Chemical and photochemical functionality of the first molecular bismuth vanadium oxide.

Chemical and photochemical functionality of the first molecular bismuth vanadium oxide.
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第一个分子氧化钒铋的化学和光化学功能

DOI:
10.1002/chem.201200404
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发表时间:
2012
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影响因子:
--
通讯作者:
Notarnicola
Notarnicola
中科院分区:
--
文献类型:
--
作者:
Tucher;Ivanovic-Burmazovic;Notarnicola

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阴离子金属氧化物簇,所谓的聚氧乙烯酸盐,可以被开发为分子模型化合物,以在分子水平上模拟固态金属氧化物的化学和光化学反应性。受众所周知的可见光光催化剂BiVO 4的启发,合成了第一个分子铋钒氧化物,以研究固态和分子化合物之间的化学和光化学相似性。簇合物H3[(Bi(dmso)3)4V 13 O 40]是一个单原子簇。从简单的前体以几乎定量的产率获得4 DMSO。结构分析表明,簇壳是基于不寻常的全钒ε-Keggin框架[ε-V12 O 40]15−,它通过四个BiIII中心的配位来稳定。通过滴定研究证明了三个簇质子的酸性特征。该簇合物在可见光光氧化反应中表现出良好的光催化性能,具有高活性(转换数>1200),高量子产率(Φ= 7.6%)和良好的可回收性,这使其成为一类有希望的新型杂金属多氧杂环丁烷酸盐的第一个例子。
Anionic metal oxide clusters, so‐called polyoxometalates, can be developed as molecular model compounds to mimic the chemical and photochemical reactivity of solid‐state metal oxides on the molecular level. Inspired by the well‐known visible‐light photocatalyst BiVO4, the first molecular bismuth vanadium oxide has been synthesized to investigate the chemical and photochemical similarities between the solid‐state and molecular compounds. The cluster H3[(Bi(dmso)3)4V13O40]⋅ca. 4 DMSO was obtained from simple precursors in almost quantitative yield. Structural analysis showed that the cluster shell is based on the unusual all‐vanadium ε‐Keggin framework [ε‐V12O40]15−, which is stabilized by coordination of four BiIIIcenters. The acidic character of the three cluster protons was demonstrated by titration studies. The cluster shows promising photocatalytic properties in visible‐light photooxidation reactions and has high activity (turnover number >1200), high quantum yield (Φ=7.6 %), and good recyclability, which make it a promising first example of a new class of heterometallic polyoxometalates.
含有两个和三个锰(IV)离子的杂多钒酸盐:Mn2V22O6410-和Mn3V12O40H35-的不寻常结构特征
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