Carbon nanotubes (CNTs) were coated on a sample of glass fiber air filter medium at atmospheric pressure and room temperature using electro-aerodynamic deposition (EAD). In the EAD method, CNTs (diameter: 50 nm, length:...Carbon nanotubes (CNTs) were coated on a sample of glass fiber air filter medium at atmospheric pressure and room temperature using electro-aerodynamic deposition (EAD). In the EAD method, CNTs (diameter: 50 nm, length: 2-3 μm) were aerosolized, electrically charged, and injected through a nozzle. A voltage was applied externally between the ground nozzle and a planar electrode on which the sample was located. The charged CNTs were deposited on the sample in a vertically standing posture even at a low flow velocity. Before the deposition experiment, a calculation was performed to determine the applied voltage by simulating the electric field, flow field, and particle trajectory. Using CNT-coated filter samples, virus aerosol filtration and anti-viral tests were carried out using the aerosol number counting method and the plaque counting method, respectively. For this purpose, bacteriophage MS2 was aerosolized with an atomizer. The particle filtration efficiency was increased to 33.3% in the most penetration particle size zone (100 nm) and the antiviral efficiency of the CNT filter was 92% when the coating areal density was 1.5 × 10 #/cm. The susceptibility constant of virus to CNTs was 0.2 cm/μg.
Thermal reduction of graphene oxide or graphite oxide (GO) is an important processing step in the fabrication of many graphene-based materials and devices. Here we show that some bulk solid GO samples can undergo explosi...Thermal reduction of graphene oxide or graphite oxide (GO) is an important processing step in the fabrication of many graphene-based materials and devices. Here we show that some bulk solid GO samples can undergo explosive decomposition when small samples are heated slowly in inert gas environments, while others do not. These micro-explosions can occur for samples as small as few milligrams and are sufficiently energetic to cause laboratory equipment damage. Thermochemical analysis methods are used to understand the factors that lead to the explosive reduction mode. The studies show that the explosive mode of reduction is caused by the exothermicity of GO reduction coupled with a threshold sample mass/size that causes heat and mass transfer limitations leading to local temperature rise and a thermal runaway reaction. The explosive mode of reduction is not caused or promoted by interstitial water, and its onset temperature can be lowered by immersion in potassium hydroxide solution. By allowing early release of internal gas pressure, the explosive mode reduces the extent of surface area development in GO exfoliation from an optimum value of 1470 mg obtained under non-explosive reduction conditions. Explosive reduction of bulk GO poses industrial safety hazards during large-scale storage, handling, and processing.
A detailed analysis by transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) of nitroxide-functionalized graphene oxide layers (GOFT) dispersed in Nylon 6 nanofibers is reported herein. The...A detailed analysis by transmission electron microscopy (TEM) and electron energy loss spectroscopy (EELS) of nitroxide-functionalized graphene oxide layers (GOFT) dispersed in Nylon 6 nanofibers is reported herein. The functionalization and exfoliation process of graphite oxide to GOFT was confirmed by TEM using electron diffraction patterns (EDP), wherein 1 to 4 graphene layers of GOFT were observed. The distribution and alignment of GOFT layers within a sample of Nylon 6 nanofiber reveals that GOFT platelets are mainly within the fiber, but some were partially protruding from it. Furthermore, Nylon 6 nanofibers exhibit an average diameter of 225 nm with several microns in length. GOFT platelets embedded into the fiber, the pristine fiber, and amorphous carbon were analyzed by EELS where each spectra [corresponding to the carbon edge (C-K)] exhibited changes in the fine structure, allowing a clear distinction between: i) GOFT single-layers, ii) Nylon-6 nanofibers, and iii) the carbon substrate. EELS analysis is presented here for the first time as a powerful tool to identify functionalized graphene single-layers (< 4 layers of GOFT) into a Nylon 6 nanofiber composite.
