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Interplay of Orbital and Relativistic Effects in Bismuth Oxyhalides: BiOF, BiOCl, BiOBr, and BiOI

DOI: 10.1021/acs.chemmater.6b00349 DOI Help

Authors: Alex M. Ganose (University College London) , Madeleine Cuff (University College London) , Keith T. Butler (University of Bath) , Aron Walsh (University of Bath) , David O. Scanlon (University College London; Diamond Light Source)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials

State: Published (Approved)
Published: March 2016

Abstract: The optoelectronic properties of bismuth oxyhalides have led to their utility in applications such as pigments in the cosmetics industry,1,2 pharmaceuticals,3,4 phosphors,5 gas sensors,6 and catalysis.7,8 Over the past decade, interest in this family of materials has rapidly increased, fuelled by reports of their excellent photocatalytic activity.9−16 They have been studied as stand-alone photocatalysts,9,10,17 quaternary alloys, 18,19 and interfaced with other photocatalytically active materials.20−22 To date, however, an understanding of the chemical trends underpinning these successes is lacking. The BiOX series, shown in Figure 1, crystallize in the tetragonal Matlockite structure,23,24 which can be considered the simplest form of the Sillén-type structure and is commonly expressed as [M2O2][Xm].25 The crystal lattice consists of fluorite-like [M2O2] layers sandwiched between double halide [Xm] layers, to form [X−Bi−O−Bi−X] sheets, stacked in the [001] direction, with the structure held together by nonbonding van der Waals interactions along the [001] direction. It has been proposed that this structure type imparts an internal static electric field between the [M2O2]2+ and double [X]− slab along the [001] direction, which aids efficient separation of the photogenerated electron−hole pairs.

Subject Areas: Chemistry

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Added On: 31/03/2016 10:28

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