Experimental evidence for a general model of modulated MOF nanoparticle growth.

Nanoparticles of metal-organic frameworks (nanoMOFs) boast superior properties compared to their bulk analogs, yet little is known about how common synthetic parameters dictate particle sizes. Here, we provide experimental evidence for the "seesaw" model of nanoMOF growth. Solution acidity, ligand excess, and reactant concentrations are decoupled and shown to form the key independent determinants of nanoMOF sizes, thereby validating the proposal that nanoMOFs arise from coupled equilibria involving ligand deprotonation and metal-ligand complexation.

Size control over metal-organic framework porous nanocrystals.

Porous nanocrystals of metal-organic frameworks (MOFs) offer greater bioavailability, higher surface-to-volume ratios, superior control over MOF membrane fabrication, and enhanced guest-sorption kinetics compared to analogous bulk phases, but reliable synthesis of uniformly sized particles remains an outstanding challenge. Here, we identify the smallest and most probable sizes of known MOF nanocrystals and present an exhaustive comparative summary of nano- bulk-MOF syntheses. Based on critical analysis of reported size data and experimental conditions, an alternate to the LaMer model is proposed that describes nanocrystal formation as a kinetic competition between acid-base and metal-ligand reactivity.