A Physical Entangling Strategy for Simultaneous Interior and Exterior Modification of Metal–Organic Framework with Polymers

Abstract

A new strategy uses a common feature of metal–organic frameworks (MOFs), namely porosity rather than functionality, to achieve simultaneous interior and exterior modification of a MOF with polymers. We demonstrate that an anhydride‐terminated polyimide oligomer can be covalently grafted to the amine‐functionalized methacrylate polymer backbone residing underneath the MOF surface and physically entangled within the 3D nanochannels. The MOF particles were evenly coated with a thin layer of polyimide brushes on the surface thereby exhibiting increased dispersibility in solvent media as well as in polymer matrix. The MOF pores were decorated with aliphatic amine groups to endow the MOF with higher CO2 affinity at low pressure. The polyimide‐grafted surface allowed MOF particles to interact favorably with the polyimide matrix, producing defect‐free MMM with drastically improved CO2 permeability and maintaining the inherent CO2/N2 and CO2/CH4 selectivity of the neat polymeric membrane.

Molecular-caged metal-organic frameworks for energy management

“…Now, MOF-polymers are prepared by different methods such as MOF blending with polymers, covalent grafting of polymers, growth of MOF on polymer templates, and in situ polymerization with MOF (2,3). Nevertheless, a longstanding challenge arises from the exposed MOF pores, which are susceptible to penetration by small molecules like monomers and curing agents or even polymer interpenetration, leading to the reduced MOF porosity and compromised performance of MOF-polymers (4)(5)(6).…”

Establishing gas transport highways in MOF-based mixed matrix membranes

“…This suggests the formation of a MOF percolation network in the MMM. Nevertheless, at a high MOF loading, the mechanical properties and the processability of the membranes are destined to suffer greatly to a point where the resultant membranes are no longer suitable for practical applications (32)(33)(34)(35). Ideally, achieving a percolation network in a MOF-based MMM at low MOF loading can, in principle, harness the full separation potential of the MOF while maintaining the processability and mechanical advantages of the polymer matrix.…”

One-step rapid fabrication of MOF@polymer core–shell particles through non-solvent induced surface deposition

“…[15][16][17][18][19] MOF@polymer core-shell particles have recently emerged as a special group of MOF-polymer composite materials that show enhanced properties in many aspects compared to their pristine MOF counterparts. [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] Compared to simple MOF-polymer blends, MOF@polymer is characterized by the presence of a thin yet uniform polymer coating on each MOF particle. By applying such coating, the chemical stability, 24,26 dispersibility, 20,31 processability, 22,28 self-assembly behavior, 29,30 and transport properties 27,33 of the MOF particles can be readily improved.…”