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From a Cerium-Doped Polynuclear Bismuth Oxido Cluster to β-Bi2O3:Ce.
Inorganic Chemistry ( IF 4.3 ) Pub Date : 2020-01-15 , DOI: 10.1021/acs.inorgchem.9b03240
Marcus Weber 1, 2 , Tobias Rüffer 3 , Florian Speck 2, 4 , Fabian Göhler 2, 4 , Dominik P Weimann 5 , Christoph A Schalley 5 , Thomas Seyller 2, 4 , Heinrich Lang 3 , Michael Mehring 1, 2
Affiliation  

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 CeIV 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.

中文翻译:

从铈掺杂多核氧化铋簇到β-Bi2O3:Ce。

Bi(NO3)3·5H2O和Ce(NO3)3·6H2O的同时水解导致形成通式为[Bi38O45(NO3)24(DMSO)28 +δ]:Ce(DMSO)的新型异金属铋氧化物簇=二甲基亚砜;铈含量<1.50%),这通过单晶X射线衍射分析证实。铈结合到团簇核中是在氧气存在下金属硝酸盐水解和缩合相互作用的结果。漫反射紫外可见光谱和X射线光电子能谱显示,铈源氧化后,最终的铋氧化物簇中存在CeIV。铈原子统计上主要分布在[Bi38O45]簇核心的中心[Bi6O9]基序的铋原子位置上。在300-400°C的温度范围内,铋氧化物簇的水解和随后的退火处理提供了β-Bi2O3:Ce样品,与未掺杂的β-Bi2O3相比,带隙略微降低了约2.3eV(约2.4eV)。β-Bi2O3的烧结行为受到铈掺杂剂的显着影响。最后,证明了制备的β-Bi2O3:Ce和未掺杂的β-Bi2O3样品在可见光照射下杀菌剂三氯生在水溶液中的光催化分解效率不同。
更新日期:2020-01-15
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