Boosting CO₂ 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 CO₂ reduction. Herein, a synergistic strategy that introduces photosensitive components and visible light into a stable system is reported to improve the performance for CO₂ 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 CO₂ -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.