Healable and Post‐Programmable Metal–Organic Framework—Vitrimer Composites
Abstract
ABSTRACT Metal–organic framework (MOF) particles are commonly incorporated into polymer composites to impart porosity or functionality, but they often remain as fillers rather than defining the polymer network architecture. Here, we report a new design principle in which UiO‐66‐NH 2 nanoparticles are used as dynamic covalent crosslinkers for a linear polyimines to form MOF–vitrimer composites. Through imine bond formation between MOF‐bound amines and polymer aldehydes, the MOF becomes an integral network node, yielding free‐standing MOF–vitrimer composite films with high solvent resistance, while the MOF retains crystallinity. This architecture gives rise to properties beyond conventional MOF–polymer composites: dynamic imine exchange enables thermal healing, mechanical reprocessing, and chemical recycling. Furthermore, post‐synthetic tempering redistributes network connectivity and reprograms the mechanical properties from soft and extensible to stiff and strong, enabling material pluripotency and tunability to suit different applications. Unlike conventional organic crosslinkers, the MOF nodes also retain their intrinsic functions, allowing the composites to perform aqueous dye adsorption and organophosphate simulant hydrolysis while remaining easy to handle and recover. This work establishes MOFs as multifunctional dynamic crosslinkers for healable, recyclable, and post‐programmable hybrid materials, expanding MOF–polymer composites beyond passive filler architectures.
Article Details
Authors (13)
Rachel K. T. Lau
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Ai Wei Gan
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Sirin Kamarulzaman
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Tristan T. Y. Tan
Laboratory of Green Porous Materials Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Georgina E. K. K. Seah
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Sheila Y. X. Sim
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Yusuke Nishiyama
JEOL Ltd.
Ken‐ichi Otake
Laboratory of Green Porous Materials Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Angeline Y. X. Tan
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Jerry X. Z. Heng
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore
Susumu Kitagawa
Institute for Integrated Cell-Material Sciences, Kyoto University Institute for Advanced Study, Kyoto University, Yoshida Ushinomiya-cho, Sakyo-ku, Kyoto 606-8501, Japan
Jason Y. C. Lim
Institute of Materials Research and Engineering (IMRE), Agency for Science, Technology and Research (A*STAR), Fusionopolis Way, Innovis #08-03, Singapore 138634, Republic of Singapore
Shermin S. Goh
Laboratory For Green Porous Materials Institute of Materials Research and Engineering (IMRE) Agency For Science, Technology and Research (A*STAR) Singapore Republic of Singapore