Enhancing the Photocatalytic Activity of Zirconium‐Based Metal–Organic Frameworks Through the Formation of Mixed‐Valence Centers

Despite the desirability of metal–organic frameworks (MOFs) as heterogeneous photocatalysts, current strategies available to enhance the performance of MOF photocatalysts are complicated and expensive. Herein, a simple strategy is presented for improving the activity of MOF photocatalysts by regulating the atomic interface structure of the metal active sites on the MOF. In this study, MOF (PCN‐222) is hybridized with cellulose acetate (CA@PCN‐222) through an optimized atomic interface strategy, which lowers the average valence state of Zr ions. The electronic metal‐support interaction mechanism of CA@PCN‐222 is revealed by evaluating the photocatalytic CO(2) reduction reaction (CO(2)RR). The experimental results suggested that the electron migration efficiency at the atomic interface of the MOFs strongly coupled with cellulose is significantly improved. In particular, the CO(2)RR to formate activity of CA@PCN‐222 photocatalyst greatly increased from 778.2 to 2816.0 µmol g(−1) compared with pristine PCN‐222 without cellulose acetate. The findings suggest that the strongly coupled metal–ligand moiety at the atomic interface of MOFs may play a synergistic role in heterogeneous catalysts.