Hierarchical Self-Assembly of Toroidal Micelles into Multidimensional Nanoporous Superstructures

Materials with controlled porosity play a prominent role in industrial and domestic applications. Although a rich array of methods has been developed to tune the pore size over a broad range (from <1 nm to >1 μm), the fabrication of functional materials with a fully open porous structure with sub-100 nm pore size has remained a significant challenge. Herein, we report the hierarchical assembly of block copolymer toroidal micelles with an intrinsic cavity into multidimensional nanoporous superstructures (pore size 85-90 nm) by modulation of interparticle interactions. The toroids aggregate into oligo-supermicelles or 2D hexagonal arrays through van der Waals interactions upon drying on a substrate, while synergistic hydrogen bonding interactions further promote the formation of 3D nanoporous superstructures directly in solution. Thus, toroidal micelles can be manipulated as a type of distinctive building block to construct nanoporous materials.