From a Cerium-Doped Polynuclear Bismuth Oxido Cluster to β-Bi₂O₃:Ce

The simultaneous hydrolysis of Bi(NO₃)₃·5H₂O and Ce(NO₃)₃·6H₂O results in the formation of novel heterometallic bismuth oxido clusters with the general formula [Bi₃₈O₄₅(NO₃)₂₄(DMSO)_28+δ]:Ce (DMSO = dimethyl sulfoxide; cerium content <1.50%), which is demonstrated by single-crystal X-ray diffraction analysis. The incorporation of cerium into the cluster core is a result of the interplay of hydrolysis and condensation of the metal nitrates in the presence of oxygen. Diffuse-reflectance UV-vis and X-ray photoelectron spectroscopy reveal the presence of Ce^IV in the final bismuth oxido clusters as a result of oxidation of the cerium source. The cerium atoms are statistically distributed mainly on the bismuth atom positions of the central [Bi₆O₉] motif of the [Bi₃₈O₄₅] cluster core. Hydrolysis and subsequent annealing of the bismuth oxido clusters in the temperature range of 300-400 °C provides β-Bi₂O₃:Ce samples with slightly lowered band gaps of approximately 2.3 eV compared to the undoped β-Bi₂O₃ (approximately 2.4 eV). The sintering behavior of β-Bi₂O₃ is significantly affected by the cerium dopant. Finally, differences in the efficiency of the as-prepared β-Bi₂O₃:Ce and undoped β-Bi₂O₃ samples in the photocatalytic decomposition of the biocide triclosan in an aqueous solution under visible-light irradiation are demonstrated.