A Lanthanide-Incorporated Phospho(III)tungstate Aggregate Constructed from [HPIIIW8O31]10- and [W11O39]12- Building Blocks and Its Nanocomposite with CdS for Ultrasensitive Photoelectrochemical Detection of Oxytetracycline.

Abstract

A novel tartronic acid decorated hexa-CeIII-incorporated phospho(III)tungstate aggregate (C4H12NO)6Na18H2[(HPW8O31)2[W11O39]2(H2TAD)4(H2O)4W4Ce6H2P2O14]·84H2O (1, H3TAD = tartronic acid) was synthesized by a one-step assembly strategy. Its main skeleton is constructed from two [W11O39]12- fragments, two [HPIIIW8O31]10- segments and one H2TAD--ornamented dodecanuclear heterometallic [W4Ce6H2PIII2O14(H2TAD)4(H2O)4]18+ cluster. In the structure, the [HPIIIO3]2- groups not only work as the heteroatom template to induce the formation of lacunary [HPIIIW8O31]10- segments but also function as the connector to bridge Ce3+ cations. With the help of a reaction strategy of combining ultrasonication treatment with the continuous ion layer adsorption method, the 1/CdS composite was constructed and exhibits prominent photoelectrochemical activity. The 1/CdS composite was used as a photoelectrochemical sensor for oxytetracycline detection at 0 V (vs Ag/AgCl), which displays excellent properties with quick response and low limit of detection (0.042 nM). This work can provide some helpful references in the construction of novel PIII-induced polyoxometalates consisting of different building blocks and can extend the applications of polyoxometalate-based nanocomposites into photoelectrochemical detection for antibiotics as well as biomolecules.