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

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 <i>Ia</i>3̅<i>d</i> 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.