Hierarchically porous materials with large pores in the micrometer range and small pores in the nanometer range, where the large pores facilitate mass transport and the small pores supply numerous active sites, show superiority to materials with unimodal pores in the fields of separation and adsorption. Among all the methods used to prepare hierarchically porous monoliths (HPMs), the sol–gel process accompanied by spinodal decomposition (or phase separation) shows its advantages such as facile method, no template, precise structural control, good reproducibility, and availability for various kinds of materials. This review focuses on the specific process to prepare various types of HPMs including silica, metal oxides, metal phosphates, and metal–organic hybrids, via the sol–gel process accompanied by spinodal decomposition. The HPMs composed of organic polymer and their carbonized derivatives prepared by polymerization-induced phase separation are also covered in this review as an example of similar morphological formation in purely organic crosslinking reactions. This review directs the most attention to the preparation of monolithic gels (sol–gel process) and the control of macroporous structure (phase separation).

具有在微米范围内的大孔和在纳米范围内的小孔的分层多孔材料，其中大孔有利于质量传输，而小孔提供许多活性位点，在分离和吸附领域优于具有单峰孔的材料。在用于制备分级多孔整料（HPM）的所有方法中，伴随着旋节线分解（或相分离）的溶胶-凝胶工艺显示出其优点，例如方法简便，无需模板，精确的结构控制，良好的可重复性以及可用于各种用途各种材料。这篇综述着重于通过溶胶-凝胶法并伴随着旋节线分解来制备各种类型的HPM的具体过程，包括二氧化硅，金属氧化物，金属磷酸盐和金属-有机杂化物。由有机聚合物及其通过聚合反应诱导的相分离制得的碳化衍生物组成的HPM，也作为纯有机交联反应中类似形态形成的一个例子，也涵盖在本文中。这篇综述将注意力集中在整体凝胶的制备（溶胶-凝胶法）和大孔结构的控制（相分离）上。