Facile CO2 Electro-Reduction to Formate via Oxygen Bidentate Intermediate Stabilized by High-Index Planes of Bi Dendrite Catalyst

Electrochemical CO 2 conversion to chemical products is a promising strategy for sustainable industrial development. However, the success of this approach requires an in-depth understanding of catalysis because it involves highly complex multistep reactions. Herein, we suggest a rational design of a hierarchical Bi dendrite catalyst for an efficient conversion of CO 2 to formate. A high selectivity (∼89% at −0.74 V RHE ) and, more importantly, a stable performance during long-term operation (∼12 h) were achieved with the Bi dendrite. Density functional theory (DFT) is used to investigate three possible reaction pathways in terms of surface intermediate, and the one via *OCOH surface intermediate is calculated to be the most energetically feasible. DFT calculations further elucidate the plane-dependent catalytic activity and conclude that the high-index planes developed on the Bi dendrite…