Rare-earth-induced peroxo-phosphotungstates: Enhanced proton conductivity in corresponding membranes

作者：Qianqian Shang, Keqin Shen, Dongyan Zhao, Xiaoyue Wang, Yuting Wei, Haiying Wang, Guan Wang, Dongdi Zhang, Jingyang Niu · 发表于：Polyoxometalates · 年份：2024 · DOI：10.26599/pom.2024.9140077 · 被引用次数：15 · 研究领域：Polyoxometalates: Synthesis and Applications、Metal-Organic Frameworks: Synthesis and Applications、Vanadium and Halogenation Chemistry

The rare-earth induced polyoxometalate clusters, two-dimensional [Ln 2 (H 2 O) 4 (OH)P 2 W 6 (O 2 ) 4 O 23 ] 3 − ( 2D-Ln 2 , Ln = Pr, Sm) and one-dimensional [Ln(H 2 O) 4 P 4 W 6 (O 2 ) 6 (OH) 4 O 24 ] 5− ( 1D-Ln , Ln = Gd, Tb, Dy, Ho) peroxopolytungstates (peroxo-POTs), have been successfully obtained by a similar synthesis method evolved from that of {P 3 W 6 (O 2 ) 6 } cluster. But although the original building block in {P 3 W 6 (O 2 ) 6 } species remained, something completely new was made in the first two examples of peroxo-POTs lanthanide derivatives, which show different structures induced by rare-earth cations. In 2D-Ln 2 , [Ln 2 (H 2 O) 4 (OH)P 2 W 6 (O 2 ) 4 O 23 ] 3 − is composed of a {P 2 W 6 (O 2 ) 4 } polyanion unit that are linked by replacing {PW 3 (O 2 ) 3 } with {PW 3 (O 2 ) 2 }. While rare-earth cations connected with two symmetric {P 2 W 3 (O 2 ) 3 } cores form 1D-Ln . Furthermore, the proton conductivities of 2D-Ln 2 and 1D-Ln compounds were investigated. Under the condition of 65 o C and 95 % RH, 2D-Pr 2 and 1D-Tb exhibited conductivity of 2.62 × 10 -3 S cm -1 and 2.78 × 10 -3 S cm -1 , respectively. While the conductivities of their corresponding Nafion membranes were greatly improved and reached 1.65 × 10 -1 S cm -1 and 1.44 × 10 -1 S cm -1 under the same condition, respectively.