A flexible polymer can form a rigid, porous, crystalline framework when its metal-binding groups assemble with zinc. In a 2015 proof of principle, chemists led by Seth Cohen at the University of California, San Diego, made this happen with polymer chains carrying regularly spaced MOF ligands—a result that challenged assumptions about both metal–organic frameworks and polymers.
What is a polyMOF?
A polyMOF is a hybrid material that combines a polymeric ligand with a metal–organic framework (MOF). Conventional MOFs are built from metal ions connected by relatively small organic ligands. In the 2015 work, the ligand groups were built into flexible polymer chains instead. The researchers reported the result in Zhang, Nguyen, Miller and Cohen’s 2015 paper, “polyMOFs: A Class of Interconvertible Polymer-Metal-Organic-Framework Hybrid Materials”.
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How did a flexible polymer form a rigid framework?
The researchers made polymers from chains of methylene units, with regularly spaced 1,4-benzenedicarboxylic acid groups incorporated into the backbone. These acid groups serve as MOF ligands: they can coordinate with metal ions. The reported chains were approximately 20–50 repeat units long, with five to eight methylene spacers between ligand groups.
Heating the polymer in the presence of zinc produced a rigid, porous, crystalline framework. The starting polymer was amorphous, so the striking change was not simply that a polymer bound a metal; it was that the flexible, disordered precursor assembled into an ordered porous material. The report says the mechanism by which that order emerged was not yet clear.
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Why was the result unexpected?
The finding ran against two common expectations. MOF construction was associated with small, rigid ligands capable of linking metal ions into orderly structures. Polymers, meanwhile, were commonly regarded as amorphous rather than highly crystalline and porous.
Cohen called the outcome “a very surprising result.” He said it “defies conventional wisdom both for MOFs, which says you need small, rigid ligands, and for polymers, which are amorphous, not highly crystalline and not porous.” Chemistry World also quoted Martin Attfield, a MOF researcher at the University of Manchester, describing the work as a way to bring polymer and MOF chemistry together in a new class of materials. These assessments explain the conceptual significance; they do not establish that every proposed benefit was achieved.
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What forms did the researchers observe?
Reaction conditions influenced the material’s observed morphology. The report describes spheres and films among the forms produced. It does not provide enough comparative data to rank these morphologies by pore size, stability, performance or suitability for a particular use.
What might polyMOFs make possible?
The researchers and commentators presented additional functions as prospects, not demonstrated applications of the 2015 materials. For example, varying polymer functional groups might introduce new properties; electronically conducting groups in MOF pores were suggested as one possibility. Attfield also raised the prospect of improved hydrolytic or mechanical stability, or of organizing polymers more orderly.
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A 2016 follow-up listed by the Miller Research Group was titled “polyMOFs as Water Tolerant Materials for Selective Carbon Dioxide Separations.” That title indicates continued investigation of water tolerance and carbon-dioxide separation, but it does not by itself establish commercial performance or deployment. The 2015 report demonstrates formation of the hybrid framework, not a market-ready material or proven technology.
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What the 2015 proof of principle establishes
- A polymer carrying regularly spaced MOF ligand groups can assemble with zinc into a rigid, porous, crystalline material.
- The precursor’s flexibility and amorphous character did not prevent an ordered framework from forming.
- Reaction conditions produced different observed forms, including spheres and films.
- The route by which order emerged, and the proposed functional advantages, remained unresolved or prospective in the report.
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