Transition metal-doped high-nuclear polyoxovanadates constructed from tetragonal building blocks  

由四边形结构单元构筑的过渡金属掺杂的多金属钒酸盐

作　　者：WU Shuangxue LIU Mingshuo KUAI Naibin QIN Chao WANG Xinlong SU Zhongmin 吴双雪;刘明硕;蒯乃彬;秦超;王新龙;苏忠民(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)

机构地区：[1]Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education,Northeast Normal University,Changchun 130024,China

出　　处：《分子科学学报》2024年第5期456-461,共6页Journal of Molecular Science

基　　金：financially supported by National Natural Science Foundation of China(22371032 and 22271023)

摘　　要：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),{V_(20)S_(2)In_(42)P_(12)(CO_(2))}(1),{V_(20)Mo_(2)In_(4)P_(12)(C_(2)O_(4))_(2)}(2),{V_(12)P_(6)SPb_(2)}(3)and{V_(12)P_(6)SCd_(2)}(4),were successfully synthesized under solvothermal conditions by incorporating transition metals into POVs.All the structures are constructed from the tetragonal{V_(5)(PhPO_(3))_(4)}SBB,wherein five{VO_(5)}square pyramids 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{V_(10)(PhPO_(3))_(6)(SO_(4))In_(2)}or{V_(10)(PhPO_(3))_(6)(MoO_(4))In_(2)}clusters are bridged by formate or oxalate ligands.While compounds 3 and 4 are constructed from{V_(12)(PhPO_(3))_(6)(SO_(4))}cluster doped with transition metals Pb or Cd.Notably,compound 4 demonstrated efficient catalytic activity for sulfide oxidation.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:{V_(20)S_(2)In_(42)P_(12)(CO_(2))}(1),{V_(20)Mo_(2)In_(4)P_(12)(C_(2)O_(4))_(2)}(2),{V_(12)P_(6)SPb_(2)}(3)和{V_(12)P_(6)SCd_(2)}(4)。这些结构都是由四方构筑块{V_(5)(PhPO_(3))_(4)}构建而成的,其中5个{VO_(5)}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{V_(10)(PhPO_(3))_(6)(SO_(4))In_(2)}或{V_(10)(PhPO_(3))_(6)(MoO_(4))In_(2)}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{V_(12)(PhPO_(3))_(6)(SO_(4))}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。

关 键 词：POLYOXOMETALATE POLYOXOVANADATE secondary building block catalysis sulfide oxidation 

分 类 号：O643.36[理学—物理化学]