Atomic Regulation of Zigzag‐Structured 1D Covalent Organic Frameworks for Enhanced Photocatalytic CO ₂ Reduction Performance

Abstract The exploration of 1D covalent organic frameworks (1D COFs) has been limited due to significant challenges in achieving long‐range order and high crystallinity in their highly anisotropic structures. In this work, these challenges are overcome by synthesizing three highly crystalline 1D COFs with modular edge‐site atoms (C, N, and O) through innovative molecular design. These zigzag‐structured 1D COFs feature fully exposed side chains with abundant edge sites and highly directional long‐range ordered structures. This facilitates improved active site accessibility and uninterrupted pathways for electron transfer, resulting in enhanced charge separation and minimized recombination losses. By introducing atoms with different electronegativities at the edge sites, the electron‐donating ability of the 1D COFs is effectively regulated, and their performance differences in photocatalytic CO 2 reduction exhibit a regular variation. Without the use of sacrificial agents or noble metals, the 1D‐C‐COF exhibits the best CO 2 reduction performance, achieving a CO yield of 1406 µmol g −1 . This finding provides new insights into the structural design and photocatalytic performance of the 1D COFs materials in photocatalytic CO 2 reduction.