Monolithic HPLC (high‐performance liquid chromatography) columns have emerged over the recent decades as highly attractive alternatives to conventional HPLC technology. A monolith is considered to be a continuous piece of porous material. Two types of monolithic columns have been developed for liquid chromatography (LC) applications; they are polymer monoliths and silica monoliths, which differ based on their porous properties. Polymer monoliths consist solely of macropores (pores larger than 50 nm), while silica monoliths possess both macropores and mesopores (pores between 2 and 50 nm). Silica monoliths therefore possess higher surface areas than polymer monoliths and have mainly been utilied for the separation of small molecules, where excellent separation performance has been demonstrated. Polymer monoliths on the other hand have been shown to provide excellent separation performance for larger molecules, where the convective transport of these molecules is unhindered by the presence of mesopores.
Polymer and silica monoliths can be prepared in a variety of ways, resulting in varied surface chemistries and flow properties, thus allowing their application in a wide range of chromatographic modes, including reversed‐phase (RP), ion‐exchange, hydrophilic interaction, and hydrophobic interaction chromatography (HIC), to name a few. This has allowed for the separation of a variety of analytes, from small molecules such as alkylbenzenes, to larger molecules such as peptides and proteins. They have also found application for the separation of DNA. In recent years, significant attention has been focused on improving and understanding the behavior of these materials and alternative synthetic routes for their preparation.