Emergence of Tetragonal Phase and Reentrant Transition in Tensile-Strained Bi2(La1–xBix)O4Cl Solid Solution DOI
Artem Gabov, Daichi Kato, Takamasa Tsukamoto

и другие.

Chemistry of Materials, Год журнала: 2024, Номер 37(1), С. 453 - 462

Опубликована: Дек. 25, 2024

Manipulating chemical bonding in a solid is crucial for controlling and realizing desirable properties. We have recently demonstrated that replacing the M3+ cation of Bi2MO4Cl, which contains triple-fluorite slabs, from Y3+ to larger (La3+, Bi3+) induces tensile strain Bi–O square net, resulting bond cleavage form double- single-chain structures, respectively. In this study, we synthesized solution Bi2(La1–xBix)O4Cl with almost uniform strain, revealing an unexpected tetragonal (T) phase (0.15 ≤ x 0.35), along additional monoclinic (0.425 0.475). The emergence T elongated in-plane axis likely arises competition between single double chain structures. exhibits narrower bandgap 2.2 eV (vs Bi2YO4Cl), ascribed presence Bi inner sublayer. Furthermore, undergoes reentrant transition upon heating via phase, forming high-temperature (T′) partial due spatial thermal fluctuations outer cations. This study emphasizes role promoting triple fluorite layered systems, complex transitions under external stimuli. Controlling such delicate balance offers pathway engineering physical properties functional materials, as visible-light photocatalysts.

Язык: Английский

Band engineering of layered oxyhalide photocatalysts for visible-light water splitting DOI Creative Commons
Daichi Kato, Hajime Suzuki, Ryu Abe

и другие.

Chemical Science, Год журнала: 2024, Номер 15(30), С. 11719 - 11736

Опубликована: Янв. 1, 2024

In the past decade, layered oxyhalide photocatalysts have evolved through diverse layer stacking structures. This review outlines design principles of their band structures, drawing insights from systematic studies this family.

Язык: Английский

Процитировано

10
Exploring the Photocatalytic Mechanism of BiTi4GaO11: Insights from the Electronic Structure and Chemical Bonding DOI
Guangxiang Lu, Zien Cheng, Maxim Avdeev

и другие.

Inorganic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 16, 2025

Photocatalytic water splitting and CO2 reduction offer sustainable solutions to energy environmental issues, but efficient semiconductor photocatalysts are still limited. Oxide with d0 and/or d10 metals often have wide bandgaps, incorporating d10ns2 can raise the valence band maximum (VBM) narrow bandgap. Here, we synthesized BiTi4GaO11 (BTGO), a new photocatalyst containing d106s2, d0, metals. Structural analysis via powder X-ray neutron diffraction confirmed BTGO crystallizes in space group Cmcm, Ga cooccupying all three Ti sites. Density functional theory calculations revealed that conduction minimum (CBM) of is primarily composed t2g - O 2p antibonding orbitals. Hybridization between Bi 6s orbitals leads formation orbitals, which further interact 6p form VBM. This interaction shifts VBM upward, narrows bandgap (Eg = 2.82 eV), enables visible-light absorption. Experimental results demonstrated efficiently catalyzes photocatalytic H2 production reduction. Furthermore, incorporation cocatalysts suppressed recombination photogenerated charge carriers, enhancing activity. work highlights importance electronic structure bonding understanding fundamental mechanisms photocatalysis.

Язык: Английский

Процитировано

0
Emergence of Tetragonal Phase and Reentrant Transition in Tensile-Strained Bi2(La1–xBix)O4Cl Solid Solution DOI
Artem Gabov, Daichi Kato, Takamasa Tsukamoto

и другие.

Chemistry of Materials, Год журнала: 2024, Номер 37(1), С. 453 - 462

Опубликована: Дек. 25, 2024

Manipulating chemical bonding in a solid is crucial for controlling and realizing desirable properties. We have recently demonstrated that replacing the M3+ cation of Bi2MO4Cl, which contains triple-fluorite slabs, from Y3+ to larger (La3+, Bi3+) induces tensile strain Bi–O square net, resulting bond cleavage form double- single-chain structures, respectively. In this study, we synthesized solution Bi2(La1–xBix)O4Cl with almost uniform strain, revealing an unexpected tetragonal (T) phase (0.15 ≤ x 0.35), along additional monoclinic (0.425 0.475). The emergence T elongated in-plane axis likely arises competition between single double chain structures. exhibits narrower bandgap 2.2 eV (vs Bi2YO4Cl), ascribed presence Bi inner sublayer. Furthermore, undergoes reentrant transition upon heating via phase, forming high-temperature (T′) partial due spatial thermal fluctuations outer cations. This study emphasizes role promoting triple fluorite layered systems, complex transitions under external stimuli. Controlling such delicate balance offers pathway engineering physical properties functional materials, as visible-light photocatalysts.

Язык: Английский

Процитировано

0