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HERO ID
4275770
Reference Type
Journal Article
Title
Improved CO2 Capture from Flue Gas by Basic Sites, Charge Gradients, and Missing Linker Defects on Nickel Face Cubic Centered MOFs
Author(s)
Lopez-Maya, E; Montoro, C; Colombo, V; Barea, E; Navarro, JAR
Year
2014
Is Peer Reviewed?
Yes
Journal
Advanced Functional Materials
ISSN:
1616-301X
EISSN:
1616-3028
Volume
24
Issue
39
Page Numbers
6130-6135
DOI
10.1002/adfm.201400795
Web of Science Id
WOS:000344006000005
Abstract
The adsorptive properties of the isoreticular series [Ni-8(OH)(4)(H2O)(2)(BDP_X)(6)] (H2BDP_X = 1,4-bis(pyrazol-4-yl)benzene-4-X with X = H (1), OH (2), NH2 (3)) can be enhanced by postsynthetic treatment with an excess of KOH in ethanol. In the case of X = H, NH2, this treatment leads to partial removal of the organic linkers, deprotonation of coordinated water molecules and introduction of extraframework cations, giving rise to materials of K[Ni-8(OH)(5)(EtO)-(H2O)(2)(BDP_X)(5.5)] (1@KOH, 3@KOH) formulation, in which the original framework topology is maintained. By contrast, the same treatment with KOH in the [Ni-8(OH)(4)(H2O)(2)(BDP_OH)(6)] (2) system, enclosing the more acidic phenol residues, leads to a new material containing a larger fraction of missing linker defects and extra-framework cations as well as phenolate residues, giving rise to the material K-3[Ni-8(OH)(3)(EtO)(H2O)(6)(BDP_O)(5)] (2@KOH), which also conserves the original face cubic centered (fcu) topology. It is noteworthy that the introduction of missing linker defects leads to a higher accessible pore volume with a concomitant increased adsorption capacity. Moreover, the creation of coordinatively