Dorsa Parviz

Dispersions of Non-Covalently Functionalized Graphene with Minimal Stabilizer

We demonstrate that functionalized pyrene derivatives effectively stabilize single- and few-layer graphene flakes in aqueous dispersions. The graphene/stabilizer yield obtained by this method is exceptionally high relative to conventional nanomaterial stabilizers such as surfactants or polymers. The mechanism of stabilization by pyrene derivatives is investigated by studying the effects of various parameters on dispersed graphene concentration and stability; these parameters include stabilizer concentration, initial graphite concentration, solution pH, and type and number of functional groups and counterions. The effectiveness of the pyrene derivatives is pH-tunable, as measured by zeta potential, and is also a function of the number of functional groups, the electronegativity of the functional group, the counterion, the relative polarity between stabilizer and solvent, and the distance from the functional group to the basal plane. Even if the dispersion is destabilized by extreme pH or lyophilization, the graphene does not aggregate because the stabilizer remains adsorbed on the surface. These dispersions also show promise for applications in graphene/polymer nanocomposites (examined in this paper), organic solar cells, conductive films, and inkjet-printed electronic devices.

Tailored Crumpling and Unfolding of Spray-Dried Pristine Graphene and Graphene Oxide Sheets.

For the first time, pristine graphene can be controllably crumpled and unfolded. The mechanism for graphene is radically different than that observed for graphene oxide; a multifaced crumpled, dimpled particle morphology is seen for pristine graphene in contrast to the wrinkled, compressed surface of graphene oxide particles, showing that surface chemistry dictates nanosheet interactions during the crumpling process. The process demonstrated here utilizes a spray-drying technique to produce droplets of aqueous graphene dispersions and induce crumpling through rapid droplet evaporation. For the first time, the gradual dimensional transition of 2D graphene nanosheets to a 3D crumpled morphology in droplets is directly observed; this is imaged by a novel sample collection device inside the spray dryer itself. The degree of folding can be tailored by altering the capillary forces on the dispersed sheets during evaporation. It is also shown that the morphology of redispersed crumpled graphene powder can be controlled by solvent selection. This process is scalable, with the ability to rapidly process graphene dispersions into powders suitable for a variety of engineering applications.

Adsorption and removal of graphene dispersants

We demonstrate three different techniques (dialysis, vacuum filtration, and spray drying) for removal of dispersants from liquid-exfoliated graphene. We evaluate these techniques for elimination of dispersants from both the bulk liquid phase and from the graphene surface. Thermogravimetric analysis (TGA) confirms dispersant removal by these treatments. Vacuum filtration (driving by convective mass transfer) is the most effective method of dispersant removal, regardless of the type of dispersant, removing up to ∼95 wt.% of the polymeric dispersant with only ∼7.4 wt.% decrease in graphene content. Dialysis also removes a significant fraction (∼70 wt.% for polymeric dispersants) of un-adsorbed dispersants without disturbing the dispersion quality. Spray drying produces re-dispersible, crumpled powder samples and eliminates much of the unabsorbed dispersants. We also show that there is no rapid desorption of dispersants from the graphene surface. In addition, electrical conductivity measurements demonstrate conductivities one order of magnitude lower for graphene drop-cast films (where excess dispersants are present) than for vacuum filtered films, confirming poor inter-sheet connectivity when excess dispersants are present.

Aqueous Exfoliation of Graphite into Graphene Assisted by Sulfonyl Graphene Quantum Dots for Photonic Crystal Applications

We investigate the π-π stacking of polyaromatic hydrocarbons (PAHs) with graphene surfaces, showing that such interactions are general across a wide range of PAH sizes and species, including graphene quantum dots. We synthesized a series of graphene quantum dots with sulfonyl, amino, and carboxylic functional groups and employed them to exfoliate and disperse pristine graphene in water. We observed that sulfonyl-functionalized graphene quantum dots were able to stabilize the highest concentration of graphene in comparison to other functional groups; this is consistent with prior findings by pyrene. The graphene nanosheets prepared showed excellent colloidal stability, indicating great potential for applications in electronics, solar cells, and photonic displays which was demonstrated in this work.

Tailored Network Formation in Graphene Oxide Gels

Graphene oxide (GO)-based gels are attractive because of their ability to retain individual nanosheet properties in a three-dimensional (3D) bulk material. The final morphology and properties of these 3D gel networks depend strongly on the type and density of cross-links, and these gels can be dried and annealed to form aerogels with both high conductivity (560 S/m) and high surface area (1700 m2/g). The results show that both ammonia content and the parent nanosheet morphology (crumpled vs flat) have a strong influence on the cross-linked structure and composition; notably, nitrogen is found in the gels, suggesting that ammonia actively participates in the reaction rather than as a mere catalyst. The GO nanosheet morphology may be altered using spray-drying to obtain crumpled GO (cGO) nanosheets and form cGO gels; this allows for an additional handle in the creation of GO-based gels with tunable density, electrical conductivity, and surface area.

Electrical current stimulated desorption of carbon dioxide adsorbed on graphene based structures

The objective of this study was to investigate Joule heating/electric swing adsorption (ESA) as a mode of regeneration and to compare the carbon dioxide (CO2) adsorption capacity of pristine graphene films and reduced graphene oxide (rGO) aerogels. Joule heating/ESA has not been previously demonstrated in graphene based structures. Various forms of graphene have been previously evaluated for their use as a CO2 adsorbent, but most of these studies have focused on graphene oxide powders and films. We utilize both pristine graphene and rGO; we also highlight regeneration through Joule heating in contrast to heating under vacuum or by pressure swing. The amount of CO2 captured by graphene films and rGO aerogels was 0.52 ± 0.02 and 0.94 ± 0.02 g of CO2 per g of adsorbate, respectively. This adsorption capacity of pristine graphene films and rGO aerogels was found to be stable over multiple samples and multiple cycles of adsorption and electrical current stimulated desorption.