Polyhedral Polymeric Microparticles with Interwoven 1 nm Gyroid Pores for Precise Adsorption and Nanoconfined...

Molecular-scale adsorption, catalysis, and separation demand nanoporous materials with high permeability, extensive surface areas, and pronounced nanoconfined effects. Fabricating polymeric particles with 3-D interwoven pores of ∼1 nm potentially addresses these needs. However, significant challenges remain in controlling their pore interconnectivity, uniformity, and achieving faceted particle shapes. Herein we present facile fabrication of polyhedral particles possessing interpenetrating 1 nm pores by suspension polymerization of double-gyroid (DG) liquid crystalline droplets. Mechanical stirring of the disordered phase at elevated temperatures, followed by undercooling, leads to the emulsification of DG droplets, as confirmed by synchrotron small-angle X-ray scattering (SAXS). UV-induced cross-linking of the DG droplets preserves the ordered network of 1 nm pores, as characterized by SAXS and microscopy. Intriguingly, due to the elasticity induced by the Ia3̅d periodicities, these particles adopt polyhedral shapes to avoid the elastic energy penalty associated with conventional sphericity. We demonstrate that these faceted particles, featuring 1 nm pores and efficient packing, enable rapid, size-exclusive adsorption and nanoconfined degradation of organic pollutants, driven by their 3-D permeability, high surface area, and enhanced nanoconfinement effects.