Graphene, an atomically thin material with the theoretical surface area of 2600 mg, has great potential in the fields of catalysis, separation, and gas storage if properly assembled into functional 3D materials at large...Graphene, an atomically thin material with the theoretical surface area of 2600 mg, has great potential in the fields of catalysis, separation, and gas storage if properly assembled into functional 3D materials at large scale. In ideal non-interacting ensembles of non-porous multilayer graphene plates, the surface area can be adequately estimated using the simple geometric law ~ 2600 mg/N, where N is the number of graphene sheets per plate. Some processing operations, however, lead to secondary plate-plate stacking, folding, crumpling or pillaring, which give rise to more complex structures. Here we show that bulk samples of multilayer graphene plates stack in an irregular fashion that preserves the 2600/N surface area and creates regular slot-like pores with sizes that are multiples of the unit plate thickness. In contrast, graphene oxide deposits into films with massive area loss (2600 to 40 mg) due to nearly perfect alignment and stacking during the drying process. Pillaring graphene oxide sheets by co-deposition of colloidal-phase particle-based spacers has the potential to partially restore the large monolayer surface. Surface areas as high as 1000 mg are demonstrated here through colloidal-phase deposition of graphene oxide with water-dispersible aryl-sulfonated ultrafine carbon black as a pillaring agent.
Atomic carbon chains have raised interest for their possible applications as graphene interconnectors as the thinnest nanowires; however, they are hard to synthesize and subsequently to study. We present here a reproduci...Atomic carbon chains have raised interest for their possible applications as graphene interconnectors as the thinnest nanowires; however, they are hard to synthesize and subsequently to study. We present here a reproducible method to synthesize carbon chains TEM. Moreover, we present a direct observation of the bond length alternation in a pure carbon chain by aberration corrected TEM. Also, cross bonding between two carbon chains, 5 nm long, is observed experimentally and confirmed by DFT calculations. Finally, while free standing carbon chains were observed to be straight due to tensile loading, a carbon chain inside the walls of a carbon nanotube showed high flexibility.
A facile method for preparing functionalized graphene oxide single layers with nitroxide groups is reported herein. Highly oxidized graphite oxide (GO=90.6%) was obtained, slightly modifying an improved Hummer's method....A facile method for preparing functionalized graphene oxide single layers with nitroxide groups is reported herein. Highly oxidized graphite oxide (GO=90.6%) was obtained, slightly modifying an improved Hummer's method. Oxoammonium salts (OS) were investigated to introduce nitroxide groups to GO, resulting in a one-step functionalization and exfoliation. The mechanisms of functionalization/exfoliation are proposed, where the oxidation of aromatic alcohols to ketone groups, and the formation of alkoxyamine species are suggested. Two kinds of functionalized graphene oxide layers (GOFT1 and GOFT2) were obtained by controlling the amount of OS added. GOFT1 and GOFT2 exhibited a high interlayer spacing ( = 1.12nm), which was determined by X-ray diffraction. The presence of new chemical bonds C-N (~9.5 %) and O-O (~4.3 %) from nitroxide attached onto graphene layers were observed by X-ray photoelectron spectroscopy. Single-layers of GOFT1 were observed by HRTEM, exhibiting amorphous and crystalline zones at a 50:50 ratio; in contrast, layers of GOFT2 exhibited a fully amorphous surface. Fingerprint of GOFT1 single layers was obtained by electron diffraction at several tilts. Finally, the potential use of these materials within Nylon 6 matrices was investigated, where an unusual simultaneous increase in tensile stress, tensile strain and Young's modulus was observed.
Graphene has been the subject of intense research in recent years due to its unique electrical, optical and mechanical properties. Furthermore, it is expected that quantum dots of graphene would make their way into devic...Graphene has been the subject of intense research in recent years due to its unique electrical, optical and mechanical properties. Furthermore, it is expected that quantum dots of graphene would make their way into devices due to their structure and composition which unify graphene and quantum dots properties. Graphene quantum dots (GQDs) are planar nano flakes with a few atomic layers thick and with a higher surface-to-volume ratio than spherical carbon dots (CDs) of the same size. We have developed a pulsed laser synthesis (PLS) method for the synthesis of GQDs that are soluble in water, measure 2-6 nm across, and are about 1-3 layers thick. They show strong intrinsic fluorescence in the visible region. The source of fluorescence can be attributed to various factors, such as: quantum confinement, zigzag edge structure, and surface defects. Confocal microscopy images of bacteria exposed to GQDs show their suitability as biomarkers and nano-probes in high contrast bioimaging.
