Insights into the Electrochemical CO 2 RR Performance and Binding of Small Molecules on Quaternary Thiospinels Ag 2 FeSn 3 S 8 and Cu 2 FeSn 3 S 8 .

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 (Ag 2 FeSn 3 S 8 ) and rhodostannite (Cu 2 FeSn 3 S 8 ) was discovered. Both thiospinels display faradaic efficiencies of up to 73% for CO 2 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% H 2 at 100 mA cm -2 and rhodostannite 28% CO and 37% H 2 . 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 Ag 2 FeSn 3 S 8 and Cu 2 FeSn 3 S 8 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.