Wet Chemical Functionalization of Graphene

Citations Over TimeTop 10% of 2012 papers

Abstract

The fullerenes, carbon nanotubes, and graphene have enriched the family of carbon allotropes over the last few decades. Synthetic carbon allotropes (SCAs) have attracted chemists, physicists, and materials scientists because of the sheer multitude of their aesthetically pleasing structures and, more so, because of their outstanding and often unprecedented properties. They consist of fully conjugated p-electron systems and are considered topologically confined objects in zero, one, or two dimensions. Among the SCAs, graphene shows the greatest potential for high-performance applications, in the field of nanoelectronics, for example. However, significant fundamental research is still required to develop graphene chemistry. Chemical functionalization of graphene will increase its dispersibility in solvents, improve its processing into new materials, and facilitate the combination of graphene's unprecedented properties with those of other compound classes. On the basis of our experience with fullerenes and carbon nanotubes, we have described a series of covalent and noncovalent approaches to generate graphene derivatives. Using water-soluble perylene surfactants, we could efficiently exfoliate graphite in water and prepare substantial amounts of single-layer-graphene (SLG) and few-layer-graphene (FLG). At the same time, this approach leads to noncovalent graphene derivatives because it establishes efficient π-π-stacking interactions between graphene and the aromatic perylene chromophors supported by hydrophobic interactions. To gain efficient access to covalently functionalized graphene we employed graphite intercalation compounds (GICs), where positively charged metal cations are located between the negatively charged graphene sheets. The balanced combination of intercalation combined with repulsion driven by Coulombic interactions facilitated efficient exfoliation and wet chemical functionalization of the electronically activated graphene sheets via trapping with reactive electrophilic addends. For example, the treatment of reduced graphite with aryl diazonium salts with the elimination of N(2) led to the formation of arylated graphene. We obtained alkylated graphene via related trapping reactions with alkyl iodides. These new developments have opened the door for combining the unprecedented properties of graphene with those of other compound classes. We expect that further studies of the principles of graphene reactivity, improved characterization methods, and better synthetic control over graphene derivatives will lead to a whole series of new materials with highly specific functionalities and enormous potential for attractive applications.

Related Papers

• → Predicted low thermal conductivities in antimony films and the role of chemical functionalization(2016)29 cited
• → A study on the effect of different chemical routes on functionalization of MWCNTs by various groups (-COOH, -SO3H, -PO3H2)(2011)15 cited
• → Monolithic methacrylate polymeric sorbents: Development of methods for chemical modification of the surface for the subsequent bioaffine functionalization(2008)6 cited
• A natural advantage? Using mined graphite to make graphene(2013)
• Unique synthesis of graphene-based materials for clean energy and biological sensing applications(2012)