Thermal Shrinkage Behavior of Metal–Organic Frameworks

Abstract Thermal treatment of metal–organic frameworks (MOFs) as a post‐treatment approach has grown in popularity and resulted in various MOF‐derived materials. However, the widely used extreme thermolytic conditions (usually above 500 °C) lead to degradation in the well‐defined MOFs intrinsic properties. This work demonstrates that MIL‐101 calcined at medium‐temperature range (200–280 °C) partially breaks the coordination bonds that can introduce more accessible active sites, exhibiting a 10‐fold increase in oxidation activity while retaining its intrinsic structure and porosity. Another fascinating feature of MIL‐101 calcined in this temperature range is their temperature‐dependent shrinkage behavior, which is also found in many other types of MOFs. Based on different shrinkage ratios of various MOFs, yolk–shell MOFs@MOFs structures can be constructed through nonsacrificial template method. Overall, the structural and morphological evolution process of MOFs treated in the medium‐temperature range can open new horizons to develop efficient MOFs catalysts and design complex structures.