am1c04920_si_001.pdf (1.98 MB)
In Situ Investigation of Multicomponent MOF Crystallization during Rapid Continuous Flow Synthesis
journal contributionposted on 2021-11-05, 17:03 authored by Brandon He, Lauren K. Macreadie, James Gardiner, Shane G. Telfer, Matthew R. Hill
Access to the potential applications of metal–organic frameworks (MOFs) depends on rapid fabrication. While there have been advances in the large-scale production of single-component MOFs, rapid synthesis of multicomponent MOFs presents greater challenges. Multicomponent systems subjected to rapid synthesis conditions have the opportunity to form separate kinetic phases that are each built up using just one linker. We sought to investigate whether continuous flow chemistry could be adapted to the rapid formation of multicomponent MOFs, exploring the UMCM-1 and MUF-77 series. Surprisingly, phase pure, highly crystalline multicomponent materials emerge under these conditions. To explore this, in situ WAXS was undertaken to gain an understanding of the formation mechanisms at play during flow synthesis. Key differences were found between the ternary UMCM-1 and the quaternary MUF-7, and key details about how the MOFs form were then uncovered. Counterintuitively, despite consisting of just two ligands UMCM-1 proceeds via MOF-5, whereas MUF-7 consists of three ligands but is generated directly from the reaction mixture. By taking advantage of the scalable high-quality materials produced, C6 separations were achieved in breakthrough settings.
quality materials producedmulticomponent systems subjectedmulticomponent mof crystallizationtwo ligands umcmrapid synthesis conditionsrapid synthesisthree ligandsmulticomponent mofsflow synthesisrapid formationrapid fabricationternary umcmtaking advantagesitu scale productionscalable highreaction mixturepotential applicationsphase pureone linkerkey differenceskey detailsgenerated directlyformation mechanismsdespite consistingc6 separationsbreakthrough settings77 series