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Issue 30, 2015
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Hydrophobic and moisture-stable metal–organic frameworks

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Abstract

Metal–organic frameworks (MOFs) have proved to be very attractive for applications including gas storage, separation, sensing and catalysis. In particular, CO2 separation from flue gas in post-combustion processes is one of the main focuses of research among the scientific community. One of the major issues that are preventing the successful commercialization of these novel materials is their high affinity towards water that not only compromises gas sorption capacity but also the chemical stability. In this paper, we demonstrate a novel post-synthesis modification approach to modify MOFs towards increasing hydrophobic behaviour and chemical stability against moisture without compromising CO2 sorption capacity. Our approach consists of incorporating hydrophobic moieties on the external surface of the MOFs via physical adsorption. The rationale behind this concept is to increase the surface hydrophobicity in the porous materials without the need of introducing bulky functionalities inside the pore which compromises the sorption capacity toward other gases. We herein report preliminary results on routinely studied MOF materials [MIL-101(Cr) and NiDOBDC] demonstrating that the polymer-modified MOFs retain CO2 sorption capacity while reducing the water adsorption up to three times, with respect to the un-modified materials, via an equilibrium effect. Furthermore, the water stability of the polymer-functionalized MOFs is significantly higher than the water stability of the bare material. Molecular dynamic simulations demonstrated that this equilibrium effect implies a fundamental and permanent change in the water sorption capacity of MOFs. This approach can also be employed to render moisture stability and selectivity to MOFs that find applications in gas separations, catalysis and sensing where water plays a critical role in compromising MOF performance and recyclability.

Graphical abstract: Hydrophobic and moisture-stable metal–organic frameworks

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Publication details

The article was received on 10 Feb 2015, accepted on 01 May 2015 and first published on 01 May 2015


Article type: Paper
DOI: 10.1039/C5DT00606F
Citation: Dalton Trans., 2015,44, 13490-13497
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    Hydrophobic and moisture-stable metal–organic frameworks

    C. A. Fernandez, S. K. Nune, H. V. Annapureddy, L. X. Dang, B. P. McGrail, F. Zheng, E. Polikarpov, D. L. King, C. Freeman and K. P. Brooks, Dalton Trans., 2015, 44, 13490
    DOI: 10.1039/C5DT00606F

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