Daniel P. Hashim

Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions

The establishment of covalent junctions between carbon nanotubes (CNTs) and the modification of their straight tubular morphology are two strategies needed to successfully synthesize nanotube-based three-dimensional (3D) frameworks exhibiting superior material properties. Engineering such 3D structures in scalable synthetic processes still remains a challenge. This work pioneers the bulk synthesis of 3D macroscale nanotube elastic solids directly via a boron-doping strategy during chemical vapour deposition, which influences the formation of atomic-scale “elbow” junctions and nanotube covalent interconnections. Detailed elemental analysis revealed that the “elbow” junctions are preferred sites for excess boron atoms, indicating the role of boron and curvature in the junction formation mechanism, in agreement with our first principle theoretical calculations. Exploiting this material’s ultra-light weight, super-hydrophobicity, high porosity, thermal stability, and mechanical flexibility, the strongly oleophilic sponge-like solids are demonstrated as unique reusable sorbent scaffolds able to efficiently remove oil from contaminated seawater even after repeated use.

Bottom-up Approach toward Single-Crystalline VO2-Graphene Ribbons as Cathodes for Ultrafast Lithium Storage

Although lithium ion batteries have gained commercial success owing to their high energy density, they lack suitable electrodes capable of rapid charging and discharging to enable a high power density critical for broad applications. Here, we demonstrate a simple bottom-up approach toward single crystalline vanadium oxide (VO2) ribbons with graphene layers. The unique structure of VO2-graphene ribbons thus provides the right combination of electrode properties and could enable the design of high-power lithium ion batteries. As a consequence, a high reversible capacity and ultrafast charging and discharging capability is achieved with these ribbons as cathodes for lithium storage. A full charge or discharge is capable in 20 s. More remarkably, the resulting electrodes retain more than 90% of the initial capacity after cycling more than 1000 times at an ultrahigh rate of 190C, providing the best reported rate performance for cathodes in lithium ion batteries to date.

Noncovalent Functionalization as an Alternative to Oxidative Acid Treatment of Single Wall Carbon Nanotubes with Applications for Polymer Composites

We have created stable dispersions of single wall carbon nanotubes (SWNTs) in water by employing a noncovalent functionalization scheme that allows carboxylic acid moieties to be attached to the SWNT surface by a pi-pi stacking interaction. Pyrenecarboxylic acid (PCA) is noncovalently attached to the surface of SWNTs and affords highly uniform and stable aqueous dispersions. This method was developed to provide a noncovalent alternative to the commonly used oxidative acid treatment functionalization of carbon nanotubes. This alternative strategy avoids the damage to the carbon nanotube structure inherent to oxidative acid treatments. Carbon nanotubes are commonly functionalized with oxidative acid treatment schemes to create polymer-nanotube composites and improve the adhesion between the polymer and carbon nanotubes. Composites of SWNTs and polycarbonate were prepared and tested to determine the effect of PCA on the adhesion of the SWNTs to the polymer matrix. These tests confirmed that PCA improved the SWNT-polycarbonate adhesion and improved the dispersion of the SWNTs throughout the matrix. This study demonstrates that stable dispersions of SWNTs can be achieved without substantial cutting, introduction of defects, or covalent modification, by employing a simple and effective noncovalent functionalization with PCA.

Carbon nanotube-nanocup hybrid structures for high power supercapacitor applications.

Here, we design and develop high-power electric double-layer capacitors (EDLCs) using carbon-based three dimensional (3-D) hybrid nanostructured electrodes. 3-D hybrid nanostructured electrodes consisting of vertically aligned carbon nanotubes (CNTs) on highly porous carbon nanocups (CNCs) were synthesized by a combination of anodization and chemical vapor deposition techniques. A 3-D electrode-based supercapacitor showed enhanced areal capacitance by accommodating more charges in a given footprint area than that of a conventional CNC-based device.

Functionalized Low Defect Graphene Nanoribbons and Polyurethane Composite Film for Improved Gas Barrier and Mechanical Performances

A thermoplastic polyurethane (TPU) composite film containing hexadecyl-functionalized low-defect graphene nanoribbons (HD-GNRs) was produced by solution casting. The HD-GNRs were well distributed within the polyurethane matrix, leading to phase separation of the TPU. Nitrogen gas effective diffusivity of TPU was decreased by 3 orders of magnitude with only 0.5 wt % HD-GNRs. The incorporation of HD-GNRs also improved the mechanical properties of the composite films, as predicted by the phase separation and indicated by tensile tests and dynamic mechanical analyses. The improved properties of the composite film could lead to potential applications in food packaging and lightweight mobile gas storage containers.

