Insight into the Formation and Transfer Process of the First Intermediate of CO₂ Reduction over Ag-Decorated...

It is still poorly understood how the first intermediates of CO₂ reduction are formed and converted to multi-carbon products over Cu-based electrodes. Herein, Ag is used to decorate dendritic Cu and a high Faradaic efficiency (FE) for C₂ H₄ (25 %) is obtained on a CuAg electrode, which is about five times higher than dendritic Cu. The intermediates including *CO₂ ^- , OH groups, Cu-CO, C-O rotation, and CH_x species are investigated by in situ Raman spectroscopy. This work provides spectroscopic evidence that the first intermediate of CO₂ reduction on Ag-decorated Cu is carboxylate anion *CO₂ ^- bonded with the catalyst surface through the C and O atom. The formation and evolution process of the *CO₂ ^- intermediate over the applied potential are investigated in depth as well. This research contributes to a better understanding of the mechanism of CO₂ reduction and multi-carbon product formation pathways over Ag-decorated Cu.