8.2 Graphene  (Page 2/3)

As graphite oxide is electrically insulating, it must be converted by chemical reduction to restore the electronic properties of graphene. Chemically converted graphene (CCG) is typically reduced by hydrazine or borohydride. The properties of CCG can never fully match those of graphene for two reasons:

1. Oxidation to GO introduces defects.
2. Chemical reduction does not fully restore the graphitic structure.

As would be expected, CCG is prone to aggregation unless stabilized. Graphene materials produced from pristine graphite avoid harsh oxidation to GO and subsequent (incomplete) reduction; thus, materials produced are potentially much better suited to electronics applications.

A catalytic approach to the removal of epoxides from fullerenes and SWNTs has been applied to graphene epoxide and GO. Treatment of oxidized graphenes with methyltrioxorhenium (MeReO ₃ , MTO) in the presence of PPh ₃ results in the oxygen transfer, to form O=PPh ₃ and allow for quantification of the C:O ratio.

Homogeneous graphene dispersions

An alternate approach to producing graphene materials involves the use of pristine graphite as starting material. The fundamental value of such an approach lies in its avoidance of oxidation to GO and subsequent (incomplete) reduction, thereby preserving the desirable electronic properties of graphene. There is precedent for exfoliation of pristine graphite in neat organic solvents without oxidation or surfactants. It has been reported that N , N -dimethylformamide (DMF) dispersions of graphene are possible, but no detailed characterization of the dispersions were reported. In contrast, Coleman and coworkers reported similar dispersions using N -methylpyrrolidone (NMP), resulting in individual sheets of graphene at a concentration of ≤0.01 mg/mL. NMP and DMF are highly polar solvents, and not ideal in cases where reaction chemistry requires a nonpolar medium. Further, they are hygroscopic, making their use problematic when water must be excluded from reaction mixtures. Finally, DMF is prone to thermal and chemical decomposition.

Recently, dispersions of graphene has been reported in ortho -dichlorobenzene (ODCB) using a wide range of graphite sources. The choice of ODCB for graphite exfoliation was based on several criteria:

1. ODCB is a common reaction solvent for fullerenes and is known to form stable SWNT dispersions.
2. ODCB is a convenient high-boiling aromatic, and is compatible with a variety of reaction chemistries.
3. ODCB, being aromatic, is able to interact with graphene via π-π stacking.
4. It has been suggested that good solvents for graphite exfoliation should have surface tension values of 40 – 50 mJ/m ² . ODCB has a surface tension of 36.6 mJ/m ² , close to the proposed range.

Graphite is readily exfoliated in ODCB with homogenization and sonication. Three starting materials were successfully dispersed: microcrystalline synthetic, thermally expanded, and highly ordered pyrolytic graphite (HOPG). Dispersions of microcrystalline synthetic graphite have a concentration of 0.03 mg/mL, determined gravimetrically. Dispersions from expanded graphite and HOPG are less concentrated (0.02 mg/mL).