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

Surface Functionalization of Graphene-based Materials

Graphene-based materials have generated tremendous interest in the past decade. Manipulating their characteristics using wet-chemistry methods holds distinctive value, as it provides a means towards scaling up, while not being limited by yield. The majority of this thesis focuses on the surface functionalization of graphene oxide (GO), which has drawn tremendous attention as a tunable precursor due to its readily chemically manipulable surface and richly functionalized basal plane. Firstly, a room-temperature based method is presented to reduce GO stepwise, with each organic moiety being removed sequentially. Characterization confirms the carbonyl group to be reduced first, while the tertiary alcohol is reduced last, as the optical gap decrease from 3.5 eV down to 1 eV. This provides greater control over GO, which is an inhomogeneous system, and is the first study to elucidate the order of removal of each functional group. In addition to organically manipulating GO, this thesis also reports a chemical methodology to inorganically functionalize GO and tune its wetting characteristics. A chemical method to covalently attach fluorine atoms in the form of tertiary alkyl fluorides is reported, and confirmed by MAS 13C NMR, as two forms of fluorinated graphene oxide (FGO) with varying C/F and C/O ratios are synthesized. Introducing C-F bonds decreases the overall surface free energy, which drastically reduces GO’s wetting behavior, especially in its highly fluorinated form. Ease of solution processing leads to development of sprayable inks that are deposited on a range of porous and non-porous surfaces to impart amphiphobicity. This is the first report that tunes the wetting characteristics of GO. Lastly as a part of a collaboration with ConocoPhillips, another class of carbon nanomaterials - carbon nanotubes (CNTs), have been inorganically functionalized to repel 30 wt% MEA, a critical solvent in CO2 recovery. In addition to improving the solution processability of CNTs, composite, homogeneous solutions are created with polysulfones and polyimides to fabricate CNT-polymer nanocomposites that display contact angles greater than 150o with 30 wt% MEA. This yields materials that are inherently supersolvophobic, instead of simply surface treating polymeric films, while the low density of fluorinated CNTs makes them a better alternative to superhydrophobic polymer materials

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. © 2013 SPIE

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

Quantification of the Particle Size and Stability of Graphene Oxide in a Variety of Solvents

The exceptional solution processing potential of graphene oxide (GO) is always one of its main advantages over graphene in terms of its industrial relevance in coatings, electronics, and energy storage. However, the presence of a variety of functional groups on the basal plane and edges of GO makes understanding suspension behavior in aqueous and organic solvents, a major challenge. Acoustic spectroscopy can also measure zeta potential to provide unique insight into flocculating, meta-stable, and stable suspensions of GO in deionized water and a variety of organic solvents (including ethanol, ethylene glycol, and mineral oil). As expected, a match between solvent polarity and the polar functional groups on the GO surface favors stable colloidal suspensions accompanied by a smaller aggregate size tending toward disperse individual flakes of GO. This work is significant since it describes the characteristics of GO in solution and its ability to act as a precursor for graphene-based materials

Optical Power Limiting in Fluorinated Graphene Oxide: An Insight into the Nonlinear Optical Properties

Fluorination of carbon nanomaterials has many advantages due to the unique nature of the carbon–fluorine (C–F) bond. In this work, we report the optical power limiting properties of fluorinated graphene oxide (F–GO) using the optical <i>z</i>-scan technique. In addition, we used the photoacoustic technique to gain insight into the nonlinear processes involved in the optical limiting of samples. The photoacoustic technique enabled us to confirm that optical limiting observed in F–GO at low fluence arises from nonlinear absorption, while that at higher fluence is due to nonlinear scattering. Moreover, we found that F–GO has high nonlinear absorption and nonlinear scattering and its optical limiting threshold is about an order of magnitude better than that of graphene oxide (GO)

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