Preparation of Redox‐Active Metal–Organic Frameworks via Post‐Synthetic Modification of Organic Selenium for In Situ Confinement of Metal Nanoparticles

Abstract Redox‐active metal–organic frameworks (MOFs), with switchable physicochemical properties depending on their redox state, are widely used in catalysis, selective separation, and electrochemical sensing. However, the complex fabrication process limits the applications. Herein, a post‐synthetic modification strategy is proposed to prepare redox‐active MOFs by covalent grafting organic selenium compounds. The selenium moieties can reduce metal salt to in situ generate metal nanoparticles (MNPs) without an external reducing agent, and also act as anchors to stabilize the generated MNPs. As a proof of concept, two kinds of MOFs are selected to prepare redox‐active MOFs‐Se and further fabricate MNPs@MOFs composite materials. With controllable confinement of the MNPs, the MNPs@MOFs composite show noteworthy photocatalytic and electrocatalytic activity.