Tunable Hybridized Morphologies Obtained through Flash Joule Heating of Carbon Nanotubes.

Hybrid carbon nanomaterials, such as those that incorporate carbon nanotubes into graphene sheets, have been found to display interesting mechanical and electrical properties because of their covalent bonding and π-π stacking domains. However, synthesis of these hybrid materials is limited by the high energetic cost of techniques like chemical vapor deposition. Here, we demonstrate the solvent- and gas-free synthesis of a 2D carbon nanotube/graphene network through flash Joule heating of pristine carbon nanotubes. The relative proportion of each morphology in the hybrid material can be tuned by varying the pulse time, as confirmed by Raman spectroscopy and microscopy. Triboindentation of epoxy composites made with the hybrid material shows increases of 162% and 64% to the hardness and Young's modulus, respectively, compared with the neat epoxy. These results demonstrate that flash Joule heating can be used to inexpensively convert carbon nanotubes into a hybrid network of nanotubes and graphene for use as an effective reinforcing additive in epoxy composites.

Liquid crystals of neat boron nitride nanotubes and their assembly into ordered macroscopic materials.

Boron nitride nanotubes (BNNTs) have attracted attention for their predicted extraordinary properties; yet, challenges in synthesis and processing have stifled progress on macroscopic materials. Recent advances have led to the production of highly pure BNNTs. Here we report that neat BNNTs dissolve in chlorosulfonic acid (CSA) and form birefringent liquid crystal domains at concentrations above 170 ppmw. These tactoidal domains merge into millimeter-sized regions upon light sonication in capillaries. Cryogenic electron microscopy directly shows nematic alignment of BNNTs in solution. BNNT liquid crystals can be processed into aligned films and extruded into neat BNNT fibers. This study of nematic liquid crystals of BNNTs demonstrates their ability to form macroscopic materials to be used in high-performance applications.

Laser-Induced Conversion of Teflon into Fluorinated Nanodiamonds or Fluorinated Graphene.

Laser-assisted materials fabrication is an advanced technique that has propelled recent carbon synthesis approaches. Direct laser writing on polyimide or lignocellulose materials by a CO2 laser has successfully transformed the substrates into hierarchical graphene. However, formation of other carbon allotropes such as diamond and fullerene remains challenging. Here, we report the direct synthesis of fluorinated nanodiamonds or fluorinated graphene by treating polytetrafluoroethylene (Teflon, or PTFE) with a 9.3 µm pulsed CO2 laser under argon; no exogenous fluorine source is needed. The laser is part of a commercial laser cutting/scribing system that is found in most machine shops. Therefore, it is a readily accessible tool. This discovery could inspire future development for the laser-assisted synthesis of functionalized carbon allotropes.

Graphene oxide for effective radionuclide removal.

Here we show the efficacy of graphene oxide (GO) for rapid removal of some of the most toxic and radioactive long-lived human-made radionuclides from contaminated water, even from acidic solutions (pH < 2). The interaction of GO with actinides including Am(III), Th(IV), Pu(IV), Np(V), U(VI) and typical fission products Sr(II), Eu(III) and Tc(VII) were studied, along with their sorption kinetics. Cation/GO coagulation occurs with the formation of nanoparticle aggregates of GO sheets, facilitating their removal. GO is far more effective in removal of transuranium elements from simulated nuclear waste solutions than other routinely used sorbents such as bentonite clays and activated carbon. These results point toward a simple methodology to mollify the severity of nuclear waste contamination, thereby leading to effective measures for environmental remediation.

Graphene nanoribbons as an advanced precursor for making carbon fiber.

Graphene oxide nanoribbons (GONRs) and chemically reduced graphene nanoribbons (crGNRs) were dispersed at high concentrations in chlorosulfonic acid to form anisotropic liquid crystal phases. The liquid crystal solutions were spun directly into hundreds of meters of continuous macroscopic fibers. The relationship of fiber morphology to coagulation bath conditions was studied. The effects of colloid concentration, annealing temperature, spinning air gap, and pretension during annealing on the fibers' performance were also investigated. Heat treatment of the as-spun GONR fibers at 1500 °C produced thermally reduced graphene nanoribbon (trGNR) fibers with a tensile strength of 378 MPa, Young's modulus of 36.2 GPa, and electrical conductivity of 285 S/cm, which is considerably higher than that in other reported graphene-derived fibers. This better trGNR fiber performance was due to the air gap spinning and annealing with pretension that produced higher molecular alignment within the fibers, as determined by X-ray diffraction and scanning electron microscopy. The specific modulus of trGNR fibers is higher than that of the commercial general purpose carbon fibers and commonly used metals such as Al, Cu, and steel. The properties of trGNR fibers can be further improved by optimizing the spinning conditions with higher draw ratio, annealing conditions with higher pretensions, and using longer flake GONRs. This technique is a new high-carbon-yield approach to make the next generation carbon fibers based on solution-based liquid crystal phase spinning.

