Elucidating Structural Disorder in Ultra‐Thin Bi‐Rich Bismuth Oxyhalide Photocatalysts

Marks, Melissa; Jeppesen, Henrik; Nielsen, Mads Lund Nygaard; Kong, Jintao; Ceccato, Marcel; van der Veen, Monique A.; Bøjesen, Espen Drath; Lock, Nina

doi:10.1002/smll.202401413

Title: Elucidating Structural Disorder in Ultra‐Thin Bi‐Rich Bismuth Oxyhalide Photocatalysts

Journal Article · 10 May 2024 · Small

DOI: https://doi.org/10.1002/smll.202401413 · OSTI ID:2369916

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^[2]; Nielsen, Mads Lund Nygaard ^[3]; Kong, Jintao ^[4];

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Interdisciplinary Nanoscience Centre (iNANO) Aarhus University Gustav Wieds Vej 14 Aarhus C 8000 Denmark, Department of Biological and Chemical Engineering Aarhus University Åbogade 40 Aarhus N 8200 Denmark
Deutsches Elektronen‐Synchrotron (DESY) Notkestr. 85 22607 Hamburg Germany
Interdisciplinary Nanoscience Centre (iNANO) Aarhus University Gustav Wieds Vej 14 Aarhus C 8000 Denmark
Department of Chemical Engineering Technische Universiteit Delft Delft HZ 2629 The Netherlands
Interdisciplinary Nanoscience Centre (iNANO) Aarhus University Gustav Wieds Vej 14 Aarhus C 8000 Denmark, iMAT Aarhus University Centre for Integrated Materials Research Aarhus University Langelandsgade 140 Aarhus C 8000 Denmark

Abstract Advancing the field of photocatalysis requires the elucidation of structural properties that underpin the photocatalytic properties of promising materials. The focus of the present study is layered, Bi‐rich bismuth oxyhalides, which are widely studied for photocatalytic applications yet poorly structurally understood, due to high levels of disorder, nano‐sized domains, and the large number of structurally similar compounds. By connecting insights from multiple scattering techniques, utilizing electron‐, X‐ray‐ and neutron probes, the crystal phase of the synthesized materials is allocated as layered Bi ₂₄ O ₃₁ X ₁₀ (X = Cl, Br), albeit with significant deviation from the reported 3D crystalline model. The materials comprise anisotropic platelet‐shaped crystalline domains, exhibiting significant in‐plane ordering in two dimensions but disorder and an ultra‐thin morphology in the layer stacking direction. Increased synthesis pH tailored larger, more ordered crystalline domains, leading to longer excited state lifetimes determined via femtosecond transient absorption spectroscopy (fs‐TAS). Although this likely contributes to improved photocatalytic properties, assessed via the photooxidation of benzylamine, increasing the overall surface area facilitated the most significant improvement in photocatalytic performance. This study, therefore, enabled both phase allocation and a nuanced discussion of the structure‐property relationship for complicated, ultra‐thin photocatalysts.

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Sponsoring Organization:: USDOE

OSTI ID:: 2369916

Alternate ID(s):: OSTI ID: 2349388

Journal Information:: Small, Journal Name: Small; ISSN 1613-6810

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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