Journal
ACS APPLIED MATERIALS & INTERFACES
Volume 8, Issue 40, Pages 27311-27321Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acsami.6b08954
Keywords
MOF/polymer interface; mixed matrix membrane; transmission electron microscopy; molecular modeling; polymer of intrinsic microporosity; ZIF-8
Funding
- European Community [608490, M4CO2]
- Institut Universitaire de France
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A study integrating advanced experimental and. modeling tools was undertaken to characterize the micro structural and interfacial properties of mixed matrix membranes (MMMs) composed of the zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) and two polymers of intrinsic micro porosity (PIM-1 and PIM-EA-TB). Analysis probed both the initial ZIF-8/PIM-1 colloidal suspensions and the final hybrid membranes. By combination of dynamic light scattering (DLS) and transmission electron microscopy (TEM) analytical and imaging techniques with small-angle X-ray scattering (SAXS), the colloidal suspensions were shown to consist mainly of two distinct kinds of particles, namely, polymer aggregates of about 200 nm in diameter and densely packed ZIF-8-NP aggregates of a few 100 nm in diameter with a 3 nm thick polymer top-layer. Such aggregates are likely to impart the granular texture of ZIF-8/'PIMs MMMs as shown by SEM-XEDS analysis. At the molecular scale, modeling studies showed that the surface coverage of ZIF-8 NPs by both polymers appears not to be optimal with the presence of microvoids at the interfaces that indicates only a moderate compatibility between the polymer and ZIF-8. This study shows that the microstructure of MMMs results from a complex interplay between the ZIF-8/PIM compatibility, solvent, surface chemistry of the ZIF-8 NPs, and the physicochemical properties of the polymers such as molecular structure and rigidity.
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