Chemical vapor detection using single-walled carbon nanotubes

Single-walled carbon nanotubes possess unique properties that make them a potentially ideal material for chemical sensing. However, their extremely small size also presents technical challenges for realizing a practical sensor technology. In this tutorial review we explore the transduction physics by which the presence of molecular adsorbates is converted into a measurable electronic signal, and we identify solutions to the problems such as nanotube device fabrication and large, low-frequency noise that have inhibited commercial sensor development. Finally, we examine strategies to provide the necessary chemical specificity to realize a nanotube-based detection system for trace-level chemical vapor detection.     

DNA functionalized single-walled carbon nanotubes for electrochemical detection

Single-walled carbon nanotubes (SWNTs) were effectively dispersed and functionalized by wrapping with single-stranded DNA (ssDNA). The ssDNA-SWNTs attach strongly on glass substrate and easily form a uniform film, making it possible for electrochemical analysis and sensing. The film was fabricated into a working electrode, which exhibited good electrochemical voltammetric properties, such as flat and wide potential window, well-defined quasi-reversible voltammetric responses, and quick electron transfer for a Fe(CN)6(3-)/Fe(CN)6(4) system, indicating that the ssDNA-SWNTs film should be a good analytical electrode for electrochemical detection or sensing. This was demonstrated by highly selective and sensitive detection of a low concentration of dopamine in the presence of excess ascorbic acid.     

Singling out the electrochemistry of individual single-walled carbon nanotubes in solution

Bandgap fluorescence spectroscopy of aqueous, micelle-like suspensions of SWNTs has given access to the electronic energies of individual semiconducting SWNTs, while substantially lower is the success achieved in the determination of the redox properties of SWNTs as individual entities. Here we report an extensive voltammetric and vis-NIR spectroelectrochemical investigation of true solutions of unfunctionalized SWNTs and determine the standard electrochemical potentials of reduction and oxidation as a function of the tube diameter of a large number of semiconducting SWNTs. We also establish the Fermi energy and the exciton binding energy for individual tubes in solution. The linear correlation found between the potentials and the optical transition energies is quantified in two simple equations that allow one to calculate the redox potentials of SWNTs that are insufficiently abundant or absent in the samples.     

Bioelectrochemical single-walled carbon nanotubes

Metalloproteins and enzymes can be immobilized on SWNTs of different surface chemistry. The combination of high surface area, robust immobilization and inherent nanotube electrochemical properties is of promising application in bioelectrochemistry.     

Theoretical study of the 13C NMR spectroscopy of single-walled carbon nanotubes

The 13C NMR spectroscopy of armchair and zigzag single-walled carbon nanotubes has been investigated theoretically. Spectra for (4,4), (5,5), (6,6), (6,0), (9,0), and (10,0) nanotubes have been simulated based on ab initio calculations of model systems. The calculations predict a dominant band arising from the carbon atoms in the "tube" with smaller peaks at higher chemical shifts arising from the carbon atoms of the caps. The dominant band lies in the range of 128 and 138 ppm. Its position depends weakly on the length, width, and chirality of the tubes. The calculations demonstrate how structural information may be gleaned from relatively low-resolution nanotube 13C NMR spectra.     

Lithium storage in single-walled carbon nanotubes

Here, we investigated the lithium insertion/extraction mechanism in single-walled carbon nanotubes (SWNTs) based both on the empty SWNTs and filled SWNTs, including ferrocene-filled SWNTs (Fc@SWNTs) and C₆₀-filled SWNTs (C₆₀@SWNTs). SWNTs, C₆₀@SWNTs and Fc@SWNTs were systematically investigated as anode materials for Li-ion batteries. The electrochemical performance of the C₆₀@SWNT electrode was slightly better than that of the SWNTs, and the reversible capacity of Fc@SWNTs per unit weight was ～1.7 times greater than that of the empty SWNTs due to its special tube internal structure. It was proved that the dominant reversible sites for lithium storage in empty SWNTs are the trigonal interstitial channels. Meanwhile, lithium can reversibly insert or extract the inner channels of the tubes after doping with ferrocene; the reversible capacity presented in the inner channels of Fc@SWNTs is about Li_1.13C₆.     

Soluble ultra-short single-walled carbon nanotubes

Soluble, ultra-short (length < 60 nm), carboxylated, single-walled carbon nanotubes (SWNTs) have been prepared by a scalable process. This process, predicated on oleum's (100% H2SO4 with excess SO3) ability to intercalate between individual SWNTs inside SWNT ropes, is a procedure that simultaneously cuts and functionalizes SWNTs using a mixture of sulfuric and nitric acids. The solubility of these ultra-short SWNTs (US-SWNTs) in organic solvents, superacid and water is about 2 wt %. The availability of soluble US-SWNTs could open opportunities for forming high performance composites, blends, and copolymers without inhibiting their processibility.     

