Shaping Nanoparticles for Interface Catalysis: Concave Hollow Spheres via Deflation–Inflation Asymmetric Growth

Abstract Hollow spheres are charming objects in nature. In this work, an unexpected deflation–inflation asymmetric growth (DIAG) strategy is reported, generating hollow nanoparticles with tailored concave geometry for interface catalysis. Starting from aminophenol‐formaldehyde (APF) nanospheres where the interior crosslinking degree is low, fully deflated nanobowls are obtained after etching by acetone. Due to APF etching and repolymerization reactions occuring asymmetrically within a single particle, an autonomous inflation process is observed similar to a deflated basketball that inflates back to a “normal” ball, which is rare at the nanoscale. A nucleophilic addition reaction between acetone and APF is elucidated to explain the chemistry origin of the DIAG process. Interestingly, the deflated APF hollow spheres enable preferential immobilization of lipase in the concave domain, which facilitates the stabilization of Pickering emulsion droplets for enhanced enzymatic catalysis at the oil–water interface. The study provides new understandings in the designable synthesis of hollow nanoparticles and paves the way toward a wide range of applications of asymmetric architectures.