A Sillen oxyhalide SrBi3O4Cl3 as a promising photocatalyst for water splitting: impact of the asymmetric structure on light absorption and charge carrier dynamics

Bismuth-based oxyhalides with layered Sillen(-Aurivillius) structures have attracted significant attention as photocatalysts. Recent studies have unveiled a part of the structure-property relationship of the materials; however, it has not been fully understood. In the present study, we investigated a Sillen-type oxyhalide SrBi3O4Cl3 with single and double halogen layers. Interestingly, SrBi3O4Cl3 showed a visible light response up to & SIM;460 nm, whereas SrBiO2Cl and BiOCl with single and double halogen layers, respectively, did not. Rietveld refinement and STEM-EDX mapping determined the asymmetric Bi occupation in the fluorite [Sr0.5Bi1.5O2] layer of SrBi3O4Cl3, which was derived from the coexistence of the halogen layers. DFT calculations and Madelung potential calculations showed that the asymmetric Bi occupation affords both the Bi-Bi interaction across the single halogen layer and the electrostatic destabilization of Cl in the double halogen layer, probably leading to the narrow bandgap of SrBi3O4Cl3. Another merit of possessing the two different halogen layers was revealed by time-resolved microwave conductivity measurements as well as DFT calculations; the spatial separation of the conduction band minimum and valence band maximum based on the coexistence of the halogen layers would promote charge carrier separation. Visible-light-driven Z-scheme water splitting was accomplished using a RuO2-loaded SrBi3O4Cl3 sample as an O-2-evolving photocatalyst. This study provides another option for engineering band structures and promoting the charge carrier separation of layered oxyhalides for efficient water splitting under visible light.

Automated summary

Bismuth-based oxyhalides with layered Sillen(-Aurivillius) structures have been studied as photocatalysts. A Sillen-type oxyhalide, SrBi3O4Cl3, showed visible light response up to 460 nm, attributed to the asymmetric Bi occupation and the coexistence of halogen layers. This study also revealed the spatial separation of the conduction band minimum and valence band maximum in SrBi3O4Cl3, which promotes charge carrier separation and facilitates visible-light-driven water splitting.