Insights into the Electrochemical CO2RR Performance and Binding of Small Molecules on Quaternary Thiospinels Ag2FeSn3S8 and Cu2FeSn3S8

Using a mechanical synthesis method in the form of ball milling and an additional annealing step, a novel and accelerated route for the synthesis of the thiospinels toyohaite (Ag₂FeSn₃S₈) and rhodostannite (Cu₂FeSn₃S₈) was discovered. Both thiospinels display faradaic efficiencies of up to 73% for CO₂ reduction to CO using an organic electrolyte in an H-type cell. The materials were furthermore implemented in a zero-gap electrolyzer, with toyohaite producing 22% CO and 52% H₂ at 100 mA cm^-2 and rhodostannite 28% CO and 37% H₂. The catalytically active sites are studied using density functional theory, revealing strong CO binding interactions on both Ag and Cu, whereas Sn is found to contribute to the decomposition of Ag₂FeSn₃S₈ and Cu₂FeSn₃S₈ by coordination with oxygen. Postmortem analysis of the thiospinel-based electrodes by means of SEM-EDX, XRD, XPS, and Mössbauer spectroscopy showed sulfur leaching from the catalysts after applying 100 mA cm^-2. These spectroscopic results-in conjunction with DFT calculations of the oxidized surfaces-suggest that the catalytically active species consists of metal oxides. As a conversion of the metal sulfides into the corresponding metallic species was observed via XRD, the decomposition pathways of both catalysts were also computed using DFT; thus, elucidating the energetically most favorable decomposition products and expanding the possible composition of the catalysts postelectrolysis.