Spin dynamics and relaxation in graphene nanoribbons: electron spin resonance probing.

Here we report the results of a multifrequency (~9, 20, 34, 239.2, and 336 GHz) variable-temperature continuous wave (cw) and X-band (~9 GHz) pulse electron spin resonance (ESR) measurement performed at cryogenic temperatures on potassium split graphene nanoribbons (GNRs). Important experimental findings include the following: (a) The multifrequency cw ESR data infer the presence of only carbon-related paramagnetic nonbonding states, at any measured temperature, with the g value independent of microwave frequency and temperature. (b) A linear broadening of the ESR signal as a function of microwave frequency is noticed. The observed linear frequency dependence of ESR signal width points to a distribution of g factors causing the non-Lorentzian line shape, and the g broadening contribution is found to be very small. (c) The ESR process is found to be characterized by slow and fast components, whose temperature dependences could be well described by a tunneling level state model. This work not only could help in advancing the present fundamental understanding on the edge spin (or magnetic)-based properties of GNRs but also pave the way to GNR-based spin devices.

Pristine graphite oxide.

Graphite oxide (GO) is a lamellar substance with an ambiguous structure due to material complexity. Recently published GO-related studies employ only one out of several existing models to interpret the experimental data. Because the models are different, this leads to confusion in understanding the nature of the observed phenomena. Lessening the structural ambiguity would lead to further developments in functionalization and use of GO. Here, we show that the structure and properties of GO depend significantly on the quenching and purification procedures, rather than, as is commonly thought, on the type of graphite used or oxidation protocol. We introduce a new purification protocol that produces a product that we refer to as pristine GO (pGO) in contrast to the commonly known material that we will refer to as conventional GO (cGO). We explain the differences between pGO and cGO by transformations caused by reaction with water. We produce ultraviolet-visible spectroscopic, Fourier transform infrared spectroscopic, solid-state nuclear magnetic resonance spectroscopic, thermogravimetric, and scanning electron microscopic analytical evidence for the structure of pGO. This work provides a new explanation for the acidity of GO solutions and allows us to add critical details to existing GO models.

Graphene oxide as a high-performance fluid-loss-control additive in water-based drilling fluids.

Graphene oxide (GO) performs well as a filtration additive in water-based drilling fluids at concentrations as low as 0.2 % (w/w) by carbon content. Standard American Petroleum Institute (API) filtration tests were conducted on pH-adjusted, aqueous dispersions of GO and xanthan gum. It was found that a combination of large-flake GO and powdered GO in a 3:1 ratio performed best in the API tests, allowing an average fluid loss of 6.1 mL over 30 min and leaving a filter cake ~20 µm thick. In comparison, a standard suspension (~12 g/L) of clays and polymers used in the oil industry gave an average fluid loss of 7.2 mL and a filter cake ~280 µm thick. Scanning electron microscopy imaging revealed the extreme pliability of well-exfoliated GO, as the pressure due to filtration crumpled single GO sheets, forcing them to slide through pores with diameters much smaller than the flake's flattened size. GO solutions also exhibited greater shear thinning and higher temperature stability compared to clay-based fluid-loss additives, demonstrating potential for high-temperature well applications.

Layer-by-layer removal of graphene for device patterning.

The patterning of graphene is useful in fabricating electronic devices, but existing methods do not allow control of the number of layers of graphene that are removed. We show that sputter-coating graphene and graphene-like materials with zinc and dissolving the latter with dilute acid removes one graphene layer and leaves the lower layers intact. The method works with the four different types of graphene and graphene-like materials: graphene oxide, chemically converted graphene, chemical vapor-deposited graphene, and micromechanically cleaved ("clear-tape") graphene. On the basis of our data, the top graphene layer is damaged by the sputtering process, and the acid treatment removes the damaged layer of carbon. When used with predesigned zinc patterns, this method can be viewed as lithography that etches the sample with single-atomic-layer resolution.

