Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins

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Modular chemistry: secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks.

Mohamed Eddaoudi, David Moler, Hailian Li … (2001)

Secondary building units (SBUs) are molecular complexes and cluster entities in which ligand coordination modes and metal coordination environments can be utilized in the transformation of these fragments into extended porous networks using polytopic linkers (1,4-benzenedicarboxylate, 1,3,5,7-adamantanetetracarboxylate, etc.). Consideration of the geometric and chemical attributes of the SBUs and linkers leads to prediction of the framework topology, and in turn to the design and synthesis of a new class of porous materials with robust structures and high porosity.

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The pervasive chemistry of metal-organic frameworks.

Jeffrey R Long, Omar Yaghi (2009)

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Hydrocarbon separations in a metal-organic framework with open iron(II) coordination sites.

Eric Bloch, Wendy L Queen, Rajamani Krishna … (2012)

The energy costs associated with large-scale industrial separation of light hydrocarbons by cryogenic distillation could potentially be lowered through development of selective solid adsorbents that operate at higher temperatures. Here, the metal-organic framework Fe(2)(dobdc) (dobdc(4-) : 2,5-dioxido-1,4-benzenedicarboxylate) is demonstrated to exhibit excellent performance characteristics for separation of ethylene/ethane and propylene/propane mixtures at 318 kelvin. Breakthrough data obtained for these mixtures provide experimental validation of simulations, which in turn predict high selectivities and capacities of this material for the fractionation of methane/ethane/ethylene/acetylene mixtures, removal of acetylene impurities from ethylene, and membrane-based olefin/paraffin separations. Neutron powder diffraction data confirm a side-on coordination of acetylene, ethylene, and propylene at the iron(II) centers, while also providing solid-state structural characterization of the much weaker interactions of ethane and propane with the metal.