This paper presents a novel electrostatically driven self-assembly approach for synthesizing a photocatalyst with bifunctional LaNi sites within a covalent organic framework (COF). The La site acts as the optically active center, generating photocarriers, while the Ni site serves as the catalytically active center for highly selective CO₂-to-CO reduction. Theoretical calculations and in-situ characterization reveal directional charge transfer between La-Ni sites, enhancing CO₂-to-CO conversion. The resulting LaNi-Phen/COF-5 photocatalyst shows a 15.2-fold increase in CO₂ reduction rate (605.8 µmol·g⁻¹h⁻¹) compared to a benchmark COF and high CO selectivity (98.2%). This work offers a promising strategy for designing efficient photocatalysts for CO₂ reduction.

Min Zhou, Zhiqing Wang, Aohan Mei, Zifan Yang, Wen Chen, Siyong Ou, Shengyao Wang, Keqiang Chen, Peter Reiss, Kun Qi, Jingyuan Ma, Yueli Liu