Post-synthetic modifications (PSM) on metal-organic frameworks (MOFs) for visible-light-initiated photocatalysis.

The utilization of green and sustainable solar energy via photocatalysis is regarded as a promising strategy to tackle the ever-increasing energy shortage and environmental deterioration. In addition to traditional semiconductor-based photocatalysts, metal-organic frameworks (MOFs), a class of crystalline micro-mesoporous hybrid materials constructed from metal or metal nodes interconnected with multi-dentate organic linkers, are emerging as a new type of photocatalytic material. Post-synthetic modifications (PSM) on MOFs, in which chemical transformations or exchanges are made on pre-synthesized MOF materials, are found to be a powerful strategy for fabricating photoactive MOFs based on already existing MOFs. In this frontier article, different PSM strategies for the development of photoactive MOFs, including coordination on unsaturated metal sites, metalation on open coordinated sites, covalent modifications on ligands, ligand exchange, metal exchange and cavity encapsulation, have been summarized. Our views on the challenges and the direction in developing photocatalytic MOFs by PSM are also addressed. We hope that this frontier article can provide some guidance for rational designing of highly efficient MOF-based photocatalysts via PSM strategies and to stimulate more research interest to be devoted to this promising yet largely unexplored field.