Carbon nanotubes (CNTs) have one of the highest production volumes among carbonaceous engineered nanoparticles (ENPs) worldwide and are have potential uses in applications including biomedicine, nanocomposites, and energ...Carbon nanotubes (CNTs) have one of the highest production volumes among carbonaceous engineered nanoparticles (ENPs) worldwide and are have potential uses in applications including biomedicine, nanocomposites, and energy conversion. However, CNTs possible widespread usage and associated likelihood for biological exposures have driven concerns regarding their nanotoxicity and ecological impact. In this work, we probe the responses of planar suspended lipid bilayer membranes, used as model cell membranes, to functionalized multi-walled carbon nanotubes (MWCNT), CdSe/ZnS quantum dots, and a control organic compound, melittin, using an electrophysiological measurement platform. The electrophysiological measurements show that MWCNTs in a concentration range of 1.6 to 12 ppm disrupt lipid membranes by inducing significant transmembrane current fluxes, which suggest that MWCNTs insert and traverse the lipid bilayer membrane, forming transmembrane carbon nanotubes channels that allow the transport of ions. This paper demonstrates a direct measurement of ion migration across lipid bilayers induced by CNTs. Electrophysiological measurements can provide unique insights into the lipid bilayer-ENPs interactions and have the potential to serve as a preliminary screening tool for nanotoxicity.
The benzyne functionalization of chemical vapor deposition grown large area graphene and graphite was performed using a mixture of o-trimethylsilylphenyl triflate and cesium fluoride that react with the carbon surface. T...The benzyne functionalization of chemical vapor deposition grown large area graphene and graphite was performed using a mixture of o-trimethylsilylphenyl triflate and cesium fluoride that react with the carbon surface. The reaction requires at least 2 days of treatment before the appearance of Raman and energy-dispersive X-ray spectral signatures that verify modification. Raman spectra of modified graphene and graphite show a rich structure of lines corresponding to C=C-C, C-H, and low frequency modes of surface-attached benzyne rings.
We report a simple method to fabricate macroscopic, 3-D, free standing, all-carbon scaffolds (porous structures) using multiwalled carbon nanotubes (MWCNTs) as the starting materials. The scaffolds prepared by radical in...We report a simple method to fabricate macroscopic, 3-D, free standing, all-carbon scaffolds (porous structures) using multiwalled carbon nanotubes (MWCNTs) as the starting materials. The scaffolds prepared by radical initiated thermal crosslinking, and annealing of MWCNTs possess macroscale interconnected pores, robust structural integrity, stability, and conductivity. The porosity of the three-dimensional structure can be controlled by varying the amount of radical initiator, thereby allowing the design of porous scaffolds tailored towards specific potential applications. This method also allows the fabrication of 3-D scaffolds using other carbon nanomaterials such as single-walled carbon nanotubes, fullerenes, and graphene indicating that it could be used as a versatile method for 3-D assembly of carbon nanostructures with pi bond networks.
Large-area mono- and bilayer graphene films were synthesized on Cu foil (~ 1 inch(2)) in about 1 min by a simple ethanol-chemical vapor deposition (CVD) technique. Raman spectroscopy and high resolution transmission elec...Large-area mono- and bilayer graphene films were synthesized on Cu foil (~ 1 inch(2)) in about 1 min by a simple ethanol-chemical vapor deposition (CVD) technique. Raman spectroscopy and high resolution transmission electron microscopy revealed the synthesized graphene films to have polycrystalline structures with 2-5 nm individual crystallite size which is a function of temperature up to 1000°C. X-ray photoelectron spectroscopy investigations showed about 3 atomic% carboxylic (COOH) functional groups were formed during growth. The field-effect transistor devices fabricated using polycrystalline graphene as conducting channel (L(c)=10 μm; W(c)=50 μm) demonstrated a p-type semiconducting behavior with high drive current and Dirac point at ~35 V. This simple one-step method of growing large area polycrystalline graphene films with semiconductor properties and easily functionalizable groups should assist in the realization of potential of polycrystalline graphene for nanoelectronics, sensors and energy storage devices.
Better understanding of electron transfer (ET) taking place at the nano-bio interface can guide design of more effective functional materials used in fuel cells, biosensors, and medical devices. Single-walled carbon nano...Better understanding of electron transfer (ET) taking place at the nano-bio interface can guide design of more effective functional materials used in fuel cells, biosensors, and medical devices. Single-walled carbon nanotube (SWCNT) coupled with biological enzymes serves as a model system for studying the ET mechanism, as demonstrated in the present study. SWCNT enhanced the activity of horseradish peroxidase (HRP) in the solution-based redox reaction by binding to HRP at a site proximate to the enzyme's activity center and participating in the ET process. ET to and from SWCNT was clearly observable using near-infrared spectroscopy. The capability of SWCNT in receiving electrons and the direct attachment of HRP to the surface of SWCNT strongly affected the enzyme activity due to the direct involvement of SWCNT in ET.
Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diaz...Uniform ultrathin Pt films were electrodeposited onto an aligned array of carbon nanotubes (CNTs) for high-area chemically stable methanol fuel cell anodes. Electrochemical treatment of the graphitic CNT surfaces by diazoniumbenzoic acid allowed for uniform Pt electroplating. The mass activity of the Pt thin film can reach 400 A/g at a scan rate of 20 mV/s and in a solution of 1 M CHOH/0.5 M HSO. A programmed pulse potential at 0V was also seen to nearly eliminate the effects of carbon monoxide poisoning. The mass activity of Pt for methanol oxidation can be maintained at 300 A/g for more than 3000 s, which is 19 times of that under a constant potential of 0.7 V (vs Ag/AgCl).
Maghemite (γ-Fe(2)O(3))/multi-walled carbon nanotubes (MWCNTs) hybrid-materials were synthesized and their anisotropic electrical conductivities as a result of their alignment in a polymer matrix under an external magnet...Maghemite (γ-Fe(2)O(3))/multi-walled carbon nanotubes (MWCNTs) hybrid-materials were synthesized and their anisotropic electrical conductivities as a result of their alignment in a polymer matrix under an external magnetic field were investigated. The tethering of γ-Fe(2)O(3) nanoparticles on the surface of MWCNT was achieved by a modified sol-gel reaction, where sodium dodecylbenzene sulfonate (NaDDBS) was used in order to inhibit the formation of a 3D iron oxide gel. These hybrid-materials, specifically, magnetized multi-walled carbon nanotubes (m-MWCNTs) were readily aligned parallel to the direction of a magnetic field even when using a relatively weak magnetic field. The conductivity of the epoxy composites formed in this manner increased with increasing m-MWCNT mass fraction in the polymer matrix. Furthermore, the conductivities parallel to the direction of magnetic field were higher than those in the perpendicular direction, indicating that the alignment of the m-MWCNT contributed to the enhancement of the anisotropic electrical properties of the composites in the direction of alignment.
Micro/mesoporous activated carbons containing oxygen and phosphorus heteroatoms were modified by incorporation of nitrogen using melamine and urea precursors. The surface chemistry was analyzed by the means of elemental...Micro/mesoporous activated carbons containing oxygen and phosphorus heteroatoms were modified by incorporation of nitrogen using melamine and urea precursors. The surface chemistry was analyzed by the means of elemental analysis, XPS, and (31)P MAS NMR. The results indicate that upon the incorporation of nitrogen at high temperatures not only new species involving carbon/nitrogen/oxygen are formed but also the phosphorous environment is significantly altered. Both urea and melamine precursors have similar effects on formation of P-N and P-C bonds. These compounds, although present in small but measurable quantities seem to affect the performance of carbons in electrochemical capacitors. With an increase in the heterogeneity of phosphorus containing species and with a decrease in the content pyrophosphates the capacitance increases and the retention ratio of the capacitor is improved.
Recent research has led to increased concern about the potential adverse human health impacts of carbon nanotubes, and further work is needed to better characterize those risks and develop risk management strategies. One...Recent research has led to increased concern about the potential adverse human health impacts of carbon nanotubes, and further work is needed to better characterize those risks and develop risk management strategies. One of the most important determinants of the chronic pathogenic potential of a respirable fiber is its biological durability, which affects the long-term dose retained in the lungs, or biopersistence. The present article characterizes the biodurability of single-walled carbon nanotubes using an in vitro assay simulating the phagolysosome. Biodurability is observed to depend on the chemistry of nanotube surface functionalization. Single-walled nanotubes with carboxylated surfaces are unique in their ability to undergo 90-day degradation in a phagolysosomal simulant leading to length reduction and accumulation of ultrafine solid carbonaceous debris. Unmodified, ozone-treated, and aryl-sulfonated tubes do not degrade under these conditions. We attribute the difference to the unique chemistry of acid carboxylation, which not only introduces COOH surface groups, but also causes collateral damage to the tubular graphenic backbone in the form of neighboring active sites that provide points of attack for further oxidative degradation. These results suggest the strategic use of surface carboxylation in nanotube applications where biodegradation may improve safety or add function.
