Synthesis and Structure of the Double-Layered Sillén–Aurivillius Perovskite Oxychloride La(2.1)Bi(2.9)Ti(2)O(11)Cl as a Potential Photocatalyst for Stable Visible Light Solar Water Splitting

[Image: see text] Exploring photocatalysts for solar water splitting is a relevant step toward sustainable hydrogen production. Sillén–Aurivillius-type compounds have proven to be a promising material class for photocatalytic and photoelectrochemical water splitting with the advantage of visible light activity coupled to enhanced stability because of their unique electronic structure. Especially, double- and multilayered Sillén–Aurivillius compounds [A(n–1)B(n)O(3n+1)][Bi(2)O(2)](2)X(m), with A and B being cations and X a halogen anion, offer a great variety in material composition and properties. Yet, research in this field is limited to only a few compounds, all of them containing mainly Ta(5+) or Nb(5+) as cations. This work takes advantage of the outstanding properties of Ti(4+) demonstrated in the context of photocatalytic water splitting. A fully titanium-based oxychloride, La(2.1)Bi(2.9)Ti(2)O(11)Cl, with a double-layered Sillén–Aurivillius intergrowth structure is fabricated via a facile one-step solid-state synthesis. A detailed crystal structure analysis is performed via powder X-ray diffraction and correlated to density functional theory calculations, providing a detailed understanding of the site occupancies in the unit cell. The chemical composition and the morphology are studied using scanning and transmission electron microscopy together with energy-dispersive X-ray analysis. The capability of the compound to absorb visible light is demonstrated by UV–vis spectroscopy and analyzed by electronic structure calculations. The activity toward the hydrogen and the oxygen evolution reaction is evaluated by measuring anodic and cathodic photocurrent densities, oxygen evolution rates, and incident-current-to-photon efficiencies. Thanks to the incorporation of Ti(4+), this Sillén–Aurivillius-type compound enables best-in-class photoelectrochemical water splitting performance at the oxygen evolution side under visible light irradiation. Thus, this work highlights the potential of Ti-containing Sillén–Aurivillius-type compounds as stable photocatalysts for visible light-driven solar water splitting.