Highly conductive graphene nanoribbons by longitudinal splitting of carbon nanotubes using potassium vapor.

Here we demonstrate that graphene nanoribbons (GNRs) free of oxidized surfaces can be prepared in large batches and 100% yield by splitting multiwalled carbon nanotubes (MWCNTs) with potassium vapor. If desired, exfoliation is attainable in a subsequent step using chlorosulfonic acid. The low-defect density of these GNRs is indicated by their electrical conductivity, comparable to that of graphene derived from mechanically exfoliated graphite. The possible origins of directionally selective splitting of MWCNTs have been explored using computer modeling, and plausible explanations for the unique role of potassium were found.

Graphene nanoribbon devices produced by oxidative unzipping of carbon nanotubes.

We demonstrate that graphene nanoribbons (GNRs), produced by the chemical unzipping of carbon nanotubes, can be conveniently used from solution to hand-paint unidirectional arrays of GNRs atop silicon oxide. Through this simple alignment technique, numerous GNR-based devices, including field effect transistors, sensors, and memories can be easily fabricated on a single chip, and then used to generate statistically relevant device assessments. Such studies immediately give insights into, for example, multilayering properties on conductance, the profound effects that atmospheric adsorbates have upon the transfer characteristics of graphene, and other phenomena affecting the performance of GNR devices.

Improved synthesis of graphene oxide.

An improved method for the preparation of graphene oxide (GO) is described. Currently, Hummers' method (KMnO(4), NaNO(3), H(2)SO(4)) is the most common method used for preparing graphene oxide. We have found that excluding the NaNO(3), increasing the amount of KMnO(4), and performing the reaction in a 9:1 mixture of H(2)SO(4)/H(3)PO(4) improves the efficiency of the oxidation process. This improved method provides a greater amount of hydrophilic oxidized graphene material as compared to Hummers' method or Hummers' method with additional KMnO(4). Moreover, even though the GO produced by our method is more oxidized than that prepared by Hummers' method, when both are reduced in the same chamber with hydrazine, chemically converted graphene (CCG) produced from this new method is equivalent in its electrical conductivity. In contrast to Hummers' method, the new method does not generate toxic gas and the temperature is easily controlled. This improved synthesis of GO may be important for large-scale production of GO as well as the construction of devices composed of the subsequent CCG.

Effective drug delivery, in vitro and in vivo, by carbon-based nanovectors noncovalently loaded with unmodified Paclitaxel.

Many new drugs have low aqueous solubility and high therapeutic efficacy. Paclitaxel (PTX) is a classic example of this type of compound. Here we show that extremely small (<40 nm) hydrophilic carbon clusters (HCCs) that are PEGylated (PEG-HCCs) are effective drug delivery vehicles when simply mixed with paclitaxel. This formulation of PTX sequestered in PEG-HCCs (PTX/PEG-HCCs) is stable for at least 20 weeks. The PTX/PEG-HCCs formulation was as effective as PTX in a clinical formulation in reducing tumor volumes in an orthotopic murine model of oral squamous cell carcinoma. Preliminary toxicity and biodistribution studies suggest that the PEG-HCCs are not acutely toxic and, like many other nanomaterials, are primarily accumulated in the liver and spleen. This work demonstrates that carbon nanomaterials are effective drug delivery vehicles in vivo when noncovalently loaded with an unmodified drug.

Spontaneous high-concentration dispersions and liquid crystals of graphene.

Graphene combines unique electronic properties and surprising quantum effects with outstanding thermal and mechanical properties. Many potential applications, including electronics and nanocomposites, require that graphene be dispersed and processed in a fluid phase. Here, we show that graphite spontaneously exfoliates into single-layer graphene in chlorosulphonic acid, and dissolves at isotropic concentrations as high as approximately 2 mg ml(-1), which is an order of magnitude higher than previously reported values. This occurs without the need for covalent functionalization, surfactant stabilization, or sonication, which can compromise the properties of graphene or reduce flake size. We also report spontaneous formation of liquid-crystalline phases at high concentrations ( approximately 20-30 mg ml(-1)). Transparent, conducting films are produced from these dispersions at 1,000 Omega square(-1) and approximately 80% transparency. High-concentration solutions, both isotropic and liquid crystalline, could be particularly useful for making flexible electronics as well as multifunctional fibres.

Corrugation of chemically converted graphene monolayers on SiO(2).

