Enhanced Electroreduction of Carbon Dioxide to Methanol Using Zinc Dendrites Pulse‐Deposited on Silver Foam

The electrocatalytic CO 2 reduction reaction (CO 2 RR) can dynamise the carbon cycle by lowering anthropogenic CO 2 emissions and sustainably producing valuable fuels and chemical feedstocks. Methanol is arguably the most desirable C 1 product of CO 2 RR, although it typically forms in negligible amounts. In our search for efficient methanol‐producing CO 2 RR catalysts, we have engineered Ag‐Zn catalysts by pulse‐depositing Zn dendrites onto Ag foams (PD‐Zn/Ag foam). By themselves, Zn and Ag cannot effectively reduce CO 2 to CH 3 OH, while their alloys produce CH 3 OH with Faradaic efficiencies of approximately 1 %. Interestingly, with nanostructuring PD‐Zn/Ag foam reduces CO 2 to CH 3 OH with Faradaic efficiency and current density values reaching as high as 10.5 % and −2.7 mA cm −2 , respectively. Control experiments and DFT calculations pinpoint strained undercoordinated Zn atoms as the active sites for CO 2 RR to CH 3 OH in a reaction pathway mediated by adsorbed CO and formaldehyde. Surprisingly, the stability of the *CHO intermediate does not influence the activity.