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Layered Perovskite Oxyiodide with Narrow Band Gap and Long Lifetime Carriers for Water Splitting Photocatalysis
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-05-17 , DOI: 10.1021/jacs.1c02763 Kanta Ogawa 1, 2 , Hajime Suzuki 1 , Chengchao Zhong 1 , Ryota Sakamoto 1 , Osamu Tomita 1 , Akinori Saeki 3 , Hiroshi Kageyama 1 , Ryu Abe 1, 2
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-05-17 , DOI: 10.1021/jacs.1c02763 Kanta Ogawa 1, 2 , Hajime Suzuki 1 , Chengchao Zhong 1 , Ryota Sakamoto 1 , Osamu Tomita 1 , Akinori Saeki 3 , Hiroshi Kageyama 1 , Ryu Abe 1, 2
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The development of semiconductors with narrow band gap and high stability is crucial for achieving solar to chemical energy conversion. Compounds with iodine, which has a high polarizability, have attracted attention because of their narrow band gap and long carrier lifetime, as typified by halide perovskite solar cells; however, they have been regarded as unsuitable for harsh photocatalytic water splitting because iodine is prone to self-oxidation. Here, we demonstrate that Ba2Bi3Nb2O11I, a layered Sillén–Aurivillius oxyiodide, not only has access to a wider range of visible light than its chloride and bromide counterparts, but also functions as a stable photocatalyst, efficiently oxidizing water. Density functional theory calculations reveal that the oxygen 2p orbitals in the perovskite block, rather than the fluorite Bi2O2 block as previously pointed out, anomalously push up the valence band maximum, which can be explained by a modified Madelung potential analysis that takes into account the high polarizability of iodine. In addition, the highly polarizable iodide contributes to longer carrier lifetime of Ba2Bi3Nb2O11I, allowing for a significantly higher quantum efficiency than its chloride and bromide counterparts. Visible-light-driven Z-scheme water splitting was achieved for the first time in an iodine-based system using Ba2Bi3Nb2O11I as an oxygen-evolution photocatalyst. The present study provides a novel approach for incorporating polarizable “soft” anions into building blocks of layered materials to manipulate the band structure and improve the carrier dynamics for visible-light responsive functions.
中文翻译：
用于水分解光催化的具有窄带隙和长寿命载体的层状钙钛矿氧碘化物
具有窄带隙和高稳定性的半导体的发展对于实现太阳能到化学能的转换至关重要。具有高极化率的含碘化合物因其窄带隙和长载流子寿命而备受关注，例如卤化物钙钛矿太阳能电池；然而，它们被认为不适合苛刻的光催化水分解，因为碘易于自氧化。在这里，我们证明了 Ba 2 Bi 3 Nb 2 O 11I，一种分层的 Sillén-Aurivilius 氧碘化物，不仅比其氯化物和溴化物更能接触到更广泛的可见光，而且还可以作为稳定的光催化剂，有效地氧化水。密度泛函理论计算表明，钙钛矿块中的氧 2p 轨道，而不是之前指出的萤石 Bi 2 O 2块，异常推高价带最大值，这可以通过修正的马德隆势分析来解释，该分析考虑到考虑到碘的高极化率。此外，高度极化的碘化物有助于延长 Ba 2 Bi 3 Nb 2 O 11 的载流子寿命I，允许比其氯化物和溴化物对应物显着更高的量子效率。在使用 Ba 2 Bi 3 Nb 2 O 11 I 作为析氧光催化剂的碘基体系中首次实现了可见光驱动的 Z 型水分解。本研究提供了一种将可极化的“软”阴离子结合到层状材料的构建块中以操纵带结构并改善可见光响应功能的载流子动力学的新方法。
更新日期：2021-06-09
中文翻译：
用于水分解光催化的具有窄带隙和长寿命载体的层状钙钛矿氧碘化物
具有窄带隙和高稳定性的半导体的发展对于实现太阳能到化学能的转换至关重要。具有高极化率的含碘化合物因其窄带隙和长载流子寿命而备受关注，例如卤化物钙钛矿太阳能电池；然而，它们被认为不适合苛刻的光催化水分解，因为碘易于自氧化。在这里，我们证明了 Ba 2 Bi 3 Nb 2 O 11I，一种分层的 Sillén-Aurivilius 氧碘化物，不仅比其氯化物和溴化物更能接触到更广泛的可见光，而且还可以作为稳定的光催化剂，有效地氧化水。密度泛函理论计算表明，钙钛矿块中的氧 2p 轨道，而不是之前指出的萤石 Bi 2 O 2块，异常推高价带最大值，这可以通过修正的马德隆势分析来解释，该分析考虑到考虑到碘的高极化率。此外，高度极化的碘化物有助于延长 Ba 2 Bi 3 Nb 2 O 11 的载流子寿命I，允许比其氯化物和溴化物对应物显着更高的量子效率。在使用 Ba 2 Bi 3 Nb 2 O 11 I 作为析氧光催化剂的碘基体系中首次实现了可见光驱动的 Z 型水分解。本研究提供了一种将可极化的“软”阴离子结合到层状材料的构建块中以操纵带结构并改善可见光响应功能的载流子动力学的新方法。
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