Nanocrystalline metal–organic frameworks boast superior properties compared to their bulk analogs, yet little is known about what dictates particle sizes. Here, we provide experimental evidence for a general model of MOF growth. Solution acidity, ligand excess, and reactant concentrations are shown to form the key independent determinants of particle sizes, hence validating the proposal that nanocrystalline MOFs arise from coupled equilibria involving ligand deprotonation and metal–ligand complexation. As a complement to existing models of polymer formation and crystal growth, our model therefore offers a powerful tool for reliable control over nanoMOF sizes. These particles often exhibit remarkable colloidal stability, even without surfactant ligands. We show through spectroscopic, calorimetric, and suite of other experimental methods that this colloidal stability involves strong solvent-MOF interactions that depart radically from conventional colloidal nanocrystals.

The growth and surface chemistry of metal-organic framework nanocrystals

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ACS Fall 2022

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