Boosting CO 2 Electroreduction via the Synergistic Effect of Tuning Cationic Clusters and Visible‐Light Irradiation

Introducing an external light field can increase the intrinsic activity and energy efficiency for electrochemical CO 2 reduction. Herein, a synergistic strategy that introduces photosensitive components and visible light into a stable system is reported to improve the performance for CO 2 reduction. The catalytic kinetics studies indicate that the synergistic effect of implantation of cationic Ti and additional light driving is the primary responsibility for accelerating the first electron transfer to form a *COO − intermediate. This leads to a satisfactory CO 2 ‐to‐CO conversion for Zr/Ti‐NB‐Co in terms of high selectivity (Faradaic efficiency of 93.6% at −0.7 V), remarkable catalytic activity (production rate up to 546 mmol g −1 h −1 at −1.1 V), excellent long‐term stability (without performance decay over 11 h), and large turnover frequency of 1028 h −1 at −1.1 V under visible light. These results imply that the photodriven Ti‐based porphyrin catalyst not only can deliver more electrons, but also can act as a photoswitch to adjust the electron transfer pathway.