Utilizing 3D SERS Active Volumes in Aligned Carbon Nanotube Scaffold Substrates

Gold and silver nanoparticles and nanostructures exhibit plasmon resonances that result in strong scattering and absorption of light, as well as enhanced optical fi elds near the metal surface. The resonant fi eld enhancement dramatically enhances the weak Raman scattering signals from molecules near the metal surface. [ 1 ] This effect, called surface enhanced Raman scattering (SERS), has been widely pursued as a molecular sensing technology over the past decade. [ 2 , 3 ] SERS is non-destructive, suffi ciently sensitive for single molecule detection, and provides inherent molecular specifi city since it yields molecular vibrational spectra. While fi eld enhancement occurs over an entire nanostructure surface, SERS signals are strongest from small gaps between nanoparticles referred to as “hot spots” where the fi eld enhancement is maximal. [ 4 , 5 ] Most SERS work to date has focused on detection with substrates that are designed to maximize the density, sensitivity, and reproducibility of hot spots in order to give the strongest possible SERS signal. Many substrates have been developed which refl ect the variety of nanofabrication, synthesis, and assembly strategies that have emerged over the past decade. These

Macroscopic Nanotube Fibers Spun from Single-Walled Carbon Nanotube Polyelectrolytes

In this work, single-walled carbon nanotube (SWCNT) fibers were produced from SWCNT polyelectrolyte dispersions stabilized by crown ether in dimethyl sulfoxide and coagulated into aqueous solutions. The SWCNT polyelectrolyte dispersions had concentrations up to 52 mg/mL and showed liquid crystalline behavior under polarized optical microscopy. The produced SWCNT fibers are neat (i.e., not forming composites with polymers) and showed a tensile strength up to 124 MPa and a Youngs modulus of 14 GPa. This tensile strength is comparable to those of SWCNT fibers spun from strong acids. Conductivities on the order of 10(4) S/m were obtained by doping the fibers with iodine.

Functionalization of nitrogen-doped carbon nanotubes with gallium to form Ga-CN(x)-multi-wall carbon nanotube hybrid materials.

In an effort to combine group III-V semiconductors with carbon nanotubes, a simple solution-based technique for gallium functionalization of nitrogen-doped multi-wall carbon nanotubes has been developed. With an aqueous solution of a gallium salt (GaI(3)), it was possible to form covalent bonds between the Ga(3+) ion and the nitrogen atoms of the doped carbon nanotubes to form a gallium nitride-carbon nanotube hybrid at room temperature. This functionalization was evaluated by x-ray photoelectron spectroscopy, energy dispersive x-ray spectroscopy, Raman spectroscopy, scanning electron microscopy and transmission electron microscopy.

Carbon nanotube core graphitic shell hybrid fibers.

A carbon nanotube yarn core graphitic shell hybrid fiber was fabricated via facile heat treatment of epoxy-based negative photoresist (SU-8) on carbon nanotube yarn. The effective encapsulation of carbon nanotube yarn in carbon fiber and a glassy carbon outer shell determines their physical properties. The higher electrical conductivity (than carbon fiber) of the carbon nanotube yarn overcomes the drawbacks of carbon fiber/glassy carbon, and the better properties (than carbon nanotubes) of the carbon fiber/glassy carbon make up for the lower thermal and mechanical properties of the carbon nanotube yarn via synergistic hybridization without any chemical doping and additional processes.

Correlation between droplet-induced strain actuation and voltage generation in single-wall carbon nanotube films.

In this paper, a method of strain actuation of single-walled carbon nanotube (SWNT) films using droplets is examined, and the physical origin of an open-circuit voltage (Voc)-observed across the film during this process-is explored. We demonstrate that droplet actuation is driven by the formation of a capillary bridge between the suspended SWNT films and the substrates, which deforms the films by wetting forces during evaporation. The induced strain is further evaluated and analyzed using dynamic Raman and two-dimensional correlation spectra. Supported by theoretical calculations, our experiments reveal the time and strain dependency of the capillary bridges midpoint directional movement. This relationship is applied to display the correlation between the induced strain and the measured Voc.