Atomic Interlayer Mo–N ₄ Sites Enable Rapid Charge Transfer and Efficient CO ₂ Photoreduction

ABSTRACT Photocatalytic CO ₂ reduction is a promising route for sustainable carbon conversion, but its efficiency is often limited by poor charge separation and a lack of functional active sites. Here, we address these challenges by constructing an atomic Mo–N ₄ interlayer electron bridge (IEB) within a bipyridine‐based covalent organic framework (COF) via a photoreduction method. Guided by DFT screening, Mo was identified as the optimal metal center, enabling simultaneous CO ₂ activation and ultrafast vertical electron transfer. The resulting Mo@Tp‐Bpy catalyst achieves co‐production rates of 948.0 µmol g ⁻¹ h ⁻¹ for CO and 3741.7 µmol g ⁻¹ h ⁻¹ for anisaldehyde via coupled CO ₂ reduction and 4‐methoxybenzyl alcohol oxidation, corresponding to 6.2‐fold and 5.0‐fold enhancements over the pristine Tp‐Bpy COF, respectively. Mechanistic studies reveal that the Mo–N ₄ sites facilitate interlayer charge kinetics and lower thermodynamic barriers for both half‐reactions. This work presents a rational atomic‐level strategy for integrating charge management and catalytic function in layered materials toward efficient photoredox catalysis.