Progress in Sol-Gel-Derived Phenolic Aerogels: Control of Network Topology, Drying Technologies, and Functional Modification.

Phenolic aerogels, owing to their low density, high char yield, large specific surface area, and well-defined three-dimensional topological networks, hold considerable promise for applications in extreme thermal protection and multifunctional material systems. The sol-gel process, a cornerstone methodology for constructing the three-dimensional nanoporous architecture of these materials, critically governs the resulting microstructural topology and macroscopic performance through its reaction kinetics, phase-separation behavior, and drying dynamics. This review systematically surveys recent advances in the sol-gel synthesis of phenolic aerogels, focusing on the polycondensation mechanisms operative under acidic and basic catalytic conditions, nucleation-and-growth kinetics, and strategies for tailoring multiscale pore structures. It further provides a comparative analysis of interfacial regulation mechanisms for capillary-stress elimination across supercritical drying, freeze-drying, and ambient-pressure drying routes. We also dissect the structure-property relationships underpinning Knudsen-effect-mediated gaseous thermal insulation, multi-scale hybrid network toughening, and inorganic phase-transition-induced in situ ceramization for thermal protection, demonstrating the synergistic optimization of thermal insulation, structural load-bearing, and ablation resistance. Finally, we summarise current applications in extreme thermal protection, environmental adsorption, electromagnetic interference shielding, and electrochemical energy storage and highlight future directions towards green, scalable manufacturing and intelligent materials design.