http://pubs.rsc.org/en/content/articlelanding/2016/ee/c5ee02660a

Enhanced permeation arising from dual transport pathways in hybrid
polymer–MOF membranes

Norman C. Su, Daniel T. Sun, Christine M. Beavers, David K. Britt, Wendy L.
Queen and Jeffrey J. Urban
Energy Environ. Sci., 2016,9, 922-931
DOI: 10.1039/C5EE02660A

Abstract

The rise of anthropogenic global warming has sparked new interest in
developing strategies to mitigate carbon dioxide emissions. Conventional
carbon capture processes are not economically viable at scale due to their
enormous energy cost. Membrane-based separation is a promising alternative,
but its separation performance has traditionally been limited by a
well-known trade-off between permeability and selectivity. Here, we report
a hybrid polymer/inorganic membrane with dual transport pathways, which
allows us to overcome this traditional limitation. The inorganic phase
consists of a metal–organic framework (MOF), which is an ideal inorganic
dispersant to construct dual transport pathways as the crystalline porous
structure of MOFs is more amenable to molecular diffusion than polymers.
Previous hybrid membrane research has failed to achieve sufficiently high
loadings to establish a percolative network necessary for dual transport,
often due to mechanical failure of the membrane at high loading. Using
polysulfone and UiO-66-NH2 MOF as a model system, we achieve high MOF
loadings (50 wt%) and observe the evolution from single mode to dual
transport regimes. The newly formed percolative pathway through the MOF,
which has not previously been observed, acts as a molecular highway for
gases. As the MOF loading increases to 30 wt%, CO2 permeability increases
linearly from 5.6 barrers in polysulfone homopolymer to 18 barrers.
Crucially, between 30 and 40 wt%, a percolative MOF network arises and the
CO2 permeability dramatically rises from 18 to 46 barrers; an eight-fold
increase over pure polysulfone, while maintaining selectivity over methane
and nitrogen near the pure polymer at 24 and 26, respectively. A similar
phenomenon is observed in the measurement of the diffusion coefficient and
is consistent with the formation of dual transport pathways. The findings
in this study enable new approaches towards designing hybrid membranes with
dual transport pathways. This is an important step towards a competitive
membrane-based carbon capture process.

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