Liu Qingda, Zhang Qinghua, Shi Wenxiong, Hu Hanshi, Zhuang Jing, Wang Xun
Key Lab of Organic Optoelectronics and Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing, China.
Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing, China.
Nat Chem. 2022 Apr;14(4):433-440. doi: 10.1038/s41557-022-00889-1. Epub 2022 Feb 10.
Two-dimensional (2D) structures have been shown to possess interesting and potentially useful properties. Because of their isotropic structure, however, clusters tend to assemble into 3D architectures. Here we report the assembly of polyoxometalate clusters into layered structures that feature uniform hexagonal pores and in-plane electron delocalization properties. Because these structures are 2D and visually reminiscent of graphene, they are referred to as 'clusterphenes'. A series of multilayer and monolayer clusterphenes have been constructed with 13 types of polyoxometalate cluster. The resulting clusterphenes were shown to exhibit substantially improved stability and catalytic efficiency towards olefin epoxidation reactions, with a turnover frequency of 4.16 h, which is 76.5 times that of the unassembled clusters. The catalytic activity of the clusterphenes derives from the electron delocalization between identical clusters within the 2D layer, which efficiently reduces the activation energy of the catalytic reaction.
二维（2D）结构已被证明具有有趣且可能有用的特性。然而，由于其各向同性结构，团簇倾向于组装成三维结构。在此，我们报告了多金属氧酸盐团簇组装成具有均匀六边形孔和面内电子离域特性的层状结构。由于这些结构是二维的，并且在视觉上让人联想到石墨烯，因此它们被称为“团簇烯”。已用13种多金属氧酸盐团簇构建了一系列多层和单层团簇烯。结果表明，所得团簇烯对烯烃环氧化反应表现出显著提高的稳定性和催化效率，周转频率为4.16 h，是未组装团簇的76.5倍。团簇烯的催化活性源于二维层内相同团簇之间的电子离域，这有效地降低了催化反应的活化能。