There is substantial evidence for toxicity and/or carcinogenicity upon inhalation of pure transition metals in fine particulate form. Carbon nanotube catalyst residues may trigger similar metal-mediated toxicity, but onl...There is substantial evidence for toxicity and/or carcinogenicity upon inhalation of pure transition metals in fine particulate form. Carbon nanotube catalyst residues may trigger similar metal-mediated toxicity, but only if the metal is bioavailable and not fully encapsulated within fluid-protective carbon shells. Recent studies have documented the presence of bioavailable iron and nickel in a variety of commercial as-produced and vendor "purified" nanotubes, and the present article examines techniques to avoid or remove this bioavailable metal. First, data are presented on the mechanisms potentially responsible for free metal in "purified" samples, including kinetic limitations during metal dissolution, the re-deposition or adsorption of metal on nanotube outer surfaces, and carbon shell damage during last-step oxidation or one-pot purification. Optimized acid treatment protocols are presented for targeting the free metal, considering the effects of acid strength, composition, time, and conditions for post-treatment water washing. Finally, after optimized acid treatment, it is shown that the remaining, non-bioavailable (encapsulated) metal persists in a stable and biologically unavailable form up to two months in an in vitro biopersistence assay, suggesting that simple removal of bioavailable (free) metal is a promising strategy for reducing nanotube health risks.
A set of carbon materials was treated by a choice of common oxidizers to investigate the mercury capture capacities at varying temperature conditions. It was found that ozone treatment dramatically increases the mercury...A set of carbon materials was treated by a choice of common oxidizers to investigate the mercury capture capacities at varying temperature conditions. It was found that ozone treatment dramatically increases the mercury capture capacity of carbon surfaces by factors up to 134, but the activity is easily destroyed by exposure to the atmosphere, to water vapor, or by mild heating. Freshly ozone-treated carbon surfaces are shown to oxidize iodide to iodine in solution and this ability fades with aging. FTIR analysis shows broad C-O stretch features from 950 to 1300 cm(-1), which decay upon atmospheric exposure and are similar to the C-O-C asymmetric stretch features of ethylene secondary ozonide. The combined results suggest that the ultra-high mercury capture efficiency is due to a subset of labile C-O functional groups with residual oxidizing power that are likely epoxides or (epoxide-containing) secondary ozonides. The results open the possibility for in situ ozonolysis to create high-performance carbon-based Hg sorbents.
This work investigates the physical interactions between carbon nanomaterials and tocopheryl polyethylene glycol succinate (TPGS). TPGS is a synthetic amphiphile that undergoes enzymatic cleavage to deliver the lipophili...This work investigates the physical interactions between carbon nanomaterials and tocopheryl polyethylene glycol succinate (TPGS). TPGS is a synthetic amphiphile that undergoes enzymatic cleavage to deliver the lipophilic antioxidant, alpha-tocopherol (vitamin E) to cell membranes, and is FDA approved as a water-soluble vitamin E nutritional supplement and drug delivery vehicle. Here we show that TPGS 1000 is capable of dispersing multi-wall and single-wall carbon nanotubes in aqueous media, and for multiwall tubes is more effective than the commonly used non-ionic surfactant Triton X-100. TPGS is also capable of solubilizing C(60) in aqueous phases by dissolving fullerene in the core of its spherical micelles. Drying of these solutions leads to fullerene/TPGS phase separation and the self-assembly of highly ordered asymmetric nanoparticles, with fullerene nanocrystals attached to the hydrophobic end of crystalline TPGS nanobrushes. The article discusses surface charge, colloidal stability, and the potential applications of TPGS as a safe surfactant for "green" processing of carbon nanomaterials.
There is a pressing need to develop rapid whole animal-based testing assays to assess the potential toxicity of engineered nanomaterials. To meet this challenge, the embryonic zebrafish model was employed to determine th...There is a pressing need to develop rapid whole animal-based testing assays to assess the potential toxicity of engineered nanomaterials. To meet this challenge, the embryonic zebrafish model was employed to determine the toxicity of fullerenes. Embryonic zebrafish were exposed to graded concentrations of fullerenes [C(60), C(70), and C(60)(OH)(24)] during early embryogenesis and the resulting morphological and cellular responses were defined. Exposure to 200 μg/L C(60) and C(70) induced a significant increased in malformations, pericardial edema, and mortality; while the response to C(60)(OH)(24) exposure was less pronounced at concentrations an order of magnitude higher. Exposure to C(60) induced both necrotic and apoptotic cellular death throughout the embryo. While C(60)(OH)(24) induced an increase in embryonic cellular death, it did not induce apoptosis. Our findings concur with results obtained in other models indicating that C(60)(OH)(24) is significantly less toxic than C(60). These studies also suggest that that the embryonic zebrafish model is well-suited for the rapid assessment of nanomaterial toxicity.