Surface Coverage as an Important Parameter for Predicting Selectivity Trends in Electrochemical CO Reduction.

The electrochemical CO reduction reaction (CORR) is important for a sustainable future. Key insights into the reaction pathways have been obtained by density functional theory (DFT) analysis, but so far, DFT has been unable to give an overall understanding of selectivity trends without important caveats. We show that an unconsidered parameter in DFT models of electrocatalysts-the surface coverage of reacting species-is crucial for understanding the CORR selectivities for different surfaces.