Synergistic Molecular Network and Porous Architecture Engineering for High-Performance Shape-Memory Polymer Aerogels

Shape-memory aerogels with complex geometries and large deformability hold great promise for advanced applications, yet their development is hindered by the difficulty in simultaneously achieving robust mechanical properties, excellent shape-memory performance, and structural stability. Herein, we present a high-performance shape-memory aerogel based on a polyimide–polysiloxane (PI–PSi) block copolymer. Its function stems from multiscale structural cooperation: reversible conformational changes of flexible polysiloxane segments and stable π–π stacking of rigid polyimide segments are synergistically coupled with the reversible deformation of a three-dimensional porous network. The optimal PI–PSi3 aerogel exhibits outstanding shape-memory performance (shape fixity ratio of 96.5%, recovery ratio of 97.8%), low density (∼0.1 g cm –3 ), and remarkable thermal insulation. As a proof-of-concept, a Kresling origami-inspired deployable capsule demonstrates its potential for intelligent thermal protection and adaptive space structures.