Dispersion of single-walled carbon nanotubes in aqueous solution with a thermo-responsive pentablock terpolymer

Single-walled carbon nanotubes (SWNTs) were dispersed in pure water with a thermo-responsive amphiphilic PNIPAM₁₅₀-F108-PNIPAM₁₅₀ pentablock terpolymer in comparison with its precursor PEO₁₃₆-PPO₄₅-PEO₁₃₆ (F108) triblock copolymer. The stability, dispersibility, and thermo-responsive behaviors of the polymer/SWNT hybrids were characterized by UV–vis–NIR spectroscopy, thermal gravimetric analysis, viscosity measurement, Raman spectroscopy, and high-resolution transmission electron microscopy. The pentablock/SWNT hybrids showed superior ability in stabilization over F108/SWNT hybrids, and no sign of sedimentation was found at room temperature for 6 weeks or even 2 months of storage. The pentablock terpolymer can efficiently disperse SWNTs into individual tubes or small bundles with average diameter of about 5 nm, and their chains were helically wrapped onto the nanotube surface, whereas the larger bundles of the nanotubes with sizes of 15–25 nm were observed in F108/SWNT hybrids. Moreover, the pentablock/SWNT hybrids switched reversibly between the well-exfoliated and the aggregated states when cyclically increasing and decreasing temperature.     

Protein-assisted solubilization of single-walled carbon nanotubes

We report a simple method that uses proteins to solubilize single-walled carbon nanotubes (SWNTs) in water. Characterization by a variety of complementary techniques including UV-Vis spectroscopy, Raman spectroscopy, and atomic force microscopy confirmed the dispersion at the individual nanotube level. A variety of proteins differing in size and structure were used to generate individual nanotube solutions by this noncovalent functionalization procedure. Protein-mediated solubilization of nanotubes in water may be important for biomedical applications. This method of solubilization may also find use in approaches for controlling the assembly of nanostructures, and the wide variety of functional groups present on the adsorbed proteins may be used as orthogonal reactive handles for the functionalization of carbon nanotubes.     

Discrete dispersion of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWNTs) have been effectively wetted and dispersed in saturated sodium hydroxide (NaOH) alcohol-water solutions with little surface damage or shortening of the tubes; the treated material was dissolvable as individual tubes in many common organic solvents.     

Encapsulation of carbon chain molecules in single-walled carbon nanotubes

The vacuum space inside carbon nanotubes offers interesting possibilities for the inclusion, transportation, and functionalization of foreign molecules. Using first-principles density functional calculations, we show that linear carbon-based chain molecules, namely, polyynes (C(m)H(2), m = 4, 6, 10) and the dehydrogenated forms C(10)H and C(10), as well as hexane (C(6)H(14)), can be spontaneously encapsulated in open-ended single-walled carbon nanotubes (SWNTs) with edges that have dangling bonds or that are terminated with hydrogen atoms, as if they were drawn into a vacuum cleaner. The energy gains when C(10)H(2), C(10)H, C(10), C(6)H(2), C(4)H(2), and C(6)H(14) are encapsulated inside a (10,0) zigzag-shaped SWNT are 1.48, 2.04, 2.18, 1.05, 0.55, and 1.48 eV, respectively. When these molecules come inside a much wider (10,10) armchair SWNT along the tube axis, they experience neither an energy gain nor an energy barrier. They experience an energy gain when they approach the tube walls inside. Three hexane molecules can be encapsulated parallel to each other (i.e., nested) inside a (10,10) SWNT, and their energy gain is 1.98 eV. Three hexane molecules can exhibit a rotary motion. One reason for the stability of carbon chain molecules inside SWNTs is the large area of weak wave function overlap. Another reason concerns molecular dependence, that is, the quadrupole-quadrupole interaction in the case of the polyynes and electron charge transfer from the SWNT in the case of the dehydrogenated forms. The very flat potential surface inside an SWNT suggests that friction is quite low, and the space inside SWNTs serves as an ideal environment for the molecular transport of carbon chain molecules. The present theoretical results are certainly consistent with recent experimental results. Moreover, the encapsulation of C(10) makes an SWNT a (purely carbon-made) p-type acceptor. Another interesting possibility associated with the present system is the direction-controlled transport of C(10)H inside an SWNT under an external field. Because C(10)H has an electric dipole moment, it is expected to move under a gradient electric field. Finally, we derive the entropies of linear chain molecules inside and outside an open-ended SWNT to discuss the stability of including linear chain molecules inside an SWNT at finite temperatures.     