Sheets of chemically converted graphene (CCG) on the surface of Si/SiO(2) substrates exhibit nanoscopic corrugation. This corrugation has been assumed to be caused by a combination of factors including (a) thermal treatments in the device preparation, (b) different oxygen-containing addends on the CCG, and (c) the substrate roughness. In this paper, we study the interplay of these factors in the corrugation behavior of monolayer CCG flakes, prepared by reduction of graphene oxide (GO) synthesized by Hummers method, and CCG nanoribbons, produced by chemical unzipping of carbon nanotubes, followed by the reduction by hydrazine at 95 degrees C. We have studied the morphology, composition, and electrical properties of the flakes and nanoribbons before and after annealing in Ar/H(2) at 300 degrees C. Our experiments demonstrate that, despite the temperature treatment and the associated removal of the oxygen-containing addends from the basal plane of the CCG, the corrugation pattern of the CCG exhibits almost no change upon annealing. This suggests that the substrate roughness, not the chemical addends nor the thermal cycling, is the predominant determinant in the graphene corrugation. This conclusion is supported by depositing GO flakes on freshly cleaved mica. Such flakes were shown to have extremely low corrugation (rms approximately 70 pm), as dictated by the atomically flat surface of mica. Our experimental observations are in accord with the results of our molecular dynamics simulations, which show that interaction with the substrate greatly suppresses the intrinsic corrugation of graphene materials.

Lower-defect graphene oxide nanoribbons from multiwalled carbon nanotubes.

An improved method is described for the production of graphene oxide nanoribbons (GONRs) via longitudinal unzipping of multiwalled carbon nanotubes. The method produces GONRs with fewer defects and/or holes on the basal plane, maintains narrow ribbons <100 nm wide, and maximizes the high aspect ratio. Changes in the reaction conditions such as acid content, time, and temperature were investigated. The new, optimized method which introduces a second, weaker acid into the system, improves the selectivity of the oxidative unzipping presumably by in situ protection of the vicinal diols formed on the basal plane of graphene during the oxidation, and thereby prevents their overoxidation and subsequent hole generation. The optimized GONRs exhibit increased electrical conductivity over those chemically reduced nanoribbons produced by previously reported procedures.

Kinetics of diazonium functionalization of chemically converted graphene nanoribbons.

We demonstrate that graphene nanoribbons (GNRs) produced by the oxidative unzipping of carbon nanotubes can be chemically functionalized by diazonium salts. We show that functional groups form a thin layer on a GNR and modify its electrical properties. The kinetics of the functionalization can be monitored by probing the electrical properties of GNRs, either in vacuum after the grafting, or in situ in the solution. We derive a simple kinetics model that describes the change in the electrical properties of GNRs. The reaction of GNRs with 4-nitrobenzene diazonium tetrafluoroborate is reasonably fast, such that >60% of the maximum change in the electrical properties is observed after less than 5 min of grafting at room temperature.

Transforming carbon nanotube devices into nanoribbon devices.

Reported here is an extension of the nanotube longitudinal unzipping process to convert electrode-bound multiwalled carbon nanotube (MWCNT) devices into graphene nanoribbon devices. Microscopy and Raman spectroscopy were used to monitor the conversion process. The electrical properties of the devices were characterized. The efficacy of the unzipping protocol on device-bound MWCNTs is demonstrated.

Longitudinal unzipping of carbon nanotubes to form graphene nanoribbons.

Graphene, or single-layered graphite, with its high crystallinity and interesting semimetal electronic properties, has emerged as an exciting two-dimensional material showing great promise for the fabrication of nanoscale devices. Thin, elongated strips of graphene that possess straight edges, termed graphene ribbons, gradually transform from semiconductors to semimetals as their width increases, and represent a particularly versatile variety of graphene. Several lithographic, chemical and synthetic procedures are known to produce microscopic samples of graphene nanoribbons, and one chemical vapour deposition process has successfully produced macroscopic quantities of nanoribbons at 950 degrees C. Here we describe a simple solution-based oxidative process for producing a nearly 100% yield of nanoribbon structures by lengthwise cutting and unravelling of multiwalled carbon nanotube (MWCNT) side walls. Although oxidative shortening of MWCNTs has previously been achieved, lengthwise cutting is hitherto unreported. Ribbon structures with high water solubility are obtained. Subsequent chemical reduction of the nanoribbons from MWCNTs results in restoration of electrical conductivity. These early results affording nanoribbons could eventually lead to applications in fields of electronics and composite materials where bulk quantities of nanoribbons are required.