Validation and Mechanistic Studies of the Headspace Effect in MOF Synthesis

Abstract The influence of headspace volume and composition on metal–organic framework (MOF) synthesis has been largely overlooked with no mechanisms currently invoking these factors. Herein, we reveal that an increased volume of oxygen in the headspace during the synthesis of zinc carboxylate‐based MOFs (MOF‐5, MOF‐177, and IRMOF‐8) as well as UiO‐66 and ZJU‐28 accelerates crystal formation. Investigation into the underlying mechanism of this phenomenon elucidates the critical roles played by all reagents, and some of their byproducts, in MOF synthesis. These insights are the key to developing more efficient and sustainable synthetic strategies for MOF production.