Universal Strategy for Metal‐Organic Framework Growth: From Cascading‐Functional Films to MOF‐on‐MOFs

Transformation of metal-organic framework (MOF) particles into thin films is urgently needed for the persistent development of well-applicable devices, and recently emerging functional-integrated hybrid frameworks. Although some flexible polymers and exclusive modification approaches have been proposed, the additive-free and widely applicable strategy has not been reported, hampering the deep investigation of the structure-performance relationship. A universal strategy for the in situ growth of large-area and continuous MOF films with controllable microstructures is introduced, through the modification of multi-scale and multi-structure substrates with poly(4-vinylpyridine) as the anchor to capture metal ions via Coulomb attraction. Based on the clarified structure-adsorption-separation mechanisms, the customized devices fabricated by in situ growth can achieve highly selective adsorption and excellently synergetic separation of various industrially relevant isomers. In addition, this strategy is also feasible for the construction of MOF-on-MOFs with varied lattice parameters. This strategy is easy to implement and will be widely applicable to the surface growth of diverse MOFs on desired substrates, and provides a new concept for developing hybrid MOFs integrating with customized functionalities.