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Thin coatings of Bi 2 O 3  were deposited on glass substrates by ultrasonic spray coating of THF solutions of the molecular precursor [Bi 38 O 45 (OMc) 24 (DMSO) 9 ] ⋅ 2DMSO ⋅ 7H 2 O (OMc=O 2 CC 3 H 5 ) followed by hydrolysis and subsequent annealing. Depending on the synthetic protocol, the bismuth oxido cluster was transformed into either α‐ or β‐Bi 2 O 3 . The as‐synthesized Bi 2 O 3  coatings were characterized by powder X‐ray diffraction (PXRD), thickness measurements, diffuse reflectance UV‐Vis spectroscopy (DRS), photoluminescence (PL) spectroscopy, Raman spectroscopy and scanning electron microscopy (SEM). The thin coatings (thickness: 5–16 μm) were compared with regard to their performance in photocatalytic rhodamine B (RhB) decomposition under visible light irradiation. The β‐Bi 2 O 3  coatings, that showed the highest photocatalytic activity, were used for the photocatalytic decomposition of other pollutants such as triclosan and ethinyl estradiol. In addition, the interplay between the photooxidation that is induced by the excitation of the catalyst using visible light and the photosensitized decomposition pathway was studied by degradation experiments of aqueous rhodamine B solutions using β‐Bi 2 O 3  coatings.

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Thin Coatings of α‐ and β‐Bi 2 O 3  by Ultrasonic Spray Coating of a Molecular Bismuth Oxido Cluster and their Application for Photocatalytic Water Purification Under Visible Light