Steric effect induces CO electroreduction to CH4 on Cu–Au alloys.

The electrocatalytic reduction of carbon monoxide (CO) is an emerging direction with new catalyst structures, among which the bimetallic component catalysts feature both functional diversity and high-density of active sites. In this work, we demonstrate that the fine tuning of adjacent bimetallic sites can allow us to select different reaction pathways toward C₁ or C₂ products in the electroreduction of CO. Cu and Cu–Au alloy catalysts with different atomic ratios were fabricated and investigated for appropriate molecular distances. The pure Cu catalyst was found to be active for electroreducing CO to C₂H₄, as the adjacent Cu sites were beneficial for adsorbing multiple CO molecules and subsequent C–C coupling. On the other hand, alloying Cu with Au introduced steric hindrance and a larger intermolecular distance between adjacent adsorbed *CO intermediates, thus leading to a decrease of C₂H₄ selectivity but an enhanced CH₄ pathway. Our work revealed the importance of spacing between active sites for CO electroreduction, which can benefit the catalyst design to further improve activities and selectivities in electrocatalytic CO reduction. [ABSTRACT FROM AUTHOR]