Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb5(VO4)3X (X=F, Cl, Br, I)

Nakamura, Masashi; Oqmhula, Kenji; Utimula, Keishu; Eguchi, Miharu; Oka, Kengo; Hongo, Kenta; Maeda, Kazuhiko

doi:10.1002/asia.201901692

Cited by 6 publications

(1 citation statement)

References 41 publications

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“…13 They exhibit useful properties with various practical applications such as fertilizers, food additives, and bioceramics but also as catalysts and fluorescent host materials. On another hand, Pb 5 (VO 4 )X (X = F, Cl, Br, I) apatites have been recently reported 14 with light-absorption properties which opens new perspectives in this family. The iodide phase has a band gap in the visible range (2.7 eV), thanks to the contribution of the I 5p states at the top of the valence band, which allows a response in the visible range as a photoanode for photoelectric conversion.…”

Section: ■ Introductionmentioning

confidence: 99%

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases

Almoussawi,

Sen,

Saitzek

et al. 2023

Inorg. Chem.

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Section: ■ Introductionmentioning

confidence: 99%

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases

Almoussawi,

Sen,

Saitzek

et al. 2023

Inorg. Chem.

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The prediction method for standard enthalpies of apatites using the molar volume, lattice energy, and linear correlations from existing experimental data

Puzio

Manecki

2022

Contrib Mineral Petrol

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Experimental data of thermodynamic state functions and molar volume for phosphate, arsenate, and vanadate apatites containing Ca, Sr, Ba, Pb, end Cd at the cationic positions Me2+ and F, OH, Cl, Br, and I at the halide position X were collected. The apatite supergroup splits into distinct subgroups (populations) constituted by Me10(AO4)6X2 with the same Me2+ cations and tetrahedral AO43− anions but with different anions at the X position. Linear relationships between various parameters within apatite subgroups are observed. The prediction method for standard enthalpies of apatites (ΔHºf,el) is based on regression analysis of the linear correlations within the subgroups between ΔH°f,el of apatites and their molar volume Vm, lattice energy UPOT, and ΔH°f,el of their anions AO43− or X−. This allowed to predict 22 new ΔH°f,el values for apatites and materials with an apatite structure. The prediction precision is comparable to the experimental uncertainty obtained when reproducing experimental data using calorimetric measurements or dissolution experiments and can be applied to a wider range of apatites than other methods.

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Sn-Based Perovskite with a Wide Visible-Light Absorption Band Assisted by Hydride Doping

et al. 2021

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Visible-light-absorbing, narrow-gap semiconductors have attracted significant interest in recent years owing to their photofunctional applications, including heterogeneous photocatalysis and solar cells. Herein, we report a new Pb-free perovskite material with a wide range of visible-light absorption that was successfully synthesized via hydride (H–)-ion doping into BaSn0.7Y0.3O3−δ. Chemical reduction that accompanied H–-ion doping significantly reduced the optical band gap of the host BaSn0.7Y0.3O3−δ from 4.0 to 2.0 eV. Physicochemical measurements revealed that BaSn0.7Y0.3O3−δ underwent the partial reduction of Sn4+ to Sn2+ at B-sites while maintaining the cubic perovskite structure. Density functional theory calculations showed that the electronic states derived from the Sn2+ lone pair, which was located above the top of the valence band, contributed to the visible-light absorption of reduced BaSn0.7Y0.3O3−δ. The prior introduction of oxygen defects into BaSnO3 by Y3+ substitution for Sn4+ was also indispensable to realize a significant reduction of the band gap. The reduced BaSn0.7Y0.3O3−δ doped with H– ions was applied as a photoelectrode material, and a clear anodic photoresponse of up to 600 nm was observed, which demonstrates that the material can be used for photofunctional applications. The results of this work suggest that the utilization of stereoactive lone pair of electrons in combination with H– doping may provide another approach to the band gap reduction of Sn(IV)-based oxides, which are nontoxic and less expensive, but generally wide-gap semiconductors.

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Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb₅(VO₄)₃X (X=F, Cl, Br, I)

Cited by 6 publications

References 41 publications

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases

The prediction method for standard enthalpies of apatites using the molar volume, lattice energy, and linear correlations from existing experimental data

Sn-Based Perovskite with a Wide Visible-Light Absorption Band Assisted by Hydride Doping

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Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb5(VO4)3X (X=F, Cl, Br, I)

Cited by 6 publications

References 41 publications

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba5(VO4−αSα)3X (X = F, Cl, I) Phases

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba5(VO4−αSα)3X (X = F, Cl, I) Phases

The prediction method for standard enthalpies of apatites using the molar volume, lattice energy, and linear correlations from existing experimental data

Sn-Based Perovskite with a Wide Visible-Light Absorption Band Assisted by Hydride Doping

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About

Light Absorption Properties and Electronic Band Structures of Lead‐Vanadium Oxyhalide Apatites Pb₅(VO₄)₃X (X=F, Cl, Br, I)

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases

Designing Visible-Light Photoactive Thioapatites Using Thiovanadate Groups: The Ba₅(VO_4−αS_α)₃X (X = F, Cl, I) Phases