Supramolecular temperature responsive assembly of polydopamine reduced graphene oxide

Abstract

Graphene oxide (GO) and reduced graphene oxide (rGO) colloidal systems can directly respond to environmental stimuli such as pH, ionic strength, and light by themselves, but not to temperature. Here we show that surface modification of rGO with polydopamine (PDA) leads to a temperature-responsive composite material, even though neither rGO nor PDA have intrinsic temperature responsiveness. Reducing GO with dopamine results in rGO/PDA flakes with hydrophilic PDA clusters attached to hydrophobic rGO domains, which mimics the amphiphilic structure of temperature responsive poly(N-isopropylacrylamide) (PNIPAM). The rGO/PDA flakes self-assemble at temperature higher than 30 °C, causing flake aggregation and precipitation in suspensions with concentration of 0.05 g L⁻¹, which is reversible upon cooling, shaking, and re-heating. A solution-to-gelation transition occurs upon heating suspensions with concentration of 10 g L⁻¹. Nacre-like films and porous monoliths are obtained by drying rGO/PDA suspensions at different concentrations. Films and porous monoliths obtained by drying suspensions that are previously self-assembled through heat have more compact structures compared to those obtained with suspensions that are not heated. Overall, this work introduces the concept of supramolecular temperature responsive assembly of nanomaterials (STRAN), i.e., that temperature response can be introduced in nanomaterials by combining non-responsive components that function cooperatively in supramolecules, whose interactions with solvents can be modulated by temperature changes, mimicking what happens in macromolecular systems such as PNIPAM. STRAN could be applied to nanomaterials beyond GO to develop responsive systems whose self-assembly in suspension and architectural features realized upon drying can be controlled by temperature.