Jayaramulu, Kolleboyina ; Reddy, Sandeep Kumar ; Hazra, Arpan ; Balasubramanian, Sundaram ; Maji, Tapas Kumar (2012) Three-dimensional metal–organic framework with highly polar pore surface: H2 and CO2 storage characteristics Inorganic Chemistry, 51 (13). pp. 7103-7111. ISSN 0020-1669
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Official URL: https://pubs.acs.org/doi/abs/10.1021/ic202601y
Related URL: http://dx.doi.org/10.1021/ic202601y
Abstract
A three-dimensional (3D) pillared-layer metal–organic framework, [Cd(bipy)0.5(Himdc)](DMF)]n (1), (bipy =4,4′-bipyridine and Himdc = 4,5-imidazoledicarboxylate) has been synthesized and structurally characterized. The highly rigid and stable framework contains a 3D channel structure with highly polar pore surfaces decorated with pendant oxygen atoms of the Himdc linkers. The desolvated framework [Cd(bipy)0.5(Himdc)]n (1′) is found to exhibit permanent porosity with high H2 and CO2 storage capacities. Two H2 molecules occluded per unit formula of 1′ and the corresponding heat of H2 adsorption (ΔHH2) is about ∼9.0 kJ/mol. The high value of ΔHH2 stems from the preferential electrostatic interaction of H2 with the pendent oxygen atoms of Himdc and aromatic bipy linkers as determined from first-principles density functional theory (DFT) based calculations. Similarly, DFT studies indicate CO2 to preferentially interact electrostatically (Cδ+···Oδ-) with the uncoordinated pendent oxygen of Himdc. It also interacts with bipy through C–H···O bonding, thus rationalizing the high heat (ΔHCO2 ∼ 35.4 kJ/mol) of CO2 uptake. Our work unveiled that better H2 or CO2 storage materials can be developed through the immobilization of reactive hetero atoms (O, N) at the pore surfaces in a metal–organic framework.
Item Type: | Article |
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Source: | Copyright of this article belongs to American Chemical Society. |
ID Code: | 114097 |
Deposited On: | 29 May 2018 11:24 |
Last Modified: | 29 May 2018 11:24 |
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