Bloch, W.Babarao, R.Hill, M.Doonan, C.Sumby, C.2013-06-132013-06-132013Journal of the American Chemical Society, 2013; 135(28):10441-104480002-78631520-5126http://hdl.handle.net/2440/78252Here we report the synthesis and ceramic-like processing of a new metal-organic framework (MOF) material, [Cu(bcppm)H2O], that shows exceptionally selective separation for CO2 over N2 (ideal adsorbed solution theory, S(ads) = 590). [Cu(bcppm)H2O]·xS was synthesized in 82% yield by reaction of Cu(NO3)2·2.5H2O with the link bis(4-(4-carboxyphenyl)-1H-pyrazolyl)methane (H2bcppm) and shown to have a two-dimensional 4(4)-connected structure with an eclipsed arrangement of the layers. Activation of [Cu(bcppm)H2O] generates a pore-constricted version of the material through concomitant trellis-type pore narrowing (b-axis expansion and c-axis contraction) and a 2D-to-3D transformation (a-axis contraction) to give the adsorbing form, [Cu(bcppm)H2O]-ac. The pore contraction process and 2D-to-3D transformation were probed by single-crystal and powder X-ray diffraction experiments. The 3D network and shorter hydrogen-bonding contacts do not allow [Cu(bcppm)H2O]-ac to expand under gas loading across the pressure ranges examined or following re-solvation. This exceptional separation performance is associated with a moderate adsorption enthalpy and therefore an expected low energy cost for regeneration.en© 2013 American Chemical SocietyMetal‐organic Frameworkgas separationcarbon capturedynamic behaviorpost‐synthesis processingJournal article00201309512013061313140310.1021/ja40320490003221030000542-s2.0-8488034566218524Bloch, W. [0000-0003-1084-1287]Sumby, C. [0000-0002-9713-9599]