Understanding Metal–Organic Framework Densification: Solvent Effects and the Growth of Colloidal Primary Nanoparticles in Monolithic ZIF‐8

Abstract To commercialize metal–organic frameworks (MOFs), it is vital they are made easier to handle. There have been many attempts to synthesize them as pellets, tablets, or granules, though they come with innate drawbacks. Only recently have these been overcome, through the advent of self‐shaping densified or monolithic MOFs (_monoMOFs), which require minimal post‐synthetic modification and avoid poor structural integrity, intractability, and pore collapse or blockage. ZIF‐8 (zeolitic imidazolate framework‐8) has emerged as a prototypical _monoMOF in pure and in situ doped forms. Now its formation in solvent mixtures is studied to better understand the early stages of monolith formation and improve the scope of monoliths for hosting solvent‐sensitive guests. Solvent‐, temperature‐ and coagulant‐dependent control over reaction kinetics induces variations in morphology that are explained by relating the nucleation and growth rates of primary nanocrystallites to the stability of colloidal dispersions during reaction. This yields mesoporous _monoZIF‐8 with mean pore size 16 nm, S_BET >1400 m² g⁻¹, bulk density 0.76 g cm⁻³, and resistance to permanent deformation exceeding previous reports. While the study highlights the powerful manipulation of _monoMOF characteristics, a new understanding of the growth and stability of primary nanocrystallites has consequences for colloid synthesis generally.