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J Am Chem Soc. 2011 Apr 20;133(15):5664-7. doi: 10.1021/ja111411q. Epub 2011 Mar 25.

Metal-organic frameworks as adsorbents for hydrogen purification and precombustion carbon dioxide capture.

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Department of Chemistry, University of California, Berkeley, California 94720-1460, United States.


Selected metal-organic frameworks exhibiting representative properties--high surface area, structural flexibility, or the presence of open metal cation sites--were tested for utility in the separation of CO(2) from H(2) via pressure swing adsorption. Single-component CO(2) and H(2) adsorption isotherms were measured at 313 K and pressures up to 40 bar for Zn(4)O(BTB)(2) (MOF-177, BTB(3-) = 1,3,5-benzenetribenzoate), Be(12)(OH)(12)(BTB)(4) (Be-BTB), Co(BDP) (BDP(2-) = 1,4-benzenedipyrazolate), H(3)[(Cu(4)Cl)(3)(BTTri)(8)] (Cu-BTTri, BTTri(3-) = 1,3,5-benzenetristriazolate), and Mg(2)(dobdc) (dobdc(4-) = 1,4-dioxido-2,5-benzenedicarboxylate). Ideal adsorbed solution theory was used to estimate realistic isotherms for the 80:20 and 60:40 H(2)/CO(2) gas mixtures relevant to H(2) purification and precombustion CO(2) capture, respectively. In the former case, the results afford CO(2)/H(2) selectivities between 2 and 860 and mixed-gas working capacities, assuming a 1 bar purge pressure, as high as 8.6 mol/kg and 7.4 mol/L. In particular, metal-organic frameworks with a high concentration of exposed metal cation sites, Mg(2)(dobdc) and Cu-BTTri, offer significant improvements over commonly used adsorbents, indicating the promise of such materials for applications in CO(2)/H(2) separations.


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