Non-copper metals catalyzing deep CO2 electroreduction to hydrocarbon

Abstract

Copper (Cu) is recognized as a unique metal catalyst in the electrochemical CO₂ reduction reaction (CO₂RR) because its moderate *CO binding ability can accelerate deep CO₂ reduction to valuable products. Here, for the first time, we realize the CO₂RR to hydrocarbon on various non-copper metal catalysts (Pd, Ag, Zn, and Ga) through a general strategy of modifying the local reaction environment. Taking the metallic Pd catalyst as an example, whose typical products were CO and H₂ in previous studies, a total faradaic efficiency of 50% to CH₄ + C₂H₄ can be achieved by implementing a pre-electrochemical activation process on the catalysts. The activation process can facilitate the adsorption behavior of interfacial *OH. The intensive spectroscopic studies combined with theoretical calculations revealed that improved *OH coverage prohibits the surface from *CO poisoning and accelerates the *CO hydrogenation process to *COH, accounting for the deep electroreduction to hydrocarbon products. Such a strategy of modifying the local environment can be extended to other I-type metals (Ag, Zn, and Ga) to generate hydrocarbons. This work highlights a new insight for advancing the CO₂RR to hydrocarbon beyond copper metal catalysts.