Two Types of Subgroup-Valence Heteroatoms (PIII, TeIV) Synergistically Controlling Octa-CeIII-Encapsulated Heteropolyoxotungstate and Its Electrochemical Recognition Properties

• Published in: Inorganic chemistry 2022-10, Vol.61 (43), p.17166-17177
• Main Authors: Li, Juan, Song, Nizi, Wang, Menglu, Zhang, Zhimin, Li, Yanzhou, Chen, Lijuan, Zhao, Junwei
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/acs.inorgchem.2c02677

Rapid development of the synthetic chemistry of polyoxometalates (POMs) has greatly driven the generation of structurally variable innovative POM-based materials. Herein, we synthesized a novel PIII and TeIV synergistically controlling octa-CeIII-encapsulated heteropolyoxotungstate [H2N­(CH3)2]11K2Na6H11[Ce8(CH3COO)2(HPIIIO3)2W8O20(H2O)12(B-β-TeW8O30)2(B-α-TeW8O31)4]·64H2O (1). Its distinctive anion skeleton [Ce8(CH3COO)2(HPIIIO3)2W8O20(H2O)12(B-β-TeW8O30)2(B-α-TeW8O31)4]30– is built by two tetra-vacancy [B-β-TeW8O30]8– and four tetra-vacancy [B-α-TeW8O31]10– moieties linked through an inorganic–organic hybrid [Ce8(CH3COO)2(HPIIIO3)2W8O20(H2O)12]26+ {Ce8P2W8} cluster core. Interestingly, {Ce8P2W8} is assembled from four [W2O11]10– groups and two [HPIIIO3]2– anions and eight Ce3+ ions. Besides, 1 was further composited with carboxylated multiwalled carbon nanotube (CMCN), resulting in a bi-component 1/CMCN nanocomposite. An electrochemical recognition platform (named as 1/CMCN/GCE) was built by modifying 1/CMCN on a glassy carbon electrode (GCE) for electrochemical detection of dopamine (DPA) at physiological pH (pH = 7.0). The findings have shown that 1/CMCN/GCE exhibits a good detection limit of 4.95 nM for DPA. This work provides considerable inspiration to promote innovative and rational structure designs of POM-based materials and expand their applications to electrochemical and biological detection fields.