Metal–organic
frameworks (MOFs) represent the largest known
class of porous crystalline materials ever synthesized. Their narrow
pore windows and nearly unlimited structural and chemical features
have made these materials of significant interest for membrane-based
gas separations. In this comprehensive review, we discuss opportunities
and challenges related to the formation of pure MOF films and mixed-matrix
membranes (MMMs). Common and emerging separation applications are
identified, and membrane transport theory for MOFs is described and
contextualized relative to the governing principles that describe
transport in polymers. Additionally, cross-cutting research opportunities
using advanced metrologies and computational techniques are reviewed.
To quantify membrane performance, we introduce a simple membrane performance
score that has been tabulated for all of the literature data compiled
in this review. These data are reported on upper bound plots, revealing
classes of MOF materials that consistently demonstrate promising separation
performance. Recommendations are provided with the intent of identifying
the most promising materials and directions for the field in terms
of fundamental science and eventual deployment of MOF materials for
commercial membrane-based gas separations.
Supercapacitors (SCs) are energy storage devices which have high power density and long cycle life. Conventional SCs have two-dimensional planar structures. As a new family of SCs, fiber SCs utilize one-dimensional cylindrically shaped fibers as electrodes. They have attracted significant interest since 2011 and have shown great application potential either as micro-scale devices to complement or even replace micro-batteries in miniaturized electronics and microelectromechanical systems or as macro-scale devices for wearable electronics or smart textiles. This tutorial review provides an essential introduction to this new field. We first introduce the basics of performance evaluation for fiber SCs as a foundation to understand different research approaches and the diverse performance metrics reported in the literature. Next, we summarize the current state-of-the-art progress in structure design and electrode fabrication of fiber SCs. This is followed by a discussion on the integration of multiple fiber SCs and the combination with other energy harvesting or storage devices. Last, we present our perspectives on the future development of fiber SCs and highlight key technical challenges with the hope of stimulating further research progress.
Mixed-matrix membranes
(MMMs) formed by dispersing metal–organic framework (MOF) particles
in polymers have attracted significant attention because these composite
systems can potentially surpass the separation performance of pure
polymers alone. However, performance improvements are often unrealized
because of poor interfacial compatibility between the MOF and the
polymer, which results in interfacial defects. From a practical perspective,
strategies are needed to address these defects so that MMMs can be
deployed in real-world separation processes. From a fundamental perspective,
strategies are needed to reliably form defect-free MMMs so that transport
models can be applied to estimate pure MOF property sets, thereby
enabling the development of robust structure–property relationships.
To address these interfacial challenges, we have developed a method
to surface-functionalize a UiO-66-NH
2
MOF with a nanoscopic
shell of covalently tethered 4,4′-(hexafluoroisopropylidene)diphthalic
anhydride–Durene oligomers. When combined with a high-molecular-weight
polymer of identical chemical structure to that of the imide-functional
MOF surface, defect-free MMMs with uniform particle dispersions can
be formed. With this technique, both permeabilities and selectivities
of select gases in the MMMs were improved at loadings ranging from
5 to 40 wt %. At a 40 wt % loading, CO
2
permeability and
CO
2
/CH
4
selectivity were enhanced by 48 and
15%, respectively. Additionally, pure MOF permeabilities for H
2
, N
2
, O
2
, CH
4
, and CO
2
were predicted by the Maxwell model.
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