Colloidal
suspensions of Zn-based ZIF-8 metal–organic framework (MOF)
particles were synthesized (both micrometer μ-ZIF-8- and nanometer
n-ZIF-8-sized, respectively). Postsynthetic modification was carried
using 2-amino-ethanethiol (cysteamine or Cys), a thiol-bearing monodentate
ligand, and particles obtained were employed for the assembly of films
on gold-coated electrode surfaces. The results obtained show that,
aside from conferring chemical affinity toward Au, when suitable molar
ratios are employed, cysteamine modification causes partial coordinative
chemical etching of inherently microporous ZIF-8 units, thus giving
rise to additional mesoporosity. Cysteamine concentration and exposure
time were found to act as control parameters ultimately determining
the transport properties of porous films obtained, which can then
feature, e.g., size-exclusion effects. The colloidal
modification strategies like the one hereby described can be employed
for the preparation of robust nano-organized MOF thin films with hierarchical
porosity, which bear great potential for its application in separation
technologies.
We hereby report on thermodynamic and kinetic aspects of ZIF-8 MOF synthesis from methanolic solutions of precursors and 3-mercaptopropionic acid (MPA) acting as chemical modifying agent. MPA bears great interest...
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