Akshay Mathkar

Controlled, Stepwise Reduction and Band Gap Manipulation of Graphene Oxide

Graphene oxide (GO) has drawn tremendous interest as a tunable precursor in numerous areas, due to its readily manipulable surface. However, its inhomogeneous and nonstoichiometric structure makes achieving chemical control a major challenge. Here, we present a room-temperature based, controlled method for the stepwise reduction of GO, with evidence of sequential removal of each organic moiety. By analyzing signature infrared absorption frequencies, we identify the carbonyl group as the first to be reduced, while the tertiary alcohol takes the longest to be completely removed from the GO surface. Controlled reduction allows for progressive tuning of the optical gap from 3.5 eV down to 1 eV, while XPS spectra show a concurrent increase in the C/O ratio. This study is the first step toward selectively enhancing the chemical homogeneity of GO, thus providing greater control over its structure, and elucidating the order of removal of functional groups and hydrazine-vapor reduction.

Artificially stacked atomic layers: Toward new van der Waals solids

Strong in-plane bonding and weak van der Waals interplanar interactions characterize a large number of layered materials, as epitomized by graphite. The advent of graphene (G), individual layers from graphite, and atomic layers isolated from a few other van der Waals bonded layered compounds has enabled the ability to pick, place, and stack atomic layers of arbitrary compositions and build unique layered materials, which would be otherwise impossible to synthesize via other known techniques. Here we demonstrate this concept for solids consisting of randomly stacked layers of graphene and hexagonal boron nitride (h-BN). Dispersions of exfoliated h-BN layers and graphene have been prepared by liquid phase exfoliation methods and mixed, in various concentrations, to create artificially stacked h-BN/G solids. These van der Waals stacked hybrid solid materials show interesting electrical, mechanical, and optical properties distinctly different from their starting parent layers. From extensive first principle calculations we identify (i) a novel approach to control the dipole at the h-BN/G interface by properly sandwiching or sliding layers of h-BN and graphene, and (ii) a way to inject carriers in graphene upon UV excitations of the Frenkell-like excitons of the h-BN layer(s). Our combined approach could be used to create artificial materials, made predominantly from inter planar van der Waals stacking of robust bond saturated atomic layers of different solids with vastly different properties.

Designing nanoscaled hybrids from atomic layered boron nitride with silver nanoparticle deposition

We have developed a microwave assisted one-pot approach to fabricate a novel hybrid nano-composite composed of two-dimensional chemically exfoliated layered hexagonal boron nitride (h-BN) and embedded silver nanoparticles (SNP). Atomic layered h-BN exfoliated using chemical liquid showed strong in-plane bonding and weak van der Waals interplanar interactions, which is utilized for chemically interfacing SNP, indicating their ability to act as excellent nano-scaffolds. The SNP/h-BN optical response, in particular band gap, is strongly dependent on the concentration of the metallic particles. In order to gain further insight into this behavior we have also carried out ab initio density functional theory (DFT) calculations on modeled structures, demonstrating that the bandgap value of SNP/h-BN hybrids could be significantly altered by a small percentage of OH− groups located at dangling B and N atoms. Our results showed that these novel SNP/h-BN nanohybrid structures exhibited excellent thermal stability and they are expected to be applied as devices for thermal oxidation-resistant surface enhanced Raman spectroscopy (SERS). The SNP/h-BN membrane showed remarkable antibacterial activity, suggesting their potential use in water disinfection and food packaging.

Preparation of highly oxidized nitrogen-doped carbon nanotubes

A method for the preparation of highly oxidized nitrogen-doped carbon nanotubes (N-CNTs) from KMnO(4) + H(2)SO(4) solution is described. The atomic ratio of C/O in oxidized N-CNTs is as low as 1.2. The x-ray photoelectron spectroscopy results show that about 75% of the carbon atoms are oxidized and bound to oxygen-containing functional groups. The oxidation reaction mainly occurs at the outer sidewalls, which destroys the graphene stack to an sp(3)-rich structure and helps to preserve the tubular structure of the inner N-CNTs. The oxidized N-CNTs show an energy gap of ~2.1 eV.

Creating supersolvophobic nanocomposite materials

This paper illustrates two techniques that enhance the supersolvophobicity of inherently hydrophilic polymeric thin films. The first technique involves creating a perfluoro-functionalized carbon nanotube based “ink” that can be sprayed on virtually any surface, including polymeric thin films, to greatly enhance the supersolvophobicity. Our results show contact angles greater than 150° with 30 wt% monoethanolamine (MEA) on polysulfone (PSF) and polyimide films that have been treated with the CNT-based ink. The second method involves synthesizing a homogeneous, composite solution consisting of polymer (both PSF & polyimide) and perfluoro-functionalized CNTs (fCNTs). By designing a methodology for the fabrication of fCNT–polymer composite solutions, the supersolvophobicity is not only limited to the surface, but is present within the composite, thereby extending the proposed technique to a range of geometries and length scales. The ratio of polymer : fCNT was varied to locate an upper limit at which films maintain supersolvophobicity. The low density of fCNTs makes them a better alternative to conventional fluorine-based polymeric filler materials (i.e. PTFE, PVDF).

Recent advances in optical limiting properties of fluorinated graphene oxides

There is a substantial interest in finding materials with high nonlinear optical (NLO) properties of materials because of its attractive applications in optical limiting for safety protections. In an effort to develop highly performing optical limiting materials, recently we have found that fluorination of graphene oxides leads to improvement in their NLO properties.