenges associated with their toxicity arise due to their light mass and potential to enter the working environment as suspended solid matter of respirable sizes. Cell culture studies show that CNTs are cytotoxic, capable of impairing pulmonary functions by inducing inammation, epitheliloid granulomas, brosis, and biochemical toxicity if they reach the lung in sucient quantities.76

Figure 10. (A) Scanning electron micrograph (SEM) of SWNT showing mat of entangled ropes or bundles 1020 nm in diameter and many micrometers long. Scale bar is 100 nm (B) At low resolution (scale bar, 100 nm), transmission electron microscope (TEM) images show ropes of SWNT and small amounts of metal catalyst coated with amorphous carbon. From ref 44. Reprinted with permission from AAAS.

OPPORTUNITIES FOR INCLUDING CNTS IN THE UNDERGRADUATE CURRICULUM There are plenty of opportunities that exist for chemistry students to explore theoretical concepts and experimental techniques about CNTs at the undergraduate level. Using the empirical equations, plots, and data available in this article and the literature, students in a physical chemistry course can learn about basic structural features and properties of CNTs. For example, given a set of (n,m) value, the diameter and chiral angles of the CNT can be calculated as well as their chirality (armchair, zigzag, or chiral) and electronic behavior (metallic or semiconducting) can be predicted. Length and diameter measurements can be further used to calculate their molar mass, density, and tensile modulus. With the help of simple laboratory apparatus such as a sonicator and centrifuge, students in analytical chemistry can explore two of the fundamental technological problems involving insolubility, dispersibility, and bundling of CNTs. A variety of traditional techniques used
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Journal of Chemical Education Table 5. Expected Growth in Nanotubes Markets

Growth/$ millionsa Market Total Demand 2004 6 By Type Single-walled nanotubes Multi-walled nanotubes 0 6 By End Use Electronics Automotive Aerospace/Defense Other 0 1 0 5 By Region U.S. Western Europe Asia/Pacic Other
a

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dx.doi.org/10.1021/ed1005163 |J. Chem. Educ. 2012, 89, 221229

2009 215

2014 1070

95 120

600 470

90 31 10 84

395 165 65 445

2 1 3 0

57 32 113 13

290 180 500 100

Data from ref 77.

frequently in synthetic organic and inorganic chemistry laboratories may also be applied to covalently and noncovalently functionalize CNTs to overcome solubility problems and purify commercial samples. The nature of interaction of CNTs with solvents and polymers (i.e., surfactants and biomolecules such as proteins and DNA) with varying pH characteristics can be explored with the help of absorption and uorescence spectroscopy in an advanced polymer or biochemistry laboratory. Using two common undergraduate chemical instruments, nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR), organic chemistry students can be provided with experience in identifying the nature of defects and functional groups on the surface of the CNTs. In addition, many undergraduate departments now have the Raman spectrometer that provides opportunities for students in instrumental analysis to carry out a detailed structural study of CNTs that can provide quantitative information about their diameters, chirality, and defects. For even deeper educational development, the experience of studying CNTs can be enhanced several fold with the ability to obtain and analyze images using sophisticated microscopic facilities including the atomic force microscope (AFM), scanning electron microscope (SEM), and transmission electron microscope (TEM).

SUMMARY The recent growth and future prospects for the CNTs market, which is expected to grow signicantly over the next decade,77 is shown in Table 5. For this reason, it should be advantageous for the future workforce, including chemistry professionals, to be trained in synthetic techniques and instrumentation related to all aspects of CNTs. The chemists of the future are expected to have tremendous opportunities to explore in the area of CNTbased science and technology.

AUTHOR INFORMATION
Corresponding Author

*E-mail: sbdutt@westga.edu.

Journal of Chemical Education

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