Layered oxyiodides with a Sillén-Aurivillius structure ([Bi2O2][An−1BnO3n+1][Bi2O2][X]; X = halide, n = number of perovskite layers) have attracted much attention as promising photocatalysts for visible-light-induced water splitting. Changing the number of perovskite layers in oxychlorides provides broad structural variations. However, there are no reports on the synthesis of Sillén-Aurivillius oxyiodides with n ≥ 3 due to unestablished synthetic methods. Three novel oxyiodides, namely, BaBi5Ti3O14I (n = 3), Ba2Bi5Ti4O17I (n = 4), and Ba3Bi5Ti5O20I (n = 5) with triple-, quadruple-, and quintuple-perovskite layers, respectively, were synthesized in this study by investigating and optimizing the synthetic routes in the solid-state reaction. The results reveal that the key to achieving the single-phase synthesis of multi-layered oxyiodides is avoiding the use of low-reactivity Aurivillius compounds as raw materials. The obtained oxyiodides possessed narrower band gaps than their chloride and bromide counterparts, as well as appropriate band levels for water splitting. They functioned as photocatalysts for water (reduction) and oxidation under (UV-) visible light; notably BaBi5Ti3O14I exhibited significantly higher photocatalytic O2 evolution than the other oxyiodides and chloride/bromide counterparts.
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