BiSbWO6: Properties of a mixed 5s/6s lone-pair-electron system

Bainglass, Edan; Walsh, Aron; Huda, Muhammad N.

doi:10.1016/j.chemphys.2021.111117

Cited by 4 publications

(7 citation statements)

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“…Moreover, the value of the indirect bandgap of Bi 2 W 1– x Nb x O 6 and Bi 2 W 1– x Ta x O 6 gradually decreased from 2.75 to 2.72 eV for 0 ≤ x ≤ 0.1 and drastically decreased between x = 0.1 and 0.2 (Figure S2). The latter changes could be related to possible changes in the band structure together with improvements in the crystallographic symmetry . The overall trend of bandgap narrowing of Bi 2 WO 6 due to Nb or Ta doping qualitatively corresponded to that of Ba 2 (Bi TM )O 6 ( TM = Nb or Ta) or Sn 2 TM 2 O 7.…”

Section: Resultsmentioning

confidence: 84%

“…The latter changes could be related to possible changes in the band structure together with improvements in the crystallographic symmetry. 35 The overall trend of bandgap narrowing of Bi 2 WO 6 due to Nb or Ta doping qualitatively corresponded to that of Ba 2 (BiTM)O 6 (TM = Nb or Ta) 18 or Sn 2 TM 2 O 7.…”

Section: ■ Introductionmentioning

confidence: 72%

“…As previously reported, Ta 5+ more strongly attracts the surrounded electrons than Nb 5+ does. 42,47 In this circumstance, it is possible that the effective distance between the electrons of oxygen in the WO 6 octahedra and the 6s 2 lone-pair electron of Bi, with their interaction leading to the characteristic WO 6 octahedral structure in Bi 2 WO 6 , 35 could become longer for Ta 5+ doping than for Nb 5+ doping. The longer distance weakens the interaction, and hence, the distorted WO 6 octahedral structure is diminished more in Bi 2 W 1−x Ta x O 6 than in Bi 2 W 1−x Nb x O 6 .…”

Section: ■ Results and Discussionmentioning

confidence: 99%

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Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping

et al. 2023

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Based on the fundamental design concept of modulating the valence band maximum of oxides and subsequent predictions through computational approaches, several lone-pair ns 2-based p-type oxide semiconductors, such as Sn2+- or Bi3+-based complex oxides, have been developed. Thus far, the bandgap can be modified via tuning of the chemical composition, whereas the hole density cannot be intentionally controlled because of the poor chemical stability of Sn2+ and/or the formation of oxygen vacancies. The inability to control hole density prohibits the design and realization of emergent electronic devices based on p- and n-type oxide semiconductors. Herein, we report the control of hole density via intentional chemical doping in polycrystalline Bi2WO6. While the holes of polycrystalline Nb- or Ta-doped Bi2WO6 are strongly trapped by grain boundaries, the hole density obtained at high temperatures monotonically increases with the increase in the doping concentration. This study provides important insights into the development of practical p-type oxide semiconductors.

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Section: Resultsmentioning

confidence: 84%

Section: ■ Introductionmentioning

confidence: 72%

Section: ■ Results and Discussionmentioning

confidence: 99%

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Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping

et al. 2023

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“…Notably, the latter has been challenging to achieve for low-electronegative anions such as S 2– or N 3– due to facile oxidation by photogenerated holes. Additionally, the lower part of the conduction band of Sillén and Sillén–Aurivillius mainly consists of cation p orbitals favorable for electron transfer, ,, while in conventional photocatalysts, more localized cation d (Ti 3d, V 3d, Nb 4d, Ta 5d, W 5d) orbitals are present …”

Section: Introductionmentioning

confidence: 99%

“…Notably, the latter has been challenging to achieve for low-electronegative anions such as S 2− or N 3− due to facile oxidation by photogenerated holes. Additionally, the lower part of the conduction band of Silleń and Silleń−Aurivillius mainly consists of cation p orbitals favorable for electron transfer, 1,10,19 while in conventional photocatalysts, more localized cation d (Ti 3d, V 3d, Nb 4d, Ta 5d, W 5d) orbitals are present. 20 Owing to the specific electronic structure of Silleń and Silleń−Aurivillius compounds due to the s 2 lone-pair electrons of Bi or Pb, a unique strategy is required to control and design the material properties such as band gaps, band edge positions, and carrier mobilities.…”

Section: ■ Introductionmentioning

confidence: 99%

Orbital Engineering in Sillén–Aurivillius Phase Bismuth Oxyiodide Photocatalysts through Interlayer Interactions

et al. 2023

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Multicomponent inorganic compounds containing post-transition-metal cations such as Sn, Pb, and Bi are a promising class of photocatalysts, but their structure–property relationships remain difficult to decipher. Here, we report three novel bismuth-based layered oxyiodides, the Sillén–Aurivillius phase Bi4NbO8I, Bi5BaTi3O14I, and Bi6NbWO14I. We show that the interlayer Bi–Bi interaction is a key to controlling the electronic structure. The replacement of the halide layer from Cl to I negatively shifts not only the valence band but also the conduction band, thus providing lower electron affinity without sacrificing photoabsorption. The suppressed interlayer chemical interaction between the 6p orbitals of the Bi lone-pair cations reduces the conduction bandwidth. These oxyiodides have narrower band gaps and show much higher water oxidation activities under visible light than their chloride counterparts. The design strategy has not only provided three novel Bi-based photocatalysts for water splitting but also offers a pathway to control the optoelectronic properties of a wider class of lone-pair (ns2np0) semiconductors.

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Perspective—Multinary Oxide Semiconductors for Solar Fuels Generation: Closing the Performance Gap between Theory and Practice

O’Donnell¹,

Alimirzaloo²,

Rawat³

et al. 2022

ECS J. Solid State Sci. Technol.

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We address the current state-of-the-art in the development of multinary oxides—a family of compounds that has long interested Prof. John B. Goodenough. Specifically, we focus on their use as photoelectrodes for solar fuels generation. Using optical data and assuming an idealized 100% incident photon-to-electron conversion efficiency, it is possible to project the maximum short-circuit photocurrent efficiency to be expected for a given oxide semiconductor. The performance gap between this theoretical value and that realized experimentally is shown to be sizable for all but a couple candidates. The technical issues underlying this gap and strategies for closing it are presented.

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BiSbWO6: Properties of a mixed 5s/6s lone-pair-electron system

Cited by 4 publications

References 71 publications

Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping

Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping

Orbital Engineering in Sillén–Aurivillius Phase Bismuth Oxyiodide Photocatalysts through Interlayer Interactions

Perspective—Multinary Oxide Semiconductors for Solar Fuels Generation: Closing the Performance Gap between Theory and Practice

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BiSbWO6: Properties of a mixed 5s/6s lone-pair-electron system

Cited by 4 publications

References 71 publications

Control of Hole Density in Russellite Bi2WO6 via Intentional Chemical Doping

Control of Hole Density in Russellite Bi2WO6 via Intentional Chemical Doping

Orbital Engineering in Sillén–Aurivillius Phase Bismuth Oxyiodide Photocatalysts through Interlayer Interactions

Perspective—Multinary Oxide Semiconductors for Solar Fuels Generation: Closing the Performance Gap between Theory and Practice

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Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping

Control of Hole Density in Russellite Bi₂WO₆ via Intentional Chemical Doping