Zhong Li, Ping Bai, Ruixiang Du, Xiang Ma, Yi-Xin Liu, Jinyu Li, Hui Li, Ping Gao, Yan Lin, Shou‐Tian Zheng, Xun Wang
NS. Density functional theory calculations and molecular dynamics simulations reveal that incorporating metals into the POM framework modulates surface charge and ligand orientation, thereby directing the formation of distinct superstructures. Collision dynamics analyses further reveal that the surface ligand distribution affects reactant adsorption and diffusion, consequently affecting catalytic activity. This work not only establishes cluster surface engineering as a powerful strategy for constructing tailored subnanometric assemblies, but also provides deep insight into how the surface characteristics of these assemblies govern catalytic behavior.