[Show abstract][Hide abstract] ABSTRACT: A well-known limitation in the fabrication of metal-graphene composite has been the use of surfactants that strongly adsorb on the surface and reduce the performance of the catalyst. We demonstrate here a novel one-pot synthesis of gold nanoparticles by laser ablation of gold strip and in-situ decoration on graphene substrate. Not only the impregnation of nanoparticles was linker free, but also the synthesis by itself was surfactant-free. The composite materials were well characterized morphologically and functionally using electron microscopy, X-ray and electron diffraction, Raman spectroscopy, Zeta potential, electrochemical measurements and UV-Visible spectroscopic techniques. This linker-free gold-graphene based composite has been employed for catalytic applications pertaining to electrooxidation. We have explored the use of this composite as a binder-free electrode in electrocatalytic oxidation of methanol and ethanol in alkaline medium. Additionally, the onset potential for ethanol oxidation was found to be more negative, −100 mV, an indication of its promising application in direct ethanol fuel cells.
[Show abstract][Hide abstract] ABSTRACT: A facile surfactant free laser ablation mediated synthesis (LAMS) of gold-graphene composite is
reported here. The material was characterized using transmission electron microscopy, field
emission scanning electron microscopy, energy dispersive X-ray spectroscopy, powdered X-ray
diffraction, Raman spectroscopy, Zeta potential measurements and UV-Visible spectroscopic
techniques. The as-synthesized gold-graphene composite was effectively utilized as catalyst for
decolorization of 4 important textile and laser dyes. The integration of gold nanoparticles
(AuNPs) with high surface area graphene has enhanced the catalytic activity of AuNPs. This
enhanced activity is attributed to the synergistic interplay of pristine gold’s electronic relay and
π-π stacking of graphene with the dyes. This is evident when the Rhodamine B (RB) reduction
rate of the composite is nearly twice faster than that of commercial citrate capped AuNPs of
similar size. In case of Methylene blue (MB) the rate of reduction is 17000 times faster than
uncatalyzed reaction. This synthetic method opens door to laser ablation based fabrication of
metal catalysts on graphene for improved performance without the aid of linkers and surfactants
Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 05/2014; 133C. · 1.98 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Single filaments of HexTow® IM7-12K carbon fiber were subjected to tensile measurements on a device which applies a known stress σ, and measures the resulting strain ∊, and the change in resistivity Δρ. Young's modulus E, the resistivity ρ, the piezoresistivity Δρ/ρ∊, and the nonlinearity in the stress-strain relation δ, were determined to be 264.1 ± 16.0 GPa, 1.5 ± 0.1 × 10-3 Ω cm, 1.3 ± 0.1, and -4.96 ± 0.23, respectively. The values obtained for Young's modulus and the resistivity of the fiber are in reasonable agreement with the values reported by the manufacturer. To the best of our knowledge, this is the first report of a measurement of a third-order elastic constant of a single filament of HexTow® IM7-12K. Given the high elastic strains attainable in these fibers and the negative value of δ, the usual calculation of E from a linear fit to the stress-strain data leads to an incorrect higher value of E. According to the accepted thermodynamic definition of the elastic constants, one must use the initial slope of the stress-strain curve to evaluate E. We also observed that the glue used to secure the fiber has an influence on the apparent modulus of the fiber.
Journal of Materials Engineering and Performance 02/2014; 23(3). · 0.92 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Despite their wide spread applications, the mechanical behavior of helically coiled structures has evaded an accurate understanding at any length scale (nano to macro) mainly due to their geometrical complexity. The advent of helically coiled micro/nanoscale structures in nano-robotics, nano-inductors, and impact protection coatings has necessitated the development of new methodologies for determining their shear and tensile properties. Accordingly, we developed a synergistic protocol which (i) integrates analytical, numerical (i.e., finite element using COMSOL®) and experimental (harmonic detection of resonance; HDR) methods to obtain an empirically validated closed form expression for the shear modulus and resonance frequency of a singly clamped helically coiled carbon nanowire (HCNW), and (ii) circumvents the need for solving 12th order differential equations. From the experimental standpoint, a visual detection of resonances (using in situ scanning electron microscopy) combined with HDR revealed intriguing non-planar resonance modes at much lower driving forces relative to those needed for linear carbon nanotube cantilevers. Interestingly, despite the presence of mechanical and geometrical nonlinearities in the HCNW resonance behavior the ratio of the first two transverse modes f2/f1 was found to be similar to the ratio predicted by the Euler-Bernoulli theorem for linear cantilevers.
