Gradient Gyroid Aerogels With Programmable Multiscale Pore Architectures and Fibrillated Loss Networks for Electromagnetic, Thermal/Fire, and Mechanical Protection

ABSTRACT Airborne electronic systems operating in extreme environments require lightweight protective materials that combine efficient electromagnetic attenuation, thermal protection, and mechanical robustness. However, conventional aerogel absorbers typically rely on pore engineering at a single length scale, making it difficult to simultaneously optimize these properties. Herein, we develop a decoupled multiscale structural engineering strategy based on a custom‐built freeze‐printing platform, in which pore structures at different length scales are regulated through distinct mechanisms and subsequently integrated into a hierarchical Gyroid architecture spanning from the nanoscale to the millimeter scale. Notably, the amino‐functionalized metal–organic framework employed for nanopore regulation can also intercalate between MXene nanosheets through interactions between its amino groups and the polar surface terminations of MXene, thereby suppressing nanosheet restacking, generating abundant MX@MOF heterointerfaces, and realizing the coupling of structural regulation and functionality. Building on these heterointerfaces, trypan blue directs PPy growth from discrete particles into fibrillar bridges, linking MX@MOF units into continuous conductive pathways enriched with electromagnetic‐loss sites. As a result, the optimized CS‐4 aerogel achieved a minimum reflection loss of −71.5 dB at only 2.45 mm and an effective absorption bandwidth of 6.26 GHz, while maintaining excellent thermal insulation, compressive strength, flame retardancy, and smoke suppression.