Dynamic Confinement and High‐Entropy Catalytic Synergy Engineering in Hollow Nano‐Metal‐Organic Frameworks

Abstract The systematic regulation of the pore size and chemical environment of nano‐metal‐organic skeletons (n‐MOFs) has been challenged, making it difficult to study their structure‐property relationships in depth. In this study, a universal dynamic template strategy is proposed and successfully achieves the controllable construction of various hollow n‐MOFs (including ZIF‐67, Co‐BTC, etc.). Based on this, the progressive optimization mechanism of pore size limitation (3.4–18 Å), functional group modification (─H, ─NH 2 , etc.), and multi‐metal (Co, Ni, etc.) synergism on the performance of lithium–sulfur (Li–S) batteries is systematically revealed, and the long‐cycle‐life sulfur host HE‐MOF‐74 is further screened. The experimental findings and in situ characterizations collectively demonstrate that hierarchical structural optimization synergistically mitigates active material deactivation and host structure degradation. This work not only provides an integrated “synthesis‐structure‐performance” material design paradigm for Li–S batteries, but also provides a theoretical basis for extending the multiscale optimization logic to other multistep reactive systems.