Abstract
This review article is intended to provide the reader with the recent advances made in the fabrication of silica‐based monolithic capillary columns for use in capillary electrochromatography (CEC). The silica‐based monoliths can be produced by three different approaches, namely (i) fusion of silica particles by thermal sintering, (ii) cross‐linking/entrapping silica particles in a packed bed using the sol‐gel process, and (iii) polymerization of silicon alkoxide precursors using the sol‐gel process. Thus far, approach (iii) is the most widely used for fabricating silica monoliths. After providing a thorough description of each of the three approaches used for the production of silica‐based monolithic capillary columns, the analytical separations performed by CEC on each kind of monolith are discussed.

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