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

The electrocatalytic CO2 reduction reaction (CO2RR) can dynamise the carbon cycle by lowering anthropogenic CO2 emissions and sustainably producing valuable fuels and chemical feedstocks. Methanol is arguably the most desirable C-1 product of CO2RR, although it typically forms in negligible amounts. In our search for efficient methanol-producing CO2RR 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 CO2 to CH3OH, while their alloys produce CH3OH with Faradaic efficiencies of approximately 1 %. Interestingly, with nanostructuring PD-Zn/Ag foam reduces CO2 to CH3OH 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 CO2RR to CH3OH in a reaction pathway mediated by adsorbed CO and formaldehyde. Surprisingly, the stability of the *CHO intermediate does not influence the activity.