Molecular Cleavage of Metal-Organic Frameworks and Application to Energy Storage and Conversion.

The physicochemical properties of metal-organic frameworks (MOFs) significantly depend on composition, topology, and porosity, which can be tuned via synthesis. In addition to a classic direct synthesis, postsynthesis modulations of MOFs, including ion exchange, installation, and destruction, can significantly expand the application. Because of a limitation of the qualitative hard and soft acids and bases (HSAB) theory, posttreatment permits regulation of MOF structure by cleaving chemical bonds at the molecular level. Here, methods of coordination bond scission to tailor the structure are critically appraised and the application to energy storage and conversion is assessed. MOF structures synthesized by molecular-level coordination bond cleavage are described and the corresponding MOFs for electrocatalysis and renewable battery applications are evaluated. Significant emphasis is placed on various coordination bond cleavage to tune properties, including chemical groups, electronic structures, and morphologies. The review concludes with a critical perspective on practical application, together with challenges and future outlook for this emerging field.