Interwoven Porous Pristine Cobalt‐Based Metal‐Organic Framework as an Efficient Photocatalyst for CO 2 Reduction

Abstract As a desired utilization of the conversion of CO 2 into valuable carbon fuel production under solar energy, it remains challenging due to the lack of efficient catalysts. Herein, a 3D interpenetrating metal‐organic framework of [Co(Tipa)(HCOO) 2 (H 2 O)]·H 2 O (Co‐Tipa) with 1D open channel is solvothermally synthesized using a semi‐flexible ligand (Tipa = tri‐(4‐(1 H ‐imidazol‐1‐yl)‐phenyl)amine). The tridentate bridge ligand‐oriented periodicity Co‐Tipa MOF is combined with ruthenium‐based photosensitizers under mild reaction conditions to form an efficient nonhomogeneous co‐catalyst for photocatalytic CO 2 reduction reaction (CO 2 RR). As a crystalline MOFs catalyst, the CO production rate, selectivity, and the quantum yield under visible light irradiation offer outstanding performance for the synergistic advantages of structural feature, metal center, and organic ligand. The stability and reusability of the Co‐Tipa co‐catalyst in the reaction system are profited from the robust 3D entangled framework. The mechanism of how to enhance CO 2 RR performance for the Co‐Tipa is assisted in illustration through density functional theory (DFT) calculations. By leveraging the unique structural properties of entangled MOFs, this study offers innovative approaches for the development of more effective and s Co‐Tipa catalysts that can selectively CO 2 into valuable chemicals and fuels.