Electrochemical reduction of CO2 on pure and doped Cu2O(1 1 1)

Cu₂O has been demonstrated to be effective for converting CO₂ into value-added products. However, the mechanism of the carbon dioxide reduction (CO₂R) on the most stable surface, Cu₂O(1 1 1), is still under debate. Additionally, how to improve its activity and selectivity is a challenging issue too. In this work, we unravel that CO₂R can occur before Cu₂O reduction (Cu₂O-R) when the applied potential is below −0.44 V and doping can improve its catalytic performance based on first-principles calculations. The pure Cu₂O(1 1 1) surface shows high activity and selectivity for the production of formic acid (HCOOH). However, the performance of CO₂R deteriorates on the reduced Cu₂O(1 1 1). Doping p-block elements (Al, Ga, In, Tl, Sn, Pb, Bi) is proven to be a workable strategy to improve its catalytic performance by suppressing hydrogen evolution reaction (HER). Importantly, Ga-Cu₂O exhibits the favorable bonding strength for *OCHO, which is responsible for the optimal catalytic activity (−0.18 V) among other p-block elements. Our calculations thus provide an insight into CO₂ reduction mechanism of Cu₂O(1 1 1), favoring rational design of Cu₂O-based catalyst.