Molten Salts-Driven Discovery of a Polar Mixed-Anion 3D framework at the nanoscale: Zn4Si2O7Cl2, Charge Transport and Photoelectrocatalytic Water Splitting

Mixed-anion compounds widen the chemical space of attainable materials compared to single anionic compounds, but the exploration of their structural diversity is limited by common synthetic paths. Especially, oxychlorides rely mainly on layered structures, which suffer from low stability during photo(electro)catalytic processes. Herein we report a strategy to design a new polar 3D tetrahedral framework with composition Zn4Si2O7Cl2. We use a molten salt medium to enable low temperature crystallization of nanowires of this new compound, by relying on tetrahedral building units present in the melt to build the connectivity of the oxychloride. These units are combined with silicon-based connectors from a non-oxidic Zintl phase to enable precise tuning of the oxygen content. This structure brings high chemical and thermal stability, as well as strongly anisotropic hole mobility along the polar axis. These features, associated with the ability to adjust the transport properties by doping, enable to tune water splitting properties for photoelectrocatalytic H-2 evolution and water oxidation. This work then paves the way to a new family of mixed-anion solids

Automated summary

This study presents a strategy to design a new polar 3D tetrahedral framework and successfully crystallize the compound at low temperature using a molten salt medium. The resulting structure exhibits high chemical and thermal stability, as well as strong anisotropic hole mobility along the polar axis. The ability to adjust transport properties by doping enables the tuning of water splitting properties for photoelectrocatalytic H-2 evolution and water oxidation.