Unexpected high selectivity for acetate formation from CO(2) reduction with copper based 2D hybrid catalysts at ultralow potentials

Copper-based catalysts are efficient for CO(2) reduction affording commodity chemicals. However, Cu(i) active species are easily reduced to Cu(0) during the CO(2)RR, leading to a rapid decay of catalytic performance. Herein, we report a hybrid-catalyst that firmly anchors 2D-Cu metallic dots on F-doped Cu(x)O nanoplates (Cu(x)OF), synthesized by electrochemical-transformation under the same conditions as the targeted CO(2)RR. The as-prepared Cu/Cu(x)OF hybrid showed unusual catalytic activity towards the CO(2)RR for CH(3)COO(−) generation, with a high FE of 27% at extremely low potentials. The combined experimental and theoretical results show that nanoscale hybridization engenders an effective s,p-d coupling in Cu/Cu(x)OF, raising the d-band center of Cu and thus enhancing electroactivity and selectivity for the acetate formation. This work highlights the use of electronic interactions to bias a hybrid catalyst towards a particular pathway, which is critical for tuning the activity and selectivity of copper-based catalysts for the CO(2)RR.