Stability of supershort single-walled carbon nanotubes

How short can single-walled carbon nanotubes (SWNTs) be? How stable are such supershort SWNTs (ss-SWNTs)? This work is the first to address these questions. On the basis of binding energy (E(B)), standard heats of formation , and strain energy (E(S)), we found that SWNTs with only one benzene ring in the axial direction, which we refer to as supershort SWNTs (ss-SWNTs), can be thermodynamically stable. On the basis of the data of E(B), , and E(S), the relative stabilities of ss-SWNTs, fullerenes, polycyclic aromatic hydrocarbons, and butadiyne are discussed. This study has laid a theoretical foundation for the possible synthesis of ss-SWNTs.     

Infrared spectroscopy of single-walled carbon nanotubes

By using the spectral moments method, we calculate the infrared spectra of chiral and achiral single-walled carbon nanotubes (SWCNTs) of different diameters and lengths. We show that the number of the infrared modes, their frequencies, and intensities depend on the length and chirality of the nanotubes. Furthermore, the dependence of the infrared spectrum as a function of the size of the SWCNT bundle is analyzed. These predictions are useful to interpret the experimental infrared spectra of SWCNTs.     

Fluorimetric characterization of single-walled carbon nanotubes

Single-walled carbon nanotubes (SWCNTs) are a family of structurally related artificial nanomaterials with unusual properties and many potential applications. Most SWCNTs can emit spectrally narrow near-IR fluorescence at wavelengths that are characteristic of their precise diameter and chiral angle. Near-IR fluorimetry therefore offers a powerful approach for identifying the structural species present in SWCNT samples. Such characterization is increasingly important for nanotube production, study, separation, and applications. General-purpose and specialized instruments suitable for SWCNT fluorimetric analysis are described, and methods for interpreting fluorimetric data to deduce the presence and relative abundances of different SWCNT species are presented. Fluorescence methods are highly effective for detecting SWCNTs in challenging samples such as complex environmental or biological specimens because of the methods’ high sensitivity and selectivity and the near absence of interfering background emission at near-IR wavelengths. Current limitations and future prospects for fluorimetric characterization of SWCNTs are discussed.     

Long super-bundles of single-walled carbon nanotubes

200 nm-thick super bundles showing a novel polygonization and densely aligned arrangement are found in long single-walled carbon nanotube (SWNT) strands prepared by the vertical floating catalytic method.     

Functionalised endohedral fullerenes in single-walled carbon nanotubes

Atomically thin carbon nanotubes serve as transparent-test tubes for individual molecules of functionalised endohedral fullerenes. Aberration-corrected transmission electron microscopy reveals the complex dynamic behaviour of these molecules at the atomic level, and it sheds light on the mechanism of their encapsulation into nanotubes.     

Coating single-walled carbon nanotubes with phospholipids

Single-walled carbon nanotubes (SWNTs), being hydrophobic by nature, aggregate in water to form large bundles. However, isolated SWNTs possess unique physical and chemical properties that are desirable for sensing and biological applications. Conventionally isolated SWNTs can be obtained by wrapping the tubes with biopolymers or surfactants. The binding modes proposed for these solubilization schemes, however, are less than comprehensive. Here we characterize the efficacies of solubilizing SWNTs through various types of phospholipids and other amphiphilic surfactants. Specifically, we demonstrate that lysophospholipids, or single-chained phospholipids offer unprecedented solubility for SWNTs, while double-chained phospholipids are ineffective in rendering SWNTs soluble. Using transmission electron microscopy (TEM) we show that lysophospholipids wrap SWNTs as striations whose size and regularity are affected by the polarity of the lysophospholipids. We further show that wrapping is only observed when SWNTs are in the lipid phase and not the vacuum phase, suggesting that the environment has a pertinent role in the binding process. Our findings shed light on the debate over the binding mechanism of amphiphilic polymers and cylindrical nanostructures and have implications on the design of novel supramolecular complexes and nanodevices.     

Azafullerenes encapsulated within single-walled carbon nanotubes

Methods of insertion of azafullerenes in single-walled carbon nanotubes (SWNTs) at different temperatures were investigated, while the effects of the conditions applied on the structure of azafullerene-based peapods, namely, C59N@SWNTs, were explored. Morphological characteristics of C59N@SWNTs were assessed and evaluated by means of high-resolution transmission electron microscopy (HR-TEM). Pathways and chemical reactions that occur upon encapsulation of C59N within SWNTs were evaluated. Monomeric azafullerenyl radical C59N. as inserted into SWNTs at high temperature, from purified (C59N)2 in the gas phase, can undergo a variety of different transformations forming dimers, oligomers or existing in its monomeric form inside SWNTs due to the stabilization effect by nanotube side walls. However, under milder conditions, that is, at lower temperature, bisazafullerene (C59N)2 can be inserted into SWNTs in its pristine dimeric form.