Nanostructurally Engineering Covalent Organic Frameworks for Boosting CO2 Photoreduction

Abstract Herein, a series of imine‐linked covalent organic frameworks (COFs) are developed with advanced ordered mesoporous hollow spherical nanomorphology and ultra‐large mesopores (4.6 nm in size), named OMHS‐COF‐M (M = H, Co, and Ni). The ordered mesoporous hollow spherical nanomorphology is revealed to be formed via an Ostwald ripening mechanism based on a one‐step self‐templated strategy. Encouraged by its unique structural features and outstanding photoelectrical property, the OMHS‐COF‐Co material is applied as the photocatalyst for CO2‐to‐CO reduction. Remarkably, it delivers an impressive CO production rate as high as 15 874 µmol g−1 h−1, a large selectivity of 92.4%, and a preeminent cycling stability. From in/ex situ experiments and density functional theory (DFT) calculations, the excellent CO2 photoreduction performance is ascribed to the desirable cooperation of unique ordered mesoporous hollow spherical host and abundant isolated Co active sites, enhancing CO2 activation, and improving electron transfer kinetics as well as reducing the energy barriers for intermediates *COOH generation and CO desorption.