Falling-Leaves Stacking Aggregation of Two-Dimensional Macromolecular Graphene Oxide in Solution

Understanding the dynamical behaviors of two-dimensional (2D) macromolecules is of fundamental importance for the precise modulation of their assembled structures and material performances. However, considerably less is known about how discrete macromolecular sheets aggregate into extended macroscopic assemblies in solutions. The absence of a quantitative description of the assembly process limits the precise structural control of assemblies. Here, we investigated the aggregation thermodynamic transition and kinetic behavior of 2D macromolecules in the model of single layer graphene oxide (GO). Combining Flory-Huggins theory with experimental observations, we unveiled the critical thermodynamic transition of GO to correlate with the solvent property. We proposed a theoretical falling-leaf model to quantitatively describe the kinetic aggregation process of 2D GO sheets. Experimental analysis validated the theoretical prediction that the thickness of GO aggregates has a power law relation with the poor solvent content. Our work provides a fundamental understanding of phase separation of 2D macromolecules and offers an insight into modulating the aggregated structures of their assembled materials.