Emerging Hierarchical Aerogels: Self‐Assembly of Metal and Semiconductor Nanocrystals

Aerogels assembled from colloidal metal or semiconductor nanocrystals (NCs) feature large surface area, ultralow density, and high porosity, thus rendering them attractive in various applications, such as catalysis, sensors, energy storage, and electronic devices. Morphological and structural modification of the aerogel backbones while maintaining the aerogel properties enables a second stage of the aerogel research, which is defined as hierarchical aerogels. Different from the conventional aerogels with nanowire‐like backbones, those hierarchical aerogels are generally comprised of at least two levels of architectures, i.e., an interconnected porous structure on the macroscale and a specially designed configuration at local backbones at the nanoscale. This combination “locks in” the inherent properties of the NCs, so that the beneficial genes obtained by nanoengineering are retained in the resulting monolithic hierarchical aerogels. Herein, groundbreaking advances in the design, synthesis, and physicochemical properties of the hierarchical aerogels are reviewed and organized in three sections: i) pure metallic hierarchical aerogels, ii) semiconductor hierarchical aerogels, and iii) metal/semiconductor hybrid hierarchical aerogels. This report aims to define and demonstrate the concept, potential, and challenges of the hierarchical aerogels, thereby providing a perspective on the further development of these materials.