A guide to designing graphene-philic surfactants

As compared to common aliphatic surfactants, increasing the number of pendant or incorporated aromatic groups in a surfactant is expected to offer significant enhancement in the affinity for graphene surfaces. The basis for enhanced graphene-philicity of aromatic surfactants is that they can develop appreciable π – π interactions with graphene. Furthermore, charged (anionic) surfactants are expected to confer electrostatic stabilization on surfactant-graphene composites. Hence, it is expected that anionic aromatic surfactants combine these two properties for effective stabilization of graphene dispersions in water. The properties of two custom made graphene-compatible surfactants carrying two and three aromatic moieties in the hydrophobic tails, namely DC3Ph2 (sodium 1,4-dioxo-1,4-bis(3-phenylpropoxy)butane-2-sulfonate) and TC3Ph3 (sodium 1,5-dioxo-1,5-bis(3-phenylpropoxy)-3-((3-phenylpropoxy)carbonyl) pentane-2-sulfonate) were compared with other common ionic commercial surfactants. Air-water (a/w) surface tension measurements were used to assess the surfactant adsorption and interfacial packing in the absence and presence of graphene. The surfactant coverage index for graphene (Ф) was calculated using surfactant headgroup areas derived from a/w surface tension data, chain volumes, and molecular fragment volumes from literature. Increasing the number of aromatic groups and tails per surfactant was shown to increase the ability of surfactants to pack and fill space, as expressed by Ф. Comparison between the values of Ф for surfactants of different chain structure and architecture showed that the affinity for graphene increased with Ф. Hence, there is an implicit link between surfactant-graphene compatibility and the identity, chemical composition and architecture of the surfactant chains.