Cluster-Cation Pairs Mediated Assembly of Subnanometer Polyoxometalates Superstructures

作者：Zhong Li, Haoyang Li, Yan Lin, Wenxiong Shi, Xun Wang · 发表于：Journal of the American Chemical Society · 年份：2024 · DOI：10.1021/jacs.4c09034 · 被引用次数：29 · 研究领域：Polyoxometalates: Synthesis and Applications、Advanced Nanomaterials in Catalysis、Nanocluster Synthesis and Applications

Superstructures assembled by subnanometer polyoxometalate (POM) clusters are interesting for their attractive structures and excellent properties. However, the complex interactions between clusters and cations make it challenging to control the assembly of POM clusters at the subnanometer scale. Here, 20 cluster-assembled superstructures built by two types of MP 2 W 17 O 61 (M = La–Lu) clusters are successfully synthesized. The precise structures and configurations of the subnanostructures, including nanowires, tetragonal nanosheets, and rectangular nanosheets, are characterized and presented. Molecular dynamics (MD) simulations reveal that the difference in interactions of POM clusters and cations leads to the formation of distinct superstructures. Two mechanisms of superstructure formation are proposed. Furthermore, the EuP 2 W 17 nanosheet behaves with a high Faradaic efficiency of 90.2% and selectivity of 87.3% for glycolic acid in the electrocatalytic ethylene glycol oxidation reaction, which is much higher than that of isolated cluster components. This work connects the cluster topologies and cluster-cation pairs to the superstructures of cluster assemblies, providing general guidelines for the supramolecular self-assembly of POM clusters.