An Atomic-scale Explanation For The High Selectivity Towards Carbon Dioxide Reduction Observed On Liquid Metal Catalysts.

Abstract

The low-temperature liquid metals Ga-In and Ga-Snhave previously showcased >95% selectivity towards the electrochemical reduction of CO2to formate, occuring only when the alloys are melted, not solid.Here, density functional theory molecular dynamics and metadynamics simulations reveal that CO2does not directly adsorb to the Ga-alloy surface, but instead is reduced indirectly by reaction with an adsorbed hydrogen. The reaction barrier is vastly more favourable when this process occurs at In or Sn sites (average: 0.26 eV), than when it occurs on Ga (average: 0.47 eV). However, there is no difference in barrier between solid and liquid surfaces. Instead, we find that Hadsis mobile only on the liquid surface, travelling due to the motion of the liquid beneath. This process drives Hadsto In/Sn sites, allowing low-barrier CO2reduction to occur only on the liquid. Therefore, the dynamic motion of liquid metal catalysts can underpin their unique reactivity. The result has far reaching implications for any protonation reaction conducted with a liquid metal catalyst.