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Internal strain-driven bond manipulation and band engineering in Bi2-x Sb x YO4Cl photocatalysts with triple fluorite layers.
Gabov, Artem; Kato, Daichi; Ubukata, Hiroki; Aso, Ryotaro; Kakudou, Naoji; Fujita, Koji; Suzuki, Hajime; Tomita, Osamu; Saeki, Akinori; Abe, Ryu; Karazhanov, Smagul Zh; Kageyama, Hiroshi.
Afiliación
  • Gabov A; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Kato D; National Research Nuclear University MEPhI (Moscow Engineering Physics Institute) 31 Kashirskoye Shosse Moscow 115409 Russia.
  • Ubukata H; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Aso R; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Kakudou N; Department of Applied Quantum Physics and Nuclear Engineering, Kyushu University Fukuoka 819-0395 Japan.
  • Fujita K; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Suzuki H; Department of Material Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan.
  • Tomita O; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Saeki A; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Abe R; Department of Applied Chemistry, Graduate School of Engineering, Osaka University Osaka 565-0871 Japan.
  • Karazhanov SZ; Department of Energy and Hydrocarbon Chemistry, Graduate School of Engineering, Kyoto University Kyoto 615-8510 Japan daichik@scl.kyoto-u.ac.jp kage@scl.kyoto-u.ac.jp.
  • Kageyama H; Department for Solar Energy Materials and Technologies, Institute for Energy Technology Kjeller NO 2027 Norway smagul.karazhanov@ife.no.
Chem Sci ; 15(30): 11856-11864, 2024 Jul 31.
Article en En | MEDLINE | ID: mdl-39092095
ABSTRACT
In extended solid-state materials, the manipulation of chemical bonds through redox reactions often leads to the emergence of interesting properties, such as unconventional superconductivity, which can be achieved by adjusting the Fermi level through, e.g., intercalation and pressure. Here, we demonstrate that the internal 'biaxial strain' in tri-layered fluorite oxychloride photocatalysts can regulate bond formation and cleavage without redox processes. We achieve this by synthesizing the isovalent solid solution Bi2-x Sb x YO4Cl, which undergoes a structural phase transition from the ideal Bi2YO4Cl structure to the Sb2YO4Cl structure with (Bi,Sb)4O8 rings. Initially, substitution of smaller Sb induces expected lattice contraction, but further substitution beyond x > 0.6 triggers an unusual lattice expansion before the phase transition at x = 1.5. Detailed analysis reveals structural instability at high x values, characterized by Sb-O underbonding, which is attributed to tensile strain exerted from the inner Y sublayer to the outer (Bi,Sb)O sublayer within the triple fluorite block - a concept well-recognized in thin film studies. This concept also explains the formation of zigzag Bi-O chains in Bi2MO4Cl (M = Bi, La). The Sb substitution in Bi2-x Sb x YO4Cl elevates the valence band maximum, resulting in a minimized bandgap of 2.1 eV around x = 0.6, which is significantly smaller than those typically observed in oxychlorides, allowing the absorption of a wider range of light wavelengths. Given the predominance of materials with a double fluorite layer in previous studies, our findings highlight the potential of compounds endowed with triple or thicker fluorite layers as a novel platform for band engineering that utilizes biaxial strain from the inner layer(s) to finely control their electronic structures.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chem Sci Año: 2024 Tipo del documento: Article Pais de publicación: Reino Unido
Texto completo
Añadir a Mi BVS
Imprimir
XML
PubMed Links
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Chem Sci Año: 2024 Tipo del documento: Article Pais de publicación: Reino Unido