Cation-Coordinated Inner-Sphere CO₂ Electroreduction at Au-Water Interfaces

Electrochemical CO₂ reduction reaction (CO₂RR) is a promising technology for the clean energy economy. Numerous efforts have been devoted to enhancing the mechanistic understanding of CO₂RR from both experimental and theoretical studies. Electrolyte ions are critical for the CO₂RR; however, the role of alkali metal cations is highly controversial, and a complete free energy diagram of CO₂RR at Au-water interfaces is still missing. Here, we provide a systematic mechanism study toward CO₂RR via ab initio molecular dynamics simulations integrated with the slow-growth sampling (SG-AIMD) method. By using the SG-AIMD approach, we demonstrate that CO₂RR is facile at the inner-sphere interface in the presence of K cations, which promote the CO₂ activation with the free energy barrier of only 0.66 eV. Furthermore, the competitive hydrogen evolution reaction (HER) is inhibited by the interfacial cations with the induced kinetic blockage effect, where the rate-limiting Volmer step shows a much higher energy barrier (1.27 eV). Eventually, a comprehensive free energy diagram including both kinetics and thermodynamics of the CO₂RR to CO and the HER at the electrochemical interface is derived, which illustrates the critical role of cations on the overall performance of CO₂ electroreduction by facilitating CO₂ adsorption while suppressing the hydrogen evolution at the same time.