[Show abstract][Hide abstract] ABSTRACT: Recently we investigated the magnetic behavior of as-prepared and sulfur
doped chemically exfoliated graphene nano-platelets (GNPs) and single
walled carbon nanotubes (SWCNTs). The doping was achieved by annealing
desired carbon nanostructures with 0, 1.0, 1.5 and 3 at% sulfur in an
evacuated quartz tube at 1000 ^oC for 1 day, followed by
multiple rinsing in alcohol and drying in vacuum to remove excess
sulfur. The isothermal M vs. H as well as the temperature-dependent M
vs. T measurements were obtained using a vibrating sample magnetometer.
We found that sulfur doping drastically changes the magnetic behavior of
the as-prepared samples (both SWCNTs and GNPs). The results of
zero-field-cooling (ZFC) and field-cooling (FC) in M vs. T measurements
indicated the existence of large amount of coupled super-paramagnetic
domains, along with antiferromagnetic domains. The saturation
magnetization decreased in S doped GNPs, while a contrasting trend was
observed in S doped SWCNTs. The role of edge states and structural
defects in carbon nanostructures in the observed magnetic properties
will be discussed.
[Show abstract][Hide abstract] ABSTRACT: Herein, we examined the dependence of protein adsorption on the nanoparticle surface in the presence of functional groups. Our UV-visible spectrophotometry, transmission electron microscopy, infrared spectroscopy, and dynamic light scattering measurements evidently suggested that the functional groups play an important role in the formation of nanoparticle-protein corona. We found that uncoated and surfactant-free silver nanoparticles derived from a laser ablation process promoted a maximum protein (bovine serum albumin) coating due to increased changes in entropy. On the other hand, bovine serum albumin displayed a relatively lower affinity for electrostatically stabilized nanoparticles due to the constrained entropy changes.
[Show abstract][Hide abstract] ABSTRACT: The binding of proteins to a nanostructure often alters protein secondary and tertiary structures. However, the main physical mechanisms that elicit protein conformational changes in the presence of the nanostructure have not yet been fully established. Here we performed a comprehensive spectroscopic study to probe the interactions between bovine serum albumin (BSA) and carbon-based nanostructures of graphene and single-walled carbon nanotubes (SWNTs). Our results showed that the BSA "corona" acted as a weak acceptor to facilitate charge transfer from the carbon nanostructures. Notably, we observed that charge transfer occurred only in the case of SWNTs but not in graphene, resulting from the sharp and discrete electronic density of states of the former. Furthermore, the relaxation of external α-helices in BSA secondary structure increased concomitantly with the charge transfer. These results may help guide controlled nanostructure-biomolecular interactions and prove beneficial for developing novel drug delivery systems, biomedical devices and engineering of safe nanomaterials.
The Journal of Physical Chemistry C 10/2012; 116(41):22098-22103. · 4.84 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Bismuth is a fascinating material system owing to its unusual Fermi surface topology, which depends on size and temperature. Theoretical calculations predict that Bi should undergo a semimetal-to-semiconductor transition as at least one of its dimensions becomes < 50 nm. This prediction was experimentally confirmed by infrared (IR) absorption spectra, which is largely underlain by transitions between the L (electron) and T (hole) pockets of the Fermi surface. In this work, however, we report that in our nanosize samples, the observed IR peak positions are practically independent of temperature, which is hard to reconcile with the predicted behavior of the L–T transition. To help elucidate the origin of these IR peaks, we performed a careful analysis of the IR spectra of Bi nanorods, as well as those of bulk Bi, Bi samples prepared under different conditions and Bi2(CO3)O2 using Fourier transform infrared and photoacoustic spectroscopy measurements. We propose that the observed IR peaks in Bi nanorods arise from the oxygen–carbon containing secondary phases formed on the surface of Bi rather than from the Bi itself. We believe that secondary phases must be taken into account on a general basis in modeling the IR spectra of Bi and that the scenario that ascribes these IR peaks solely to the L–T transitions may not be correct. The results reported herein may also impact the research of Bi-based thermoelectric nanostructures and bulk materials.
