Understanding and controlling the nucleation and growth of metal–organic frameworks

Abstract

This review highlights the theories, parameters, and methods, which can be used to understand, control, and monitor MOF nucleation and growth.

The role of protein folding in prenucleation clusters on the activity of enzyme@metal–organic frameworks

“…Moreover, biomolecular unfolding from precursor interactions can additionally affect the formation mechanism and final MOF structure, which has been demonstrated in an FITC-BSA@ZIF-8 model. 17,32 Furthermore, while the amorphous structure that we report in 4 : 1 GOx@ZIF-8 aligns with some reports that have also observed amorphous ZIF-8 at this condition, 8 other studies have also reported crystalline sod products at the same L : M ratio. 6 We suggest that these differences may be due to the differing stabilities, structures, and purities of GOx obtained by different laboratories.…”

Deciphering Trends in Structural Parameters of RE-UiO-66 Metal–Organic Frameworks through Single Crystal Analysis

“…Upon obtaining a diffractogram, it can be compared to a simulated pattern for a known structure to confirm phase purity and overall topology of a MOF. Alternatively, and in conjunction with other characterization techniques, PXRD can be used to obtain structural information about a newly synthesized material through the Rietveld refinement method, which involves modeling the position of the ions in the unit cell. , When the crystallite size is >50 μm, then single crystal X-ray diffraction (SCXRD) can be used to obtain absolute structural information on the MOF. , To this day, obtaining a MOF sample suitable for SCXRD can be a difficult task since there is not, in most cases, a significant difference between growth and nucleation rates leading to the precipitation of microcrystalline powders versus suitable single crystals. , Furthermore, solving and refining MOF crystal structures can be very challenging due to (i) the presence of pore-occupying species, which are often highly disordered and (ii) the possibility of crystal twinning due to high symmetry . It should be noted that, in some cases, SCXRD data can be obtained for MOF crystallites <50 μm in size by using synchrotron irradiation or diffractometers with high power sources. , …”

“…25,28 To this day, obtaining a MOF sample suitable for SCXRD can be a difficult task since there is not, in most cases, a significant difference between growth and nucleation rates leading to the precipitation of microcrystalline powders versus suitable single crystals. 29,30 Furthermore, solving and refining MOF crystal structures can be very challenging due to (i) the presence of pore-occupying species, which are often highly disordered and (ii) the possibility of crystal twinning due to high symmetry. 28 It should be noted that, in some cases, SCXRD data can be obtained for MOF crystallites <50 μm in size by using synchrotron irradiation or diffractometers with high power sources.…”

Controlled Growth of Highly Defected Zirconium–Metal–Organic Frameworks via a Reaction–Diffusion System for Water Remediation

“…An alternative way to tune the size of MOF crystals involves a direct control over their mechanisms of nucleation and growth. 27 These processes are hard to monitor in solvothermal methods especially with UiO-66 where the reaction between the terephthalic acid and the Zr(IV) metal nodes is very fast making it challenging to lengthen the nucleation process. 28 Recently, our research group demonstrated that MOF materials with controlled crystal size and morphology can be generated in a hydrogel medium via self-assembly while relying on the diffusion process of metal cations and linkers.…”

“…An alternative way to tune the size of MOF crystals involves a direct control over their mechanisms of nucleation and growth . These processes are hard to monitor in solvothermal methods especially with UiO-66 where the reaction between the terephthalic acid and the Zr(IV) metal nodes is very fast making it challenging to lengthen the nucleation process .…”