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.