[Show abstract][Hide abstract] ABSTRACT: Current research efforts are aimed at controlling the electronic properties via doping graphene. Previously, dopant-induced changes in the Fermi velocity were observed to result in an effectively downshifted Raman peak below the G Prime -band for n-doped carbon nanotubes. However, in the case of N-doped graphene, we find that several Raman features vary depending upon both dopant concentration and its bonding environment. For instance, only pyridinic/pyrrolic dopants were observed to result in intense D/D Prime -bands with a concomitant downshift in the G Prime -band. Here, we correlate x-ray photoelectron measurements with Raman spectra to elucidate effects of dopant bonding configuration on vibrational properties of graphene.
[Show abstract][Hide abstract] ABSTRACT: Using open aperture z-scan measurements in tandem with XPS measurements and Raman spectroscopy, we show that nonlinear optical properties of single-walled carbon nanotubes can be tailored by substitutional doping with Boron.
Fiber Optics and Photonics (PHOTONICS), 2012 International Conference on; 01/2012
[Show abstract][Hide abstract] ABSTRACT: The recent realization of silicon core optical fibers has the potential for novel low insertion loss rack-to-rack optical interconnects and a number of other uses in sensing and biomedical applications. To the best of our knowledge, incoherent light source based rapid photothermal processing (RPP) was used for the first time to anneal glass-clad silicon core optical fibers. X-ray diffraction examination of the silicon core showed a considerable enhancement in the length and amount of single crystallinity post-annealing. Further, shifts in the Raman frequency of the silicon in the optical fiber core that were present in the as-drawn fibers were removed following the RPP treatment. Such results indicate that the RPP treatment increases the local crystallinity and therefore assists in the reduction of the local stresses in the core, leading to more homogenous fibers. The dark current-voltage characteristics of annealed silicon optical fiber diodes showed lower leakage current than the diodes based on as-drawn fibers. Photons in UV and vacuum ultraviolet (VUV) regions play a very important role in improving the bulk and carrier transport properties of RPP-treated silicon optical fibers, and the resultant annealing permits a path forward to in situ enhancement of the structure and properties of these new crystalline core optical fibers.
Journal of Applied Physics 12/2011; · 2.21 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: We demonstrate that carbon nanotube coated surfaces produce two orders of magnitude brighter hard x-ray emission, in laser produced plasmas, than planar surfaces. It is accompanied by three orders of magnitude reduction in ion debris which is also low Z and nontoxic. The increased emission is a direct consequence of the enhancement in local fields and is via the simple and well known “lightning rod” effect. We propose that this carbon nanotube hard x-ray source is a simple, inexpensive, and high repetition rate hard x-ray point source for a variety of applications in imaging, lithography, microscopy, and material processing.
Physics of Plasmas 01/2011; 18(1):014502-014502-4. · 2.38 Impact Factor
[Show abstract][Hide abstract] ABSTRACT: Here, we report rich and new resonant Raman and infrared (IR) spectral features for several sub-nanometer diameter single wall carbon nanotubes (sub-nm SWCNTs) samples grown using chemical vapor deposition technique operating at different temperatures. We find that the high curvature in sub-nm SWCNTs leads to (i) an unusual S-like dispersion of the G-band frequency due to perturbations caused by the strong electron–phonon coupling, (ii) an activation of diameter-selective intermediate frequency modes that are as intense as the radial breathing modes (RBMs), and (iii) a clear observation of the IR modes. Furthermore, an analytical approach which includes the effects of curvature into the overlap integral and the energy gap between the van Hove singularities is discussed. Lastly, we show that the phonon spectra for sub-nm SWCNTs obtained from the molecular dynamic simulations which employs a curvature-dependent force field concur with our experimental observations.Graphical abstractResearch highlights► We find that the high curvature in sub-nm SWCNTs leads to the following interesting features in the Raman and IR spectra: ► an unusual S-like dispersion of the G-band frequency due to perturbations caused by the strong electron-phonon coupling, ► an activation of diameter-selective intermediate frequency modes that are as intense as the radial breathing modes (RBMs), and ► a clear observation of the infra-red modes.
