In situ unraveling of the effect of the dynamic chemical state on selective CO2 reduction upon zinc electrocatalysts

Abstract

Unraveling the reaction mechanism behind the CO₂ reduction reaction (CO₂RR) is a crucial step for advancing the development of efficient and selective electrocatalysts to yield valuable chemicals. To understand the mechanism of zinc electrocatalysts toward the CO₂RR, a series of thermally oxidized zinc foils is prepared to achieve a direct correlation between the chemical state of the electrocatalyst and product selectivity. The evidence provided by in situ Raman spectroscopy, X-ray absorption spectroscopy (XAS) and X-ray diffraction significantly demonstrates that the Zn(II) and Zn(0) species on the surface are responsible for the production of carbon monoxide (CO) and formate, respectively. Specifically, the destruction of a dense oxide layer on the surface of zinc foil through a thermal oxidation process results in a 4-fold improvement of faradaic efficiency (FE) of formate toward the CO₂RR. The results from in situ measurements reveal that the chemical state of zinc electrocatalysts could dominate the product profile for the CO₂RR, which provides a promising approach for tuning the product selectivity of zinc electrocatalysts.