1 research outputs found
Insight and Control of the Crystal Growth of Zeolitic Imidazolate Framework ZIF-67 by Atomic Force Microscopy and Mass Spectrometry
Combination of electrospray
ionization mass spectrometry (ESI-MS)
and in situ atomic force microscopy (AFM) are applied to provide the
first nanoscopic study of the crystal growth of zeolitic imidazolate
framework ZIF-67. ZIF-67 is found to form through a process of nucleation
and spreading of metastable unenclosed substeps to form stable surface
steps of the enclosed framework structure and demonstrates that isostructural
MOFs, ZIF-67 and ZIF-8, undergo identical crystal growth mechanisms.
The information on the crystal growth species obtained from the AFM
experiments correlates well with the solution species identified by
ESI-MS indicating that the species involved in the growth under low
supersaturation conditions are methylimidazole/methylimidazolate,
monomeric nonmethylimidazole/methylimidazolate complexed Co<sup>2+</sup> ions and monomeric complexed [CoÂ(methylimidazole/methylimidazolate)<sub>1‑2</sub>] ions. Combination of the use of low supersaturation
growth solutions and in situ AFM has also allowed the successful extraction
of the synthetic conditions necessary for formation of ZIF-67 nanodots
that possesses a maximum vertical dimension of 1.2 nm which is the
smallest dimension reported for a stable ZIF-67 entity. This methodology
may be expanded to understand the formation of, and to form, complex
crystal forms of other MOFs for new or improved functionality