Synthesis and Materials Chemistry of Bismuth Tris-(di-i-propylcarbamate): Deposition of Photoactive Bi₂O₃ Thin Films

The bismuth carbamate Bi­(O₂CNPrⁱ₂)₃, a tetramer in the solid-state, has been synthesized and used to deposit mixtures of bismuth oxides by aerosol-assisted chemical vapor deposition (AACVD). The nature of the deposited oxide is a function of both temperature and run-time. Initially, δ-Bi₂O₃ is deposited, over which grows a thick layer of β-Bi₂O₃ nanowires, the latter having an increasing degree of preferred orientation at higher deposition temperatures. The photocatalytic activity of a thin film of δ-Bi₂O₃ for the degradation of methylene blue dye was found to be similar to that of a commercial TiO₂ film on glass, while the film overcoated with β-Bi₂O₃ nanowires was less active. Exposure of Bi­(O₂CNPrⁱ₂)₃ to controlled amounts of moist air affords the novel oxo-cluster Bi₈(O)₆(O₂CNPrⁱ₂)₁₂, whose structure has also been determined.