A hydrophobic CO 2 physisorbent Most materials for carbon dioxide (CO 2 ) capture of fossil fuel combustion, such as amines, rely on strong chemisorption interactions that are highly selective but can incur a large energy penalty to release CO 2 . Lin et al . show that a zinc-based metal organic framework material can physisorb CO 2 and incurs a lower regeneration penalty. Its binding site at the center of the pores precludes the formation of hydrogen-bonding networks between water molecules. This durable material can preferentially adsorb CO2 at 40% relative humidity and maintains its performance under flue gas conditions of 150°C. —PDS

Metal-organic framework (MOF) materials are a nontraditional route to ion conductors, but their crystallinity can give insight into molecular-level transport mechanisms. However, some MOFs can be structurally compromised in humid environments. A new 3D metal-organic framework, PCMOF-5, is reported which conducts protons above 10(-3) S/cm at 60 °C and 98% relative humidity. The MOF contains free phosphonic acid groups, shows high humidity stability, and resists swelling in the presence of hydration. Channels filled with crystallographically located water and acidic groups are also observed.

A metal organic framework with amine-lined pores gives high values for surface area and heat of adsorption with CO(2) gas.

Two complementary design strategies, isomorphous ligand replacement and heterocycle doping, have been applied to iteratively enhance the proton conductivity of a metal-organic framework, β-PCMOF2. The resulting materials, PCMOF2/(Pz) and PCMOF2/(Tz) (Pz = 1H-pyrazole, Tz = 1H-1,2,4-triazole), have their proton conduction raised almost 2 orders of magnitude compared to β-PCMOF2. The bulk conductivities of these materials are over 10 S cm at 85 °C and 90% relative humidity (RH), while maintaining the parent MOF structure. A solid state synthetic route for doping 1-D channels is also presented.

Using the concept of isomorphous replacement applied to entire ligands, a C(3)-symmetric trisulfonate ligand was substituted with a C(3)-symmetric tris(hydrogen phosphonate) ligand in a proton conducting metal-organic framework (MOF). The resulting material, PCMOF2½, has its proton conduction raised 1.5 orders of magnitude compared to the parent material, to 2.1 × 10(-2) S cm(-1) at 90% relative humidity and 85 °C, while maintaining the parent MOF structure.

Attempted coordination of "Ga(I)I" with two new sterically bulky, aryl substituted bis(imino)pyridine ligands lead to Ga(III) species [2,6-{ArN=CPh}(2)(NC(5)H(3))]GaI(2)(+)GaI(4)(-) (Ar = 2,5-(t)Bu(2)C(6)H(3), 2,6-(i)Pr(2)C(6)H(3) = Dipp) arising from thermodynamically favorable disproportionation reactions. Examination of these reactions lead to isolation of a neutral radical species [2,6-{DippN=CPh}(2)(NC(5)H(3))]GaI(2). Both EPR spectroscopy and DFT calculations on this compound indicate that the unpaired electron is localized in a di(imino)pyridine pi* orbital of an anionic ligand with nearly zero contribution from the Ga or I centers. Reaction of {2,5-(t)Bu(2)C(6)H(3)N=CPh}(2)(NC(5)H(3)) with AlCl(3) yielded an analogous Al(iii) product, [{2,5-(t)Bu(2)C(6)H(3)N=CPh}(2)(NC(5)H(3))]AlCl(2)(+)AlCl(4)(-).

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