Covalent and Selective Grafting of PEG Brushes at the Surface of ZIF-8 for the Processing of Membranes for Pervaporation.

Marvin Benzaqui; Rocio Semino; Florent Carn; Sérgio Rodrigues Tavares; Nicolas Menguy; Mónica Giménez-Marqués; Elena Bellido; Patricia Horcajada; Thomas Berthelot; Anna Kuzminova; Maria Dmitrenko; Anastasia Penkova; Denis Roizard; Christian Serre; Guillaume Maurin; Nathalie Steunou

Covalent and Selective Grafting of PEG Brushes at the Surface of ZIF-8 for the Processing of Membranes for Pervaporation.

Marvin Benzaqui ^{1, 2} Rocio Semino ³ Florent Carn ⁴ Sérgio Rodrigues Tavares ³ Nicolas Menguy ⁵ Mónica Giménez-Marqués ^{2, 1} Elena Bellido ¹ Patricia Horcajada ^{1, 6} Thomas Berthelot ^{7, 8} Anna Kuzminova ⁹ Maria Dmitrenko ⁹ Anastasia Penkova ⁹ Denis Roizard ¹⁰ Christian Serre ^{1, 2} Guillaume Maurin ³ Nathalie Steunou ¹

1 ILV - Institut Lavoisier de Versailles

2 IMAP UMR8004 FRE2000 - Institut des Matériaux Poreux de Paris

3 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier

4 MSC (UMR 7057) - Laboratoire Matière et Systèmes Complexes

5 IMPMC - Institut de minéralogie, de physique des matériaux et de cosmochimie

6 Instituto IMDEA Energy

7 LICSEN - Laboratoire Innovation en Chimie des Surfaces et NanoSciences

NIMBE UMR 3685 - Nanosciences et Innovation pour les Matériaux, la Biomédecine et l'Energie (ex SIS2M)

8 SPCSI - Service de Physique et de Chimie des Surfaces et Interfaces

9 SPBU - Saint Petersburg University

10 LRGP - Laboratoire Réactions et Génie des Procédés

Abstract : The so-called Graftfast reaction in water and at room temperature (RT) was applied to graft polyethylene glycol (PEG) at the surface of the microporous zeolitic imidazolate framework ZIF-8 nanoparticles (NPs) using acrylPEG of different chain lengths (480 Da and 5 kDa). In comparison to non-modified ZIF-8 NPs, both chemical and colloidal stabilities of PEGylated ZIF-8 NPs are significantly enhanced in water. A series of colloidal complex fluids by mixing PEG grafted ZIF-8 (i. e. PEG-g-ZIF-8) NPs with different amounts of polyvinylalcohol (PVA) was prepared and characterized by advanced characterization tools such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS) thereby showing their long-term colloidal stability. Finally, dense and supported mixed matrix membranes were cast from PEG-g-ZIF-8/PVA solutions and have shown high performance in isopropanol (IPA) dehydration by pervaporation. The permeation flux of the supported MMM (i. e. 0.091 kg/(m$^2$h) is eleven times higher than that of the pure PVA membrane and these MMMs present a high separation factor (i. e. 7326). These transport properties are presumably due to the molecular sieving effects induced by ZIF-8 and the good interfacial properties of the membrane. The computational exploration of the ZIF-8/PVA and PEG/PVA interfaces provides a microscopic scale explanation for the enhanced compatibility of PVA with the PEGylated MOF when compared to that for the composite based on the bare ZIF-8 as a filler.

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Journal articles

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Chemical Sciences / Material chemistry

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