A series of Sillén–Aurivillius layered oxyhalides with a single- and double-perovskite layer, Bi₄MO₈X (M = Nb, Ta; X = Cl, Br) and AA′Bi₃M₂O₁₁Cl (A, A′ = Sr, Ba, Pb, Bi; M = Ti, Nb, Ta), have been recently demonstrated as promising photocatalysts for visible-light-induced water splitting due to relatively high energy valence bands arising from strong interactions between Bi-6s and O-2p orbitals. Herein, we report the synthesis, characterization and photocatalytic property of Bi₅SrTi₃O₁₄Cl with triple-perovskite layers. The combined use of synchrotron X-ray diffraction and scanning transmission electron microscopy allowed the precise determination of the crystal structure (space group: P2an), including site occupancies. The experimental results revealed that Bi₅SrTi₃O₁₄Cl possesses a similar bandgap and valence band level as the previously reported Bi₅PbTi₃O₁₄Cl, indicating that the presence of Pb-6s is not essential for the formation of a higher energy valence band maximum. Partial density of states for both materials obtained by DFT calculations suggested considerable interactions of the Bi-6s orbitals with the O-2p orbitals, in particular those in the perovskite layers, which is the key to the formation of the higher energy valence band. Bi₅SrTi₃O₁₄Cl exhibited higher activity for O₂ evolution than Bi₅PbTi₃O₁₄Cl, suggesting the detrimental effect of Pb²⁺ on the photocatalytic activity, thereby allowing the construction of a Z-scheme water splitting system workable under visible light.

一系列Sillén-Aurivillius的分层卤氧化物与单和双钙钛矿层，铋₄中号ö ₈ X（中号=铌，钽; X =氯，溴）和A-A'的Bi ₃中号₂ ö ₁₁氯（甲，A' = Sr，Ba，Pb，Bi; M = Ti，Nb，Ta）最近被证明是有前途的光催化剂，可用于可见光诱导的水分解，因为Bi-6s之间强烈的相互作用产生了相对较高的价价带和O-2p轨道。在这里，我们报告Bi ₅ SrTi ₃的合成，表征和光催化性能O ₁₄ Cl具有三层钙钛矿层。同步加速器X射线衍射和扫描透射电子显微镜的结合使用，可以精确确定晶体结构（空间群：P 2 an），包括位置占用。实验结果表明，Bi ₅ SrTi ₃ O ₁₄ Cl具有与以前报道的Bi ₅ PbTi ₃ O ₁₄相似的带隙和价带能级。Cl，表明Pb-6s的存在对于形成更高的价带最大值不是必需的。通过DFT计算获得的两种材料的部分态密度表明Bi-6s轨道与O-2p轨道之间存在相当大的相互作用，尤其是钙钛矿层中的相互作用，这是形成较高能价带的关键。毕₅ SrTi ₃ ö ₁₄氯表现出更高的活性用于O- ₂进化与Bi ₅ PBTI ₃ ö ₁₄氯，这表明铅的有害影响²⁺ 因此，可以构建在可见光下可使用的Z方案水分解系统。