Novel Elastically Stretchable Metal–Organic Framework Laden Hydrogel with Pearl–Net Microstructure and Freezing Resistance through Post‐Synthetic Polymerization

Nanocomposite hydrogels (NCs) with mechanical properties suitable for a diverse range of applications can be made by combining polymer hydrogel networks with various inorganic nanoparticles. However, the mechanical properties and functions of conventional NCs are seriously limited by the poor structural or functional tunability of common nanofillers and by the low amounts of such fillers that can be added. Here, the fabrication of novel elastically stretchable and compressible nanocomposite hydrogels (MIL‐101‐MAAm/PAAm) with a distinctive pearl–net microstructure and a metal–organic framework (MOF) content in the range of 20–60 wt% through post‐synthetic polymerization (PSP) is reported. The MOFs, which are compatible with polymers and have a high degree of modifiability in structure and functions, are used as nanofillers. Such MOF‐laden hydrogels can withstand 500% tensile strain or 90% compressive strain without fracture and recover quickly upon unloading. They are also resistant to freezing at −25 °C. In addition, the problems associated with poor flexibility and processability of MOFs are overcome by the hybridization of hydrogel polymer matrices with MOFs. The results of this work not only provide a new perspective on preparing NCs but also indicate a promising path for applying MOFs in flexible devices. Novel elastic metal–organic framework (MOF)‐laden nanocomposite hydrogels with a unique pearl–net microstructure and high MOF content (20–60 wt%) are fabricated through the employment of modified MOF nanoparticles and a post‐synthetic polymerization strategy, which can endure 500% tensile strain or 90% compressive strain without fracture and recover quickly upon unloading and are also resistant to freezing at −25 °C.