Wan Rong, He Peipei, Liu Zhen, Ma Xinyi, Ma Pengtao, Singh Vikram, Zhang Chao, Niu Jingyang, Wang Jingping
Henan Key Laboratory of Polyoxometalate Chemistry, College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan, 475004, P. R. China.
Chemistry. 2020 Jul 17;26(40):8760-8766. doi: 10.1002/chem.201905741. Epub 2020 May 8.
A SeO -centered lacunary Keggin-type heteropolyoxovanadate (hetero-POV) K H [SeV O (SeO ) ]⋅14 H O (1) was isolated by one-pot reaction of KVO and SeO under acidic conditions. X-ray studies revealed that it comprised a single {VO }-capped trivacant B-α-type Keggin ion [SeV O (VO)] with its lacunary sites decorated by three {SeO } pyramids. Interestingly, this new basic hetero-POV building block was further used as a precursor to assemble with different transition-metal (TM) ions, yielding a series of TM-sandwiched POVs K H [(SeV O (SeO ) ) (M(H O) )]⋅24 H O (M =Mn (2), Co (3), Zn (4)). All four compounds were characterized by single-crystal X-ray structure analysis, IR, X-ray photoelectron spectroscopy (XPS), EPR, and V NMR spectroscopy. Importantly, three TM-sandwiched derivatives exhibited effective catalytic activity for the heterogeneous oxidative desulfurization of sulfides at room temperature.
通过在酸性条件下将KVO₃和SeO₂进行一锅法反应，分离得到了一种以SeO为中心的缺位Keggin型杂多钒酸盐（杂多-POV）K₈H₂[SeV₁₀O₃₄(SeO₃)₃]⋅14H₂O（1）。X射线研究表明，它由一个单一的{VO₄}封端的三缺位B-α型Keggin离子[SeV₁₀O₃₄(VO)₂]组成，其缺位位点由三个{SeO₃}金字塔修饰。有趣的是，这种新的碱性杂多-POV结构单元进一步用作前体，与不同的过渡金属（TM）离子组装，得到了一系列TM夹心的POV K₈H₂[(SeV₁₀O₃₄(SeO₃)₃)(M(H₂O)₆)]⋅24H₂O（M = Mn（2）、Co（3）、Zn（4））。所有四种化合物均通过单晶X射线结构分析、红外光谱、X射线光电子能谱（XPS）、电子顺磁共振（EPR）和⁵¹V核磁共振光谱进行了表征。重要的是，三种TM夹心衍生物在室温下对硫化物的多相氧化脱硫表现出有效的催化活性。
