Porous polymer‐derived ceramics: Flexible morphological and compositional controls through sol–gel chemistry

Abstract Porous nonoxide ceramics have exhibited impressive progress in terms of synthesis and applications over the past few decades because of their unique characteristics distinguished from the oxide counterparts. From the synthetic aspect, the preceramic polymer route, where nonoxide ceramics such as carbides and nitrides are produced from molecular precursors, offers exceptional opportunities to elaborate and control the material shape as well as the micro‐ and nanostructures in concert with various techniques. This review presents monolithic ceramic materials based on various reduced phases bearing hierarchical porosity with a focus on those obtained from macroporous preceramic monoliths prepared via the one‐pot sol–gel process accompanied by spinodal decomposition. Here, we highlight two classes of preceramic inorganic–organic hybrid gels: organometallic crosslinked polymers based on poly(silsesquioxane)s and nonorganometallic hybrid networks related to Ti without Ti–C bonds. The polymer‐to‐ceramic conversion processes are discussed with concern for the crystal transition behaviors and the variation of pore properties in different length scales upon heating. In addition, although out of the preceramic polymer category, some examples of inorganic–organic nanocomposite gels with a carbonizable polymer and/or urea for yielding porous metal carbides and nitrides in a monolithic form are introduced as well, which provides extended versatility toward a variety of transition metal systems.