Unexpected high selectivity for acetate formation from CO₂ reduction with copper based 2D hybrid catalysts at ultralow potentials

Abstract

Copper-based catalysts are efficient for CO₂ reduction affording commodity chemicals. However, Cu(i) active species are easily reduced to Cu(0) during the CO₂RR, 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 _<i>x</i> O nanoplates (Cu _<i>x</i> OF), synthesized by electrochemical-transformation under the same conditions as the targeted CO₂RR. The as-prepared Cu/Cu _<i>x</i> OF hybrid showed unusual catalytic activity towards the CO₂RR for CH₃COO^- 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 _<i>x</i> 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 CO₂RR.