MOFs as New Catalytic Platform for Covalent Adaptable Networks: Catalysis Meets Reinforcement

ABSTRACT Catalysis of bond exchange reactions is a versatile route to adjust kinetics and onset temperature of bond exchange reactions in covalent adaptable networks (CANs). In this work, we introduce a novel heterogeneous catalytic platform for CANs by immobilizing bases of low molecular weight on metal organic frameworks (MOFs). Specifically, the base 1,5,7‐triazabicyclo(4.4.0)dec‐5‐ene (TBD) was coordinated on the MOF UiO‐66. The obtained catalyst UiO‐TBD benefits from the high loading capacity of the MOF and exhibits similar catalytic activity in accelerating thiol–thioester exchange reactions in dynamic photopolymers compared to free TBD while outperforming non‐porous heterogeneous systems using ZrO 2 nanoparticles as a carrier. Moreover, it demonstrates a 37% higher thermal stability based on decreased volatility relative to free TBD. Beyond its catalytic role, UiO‐TBD simultaneously reinforces the material, leading to enhanced mechanical performance and reduced creep. This approach offers broad applicability, driven by its modularity and scalability. UiO‐TBD represents a two‐in‐one additive that not only catalyzes exchange reactions in CANs but also strengthens the network, opening new opportunities for multifunctional catalyst design in (dynamic) polymer systems.