[Show abstract][Hide abstract] ABSTRACT: Due to their unusual electronic and vibrational properties, single walled carbon nanotubes (SWCNTs) with sub-nanometer diameters d∼0.5–0.9nm have recently gained interest in the carbon community. Using UV–Vis–NIR spectroscopy and ultra-centrifugation, we have conducted a detailed study of the π plasmon energy (present at∼5–7eV) in sub-nm SWCNTs as a function of the size of the bundle. We find that the energy of the π plasmon peak E varies with the bundle diameter Dh as E=(-0.023eV)∗ln(Dh/do)+5.37eV, where do=0.5nm and corresponds to the smallest tube diameter.1In order to make our empirical relation dimensionally correct, we divide the SWCNT bundle diameter Dh with the smallest tube diameter (do=0.5 nm) present in the sub-nm SWNTs. This value for do is constant in the empirical relation and was determined from a careful Raman and photoluminescence measurements.1 This is compared with the same data for HiPCo and Carbolex SWCNTs of larger diameter (1–1.4nm) confirming a clear dependence of E on the bundle size, which is present in addition to the previously reported dependence of E on SWCNT diameter d.
[Show abstract][Hide abstract] ABSTRACT: In the preceding Comment, the authors raise several questions regarding
the properties of bismuth nanowire samples studied in the experimental
section of Phys. Rev. B 79, 165117 (2009) and the interpretation of the
resulting infrared spectra. We address their concerns by discussing each
sample in detail and providing additional relevant information.
[Show abstract][Hide abstract] ABSTRACT: Efficient coupling of laser energy is one of the primary concerns for
devising laser based photon and charged particle sources with potential
applications in a wide field of research interests. We report a two
orders of magnitude efficient moderately hard x-ray (50 - 300 keV)
source based on multi-walled carbon nanotubes (MWNT) irradiated by
moderately intense (1015 - 1017 Wcm-2)
ultra-short laser pulses. This is also accompanied by a three orders of
magnitude reduction in ion debris in comparison with conventional
metallic targets making these sources operationally safe. The
bremsstrahlung measurement reveals a two orders of magnitude increment
in x-ray flux from MWNT. Contrary to expectation that the rise in "hot"
electron temperature leads to an increment of emitted ion energies form
the plasma, a monotonic reduction of ion energies with increasing laser
intensity for MWNT is noticed. Angle resolved ion flux measurement
reveals an extremely divergent ion emission from MWNT with an evident
three orders of magnitude reduction in ion flux. Based on the scaling
laws for resonance absorption, our experimental data remarkably matches
with theoretical predictions based on electrostatic calculations. This
confirms the localized enhancement of the laser electric field near the
tip of the MWNTs yield localized hot spots in the expanding plasma
sheath layer leading to a non-planar expansion. This is characterized by
a decrease in ion accelerating potential as well as a divergent ion
emission, as observed in experiments.
[Show abstract][Hide abstract] ABSTRACT: For the first time to the best of our knowledge a glass-clad optical fiber comprising a crystalline binary III-V semiconductor core has been fabricated. More specifically, a phosphate glass-clad fiber containing an indium antimonide (InSb) core was drawn using a molten core approach. The core was found to be highly crystalline with some oxygen and phosphorus diffusing in from the cladding glass. While optical transmission measurements were unable to be made, most likely due to free carrier absorption associated with the conductivity of the core, this work constitutes a proof-of-concept that optical fibers comprising semiconductor cores of higher crystallographic complexity than previously realized can be drawn using conventional fiber fabrication techniques. Such binary semiconductors may open the door to future fiber-based nonlinear devices.
[Show abstract][Hide abstract] ABSTRACT: Intensity-dependent nonlinear optical transmission studies of cadmium sulfide (CdS) nanowires (∼ 50–100 nm diameter) suspended in dimethylformamide have been carried out in the visible region using the Z-scan technique with 7 ns pulses from the second harmonic of an Nd:YAG laser. The optical limiting threshold of CdS nanowires suspension was determined to be 1.3 J cm− 2, with normalized transmittance of 0.47, which is relatively lower when compared with those of many popular metal nanowire suspensions reported in the literature. Based on an effective three-photon absorption model, nonlinear absorption and nonlinear scattering were identified as the dominant processes for the measured reduced transmittance.