An unprecedented dumbbell-shaped pentadeca-nuclear W-Er heterometal cluster stabilizing nanoscale hexameric arsenotungstate aggregate and electrochemical sensing properties of its conductive hybrid film-modified electrode  

作　　者：Dan Wang Jun Jiang Meng-Ya Cao Sai-Sai Xie Ya-Min Li Li-Juan Chen Jun-Wei Zhao Guo-Yu Yang 

机构地区：[1]Henan Key Laboratory of Polyoxometalate Chemistry,College of Chemistry and Chemical Engineering,Henan University,Kaifeng 475004,China [2]MOE Key Laboratory of Cluster Science,School of Chemistry and Chemical Engineering,Beijing Institute of Technology,Beijing 100081,China

出　　处：《Nano Research》2022年第4期3628-3637,共10页纳米研究（英文版）

基　　金：This work was supported by the National Natural Science Foundation of China(Nos.21871077,21671054,21771052,22071042,22171070,91122028,and 21831001);the Program for Innovation Teams in Science and Technology in Universities of Henan Province(No.20IRTSTHN004).

摘　　要：Cluster-based functional materials have made remarkable progress owing to their wonderful structures and distinctive physicochemical performances,one of on-going advancements of which is basically driven by synthetic chemistry of exploring and constructing novel nanosized gigantic polyoxometalate(POM)aggregates.In this article,an unprecedented nanoscale hexameric arsenotungstate aggregate Na_(9)K_(16)H_(4)[Er_(0.5)K_(0.5)(H_(2)O)_(7)][Er_(5)W10O_(2)6(H_(2)O)_(14)][B-α-AsW_(9)O_(33)]_(6)·102H_(2)O(1)has been synthesized by the combined synthetic strategy of simultaneously using the arsenotungstate precursor and simple tungstate material in a highly acidic aqueous solution.The{[Er_(5)W_(10)O_(26)(H_(2)O)_(14)][B-α-AsW_(9)O_(33)]6}31-polyanion in 1 consists of an intriguing dumbbell-shaped pentadeca-nuclear W-Er heterometal{Er_(5)W10O_(2)6(H_(2)O)_(14)}^(23+)cluster connecting six trilacunary[B-α-AsW_(9)O_(33)]^(9-)moieties,which has never been seen previously.Furthermore,through electropolymerization of 1 and pyrrole on the conductive substrate,a thickness-controllable and robust 1-PPY(PPY=polypyrrole)hybrid film was successfully prepared,which represents the first POM-PPY film assembled from high-nuclear lanthanide(Ln)encapsulated POM and PPY hitherto.The 1-PPY film-based electrochemical biosensor exhibits a favorable recognition performance for ochratoxin A in multiple media.This work not only provides a feasible combined synthetic strategy of the POM precursor and simple tungstate material for constructing complicated multi-Ln-inserted POM aggregates,but also offers a promising electrochemical platform constructed from POM-based conductive films for identifying trace biomolecules in complex environments.

关 键 词：POLYOXOMETALATE lanthanide-inserted arsenotungstate polyoxometalate-based conductive film 

分 类 号：TB34[一般工业技术—材料科学与工程]