由四边形结构单元构筑的过渡金属掺杂的多金属钒酸盐
Transition metal-doped high-nuclear polyoxovanadates constructed from tetragonal building blocks
吴双雪 1刘明硕 1蒯乃彬 1秦超 1王新龙 1苏忠民1
作者信息
- 1. 东北师范大学多酸与网格材料化学教育部重点实验室,吉林长春 130024
- 折叠
摘要
利用次级构筑模块(SBB)设计和合成高核多金属氧酸盐(POMs)是极具吸引力和挑战性的.本文将过渡金属引入到高核多金属钒酸盐(POVs)体系中,在溶剂热条件下成功地合成了 4 种新型的高核 POVs:{V20S2In42P12(CO2)}(1),｛V20Mo2In4P12(C2O4)2}(2),{V12P6SPb2｝(3)和{V12P6SCd2}(4).这些结构都是由四方构筑块{V5(PhPO3)4｝构建而成的,其中5个{VO5｝方形金字塔通过边缘共享模式相互连接,4个苯基膦酸配体进一步与钒阳离子配位.化合物1和2具有相似的结构,是由2个{V10(PhPO3)6(SO4)In2｝或｛V10(PhPO3)6(MoO4)In2｝簇通过甲酸盐或草酸盐配体桥接而成.而化合物3和4是由掺杂过渡金属铅或镉的｛V12(PhPO3)6(SO4)｝簇构建而成.值得注意的是,化合物4对硫化物氧化具有较高的催化活性.
Abstract
The design and synthesis of high-nuclear polyoxometalates(POMs)utilizing secondary building blocks(SBB)is attractive and challenging.Herein,four new high-nuclear polyoxovanadates(POVs),{V20S2In42P12(CO2)}(1),{V20Mo2In4P12(C2O4)2}(2),{V12P6SPb2}(3)and {V12P6SCd2}(4),were successfully synthesized under solvothermal conditions by incorporating transition metals into POVs.All the structures are constructed from the tetragonal {V5(PhPO3)4} SBB,wherein five {VO5} square pyra-mids are interconnected by edge-sharing modes,and four phenylphosphonic acid ligands further coordinate with vanadium cations.Compounds 1 and 2 have similar structures in which two {V10(PhPO3)6(SO4)In2}or {V10(PhPO3)6(MoO4)In2} clusters are bridged by formate or oxalate ligands.While compounds 3 and 4 are constructed from {V12(PhPO3)6(SO4)} cluster doped with transition metals Pb or Cd.Notably,compound 4 demonstrated efficient catalytic activity for sulfide oxidation.
关键词
多金属氧酸盐/多金属钒酸盐/次级构筑块/催化/硫化物Key words
polyoxometalate/polyoxovanadate/secondary building block/catalysis/sulfide oxidation引用本文复制引用
出版年
2024
NETL
NSTL
万方数据