The insolubility in solvents and poor processability
of powder
covalent organic frameworks (COFs) considerably impede their practical
application. To address these issues and bridge the gap between powder
COFs and their practical application, the construction of monolithic
COFs has emerged as a feasible and effective solution. Monolithic
COFs (i.e., macroscopic three-dimensional architectures) with hierarchical
structures have attracted tremendous interest for environmental remediation
and exhibited good contaminant removal performances owing to their
wide distribution of pore sizes ranging from micropores to macropores,
large specific surface area, tailored chemical components, and excellent
chemical stability. Monolithic COFs can be either pure COFs with self-supporting
structures or composites of COFs with other materials. The resulting
COF-based monoliths inherit the merits of the parent powder COFs (such
as tunable pore size, tailored structure, and super chemical/thermal
stability) and the intriguing features of monolithic materials, such
as hierarchical structure, high porosity, and easy handling, endowing
them with fast mass transfer and high adsorption capacity. This review
provides a comprehensive summary of the recent advances in the synthesis
of monolithic COF materials. Additionally, the recent progress of
their application in environmental remediation is summarized, including
metal-ion removal, organic-pollutant capture, and oil–water
separation. Furthermore, this review discusses the current challenges
and provides future perspectives. We sincerely hope that it will contribute
to the further development of COF-based materials in other fields,
especially environmental remediation.