1D Covalent Organic Frameworks with Tunable Dual-Cobalt Synergistic Sites for Efficient CO Photoreduction.

Diatomic catalysts enhance photocatalytic CO reduction through synergistic effects. However, precisely regulating the distance between two catalytic centers to achieve synergistic catalysis poses significant challenges. In this study, a series of one-dimensional (1D) covalent organic frameworks (COFs) are designed with adjustable micropores to facilitate efficient CO photoreduction. CO molecules are anchored between dual-cobalt centers within micropores, thus effectively reducing their activation energy and initiating the photocatalytic process. Additionally, the formation of *COOH intermediates is significantly influenced by the coordination microenvironment around dual-cobalt sites. Notably, COF-Co-N exhibited remarkable CO photoreduction activity with a CO evolution rate of 110.3 µmol·g·h, which surpasses most of previously reported single-atom-site photocatalysts. Comprehensive characterization and density functional theory (DFT) calculations revealed that 1D COFs with dual-cobalt sites possess the ability to anchor CO molecules, thereby enhancing the efficacy of synergistic catalysis. Simultaneously, COF-Co-N with quadruple nitrogen coordination significantly reduced the energy barrier of crucial *COOH intermediate, facilitating efficient photocatalytic CO reduction. This study meticulously modulated the coordination microenvironment surrounding dual-cobalt synergistic sites, providing new insight into the design of high-performance photocatalysts.