Elucidating Structural Disorder in Ultra-Thin Bi-Rich Bismuth Oxyhalide Photocatalysts.

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.