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Soft polymers wet UiO-66 without interfacial voids

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MD shows flexible PVDF and PEG fill UiO-66 surface pockets; rigid PIM-1 and PS leave microvoids and fail as 70 wt% films.

Source

Understanding the origins of metal-organic framework/polymer compatibility

Semino R, Moreton JC, Ramsahye NA, et al. · Chemical science · 2018

doi.org/10.1039/c7sc04152gRead the full paper ↗81 citationscc by

What they did

Authors built a hydrated {101} UiO-66 slab, equilibrated PIM-1, PS, PVDF and PEG against it, and made 70–80 wt% PEG MMMs compared with PVDF, PS and PIM-1 films.

What they found

PIM-1/PS interfaces have microvoids (up to 13 Å and 8 Å) and long recovery distances (z-length A 15 and 9 Å). PVDF and PEG show no voids, chain-end pore penetration, and H-bonds at 2.0 vs 1.7 Å. PEG Young's modulus more than doubles at 70 wt% MOF, but N2 area collapses; PVDF keeps MOF porosity.

The limits

What it doesn't show

No gas-separation permeance on the new PEG MMMs; PEG pore blocking is inferred from BET, not in situ pore tomography; only one MOF topology was modelled.

Key terms

Mixed-matrix membrane (MMM)
Polymer film filled with MOF particles to combine processability and selectivity.
z-length A
Distance from the MOF surface until polymer density recovers its bulk oscillation.
λs
Polymer density in the overlap region divided by bulk polymer density.
UiO-66
Zirconium terephthalate MOF used here as a 200 nm filler.
PIM-1
Polymer of intrinsic microporosity; rigid, poorly packing chains.

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UiO-66 surface cut used in MD:

Common questions

Which polymers are compatible at 70 wt%?

PVDF and PEG form handleable films; PS and PIM-1 crack.

What molecular feature marks compatibility?

No interfacial microvoids and polymer ends in surface pores.

Why does PEG lose BET area?

Stronger OPEG···HOUiO-66 H-bonds compact the interface and block pores.

What Young's modulus cutoff is proposed?

Polymers below ~1 GPa wet the MOF surface.

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