Tailoring the ^*CO and *H Coverage for Selective CO₂ Electroreduction to CH₄ or C₂H₄

In the electrochemical CO2 reduction reaction (CO2RR), the coverages of *CO and *H intermediates on a catalyst surface are critical for the selective generation of C-1 or C-2 products. In this work, we have synthesized several CuxZnyMnz ternary alloy electrocatalysts, including Cu8ZnMn, Cu8Zn6Mn, and Cu8ZnMn2, by varying the doping compositions of Zn and Mn, which are efficient in binding *CO and *H adsorbates in the CO2 electroreduction process, respectively. The increase of *H coverage allows to promotion of the CH4 and H-2 formation, while the increase of the *CO coverage facilitates the production of C2H4 and CO. As a result, the Cu8ZnMn catalyst presented a high CO2-to-CH4 partial current density (-418 +/- 22 mA cm(-2)) with a Faradaic efficiency of 55 +/- 2.8%, while the Cu8Zn6Mn catalyst exhibited a CO2-to-C2H4 partial current density (-440 +/- 41 mA cm(-2)) with a Faradaic efficiency of 58 +/- 4.5%. The study suggests a useful strategy for rational design and fabrication of Cu electrocatalysts with different doping for tailoring the reduction products.