Boosting CO2 Photoreduction via Regulating Charge Transfer Ability in a One‐Dimensional Covalent Organic Framework

Two-dimensional (2D) imine-based covalent organic frameworks (COFs) hold potential for photocatalytic CO2 reduction. However, high energy barrier of imine linkage impede the in-plane photoelectron transfer process, resulting in inadequate efficiency of CO2 photoreduction. Herein, we present a dimensionality induced local electronic modulation strategy through the construction of one-dimensional (1D) pyrene-based covalent organic frameworks (PyTTA-COF). The dual-chain-like edge architectures of 1D PyTTA-COF enable the stabilization of aromatic backbones, thus reducing energy loss during exciton dissociation and thermal relaxation, which provides energetic photoelectron to traverse the energy barrier of imine linkages. As a result, the 1D PyTTA-COF exhibits significantly enhanced CO2 photoreduction activity under visible-light irradiation when coordinated with metal cobalt ion, yielding a remarkable CO evolution of 1003 μmol g-1 over an 8-hour period, which surpasses that of the corresponding 2D counterpart by a factor of 59. These findings present a valuable approach to address in-plane charge transfer limitations in imine-based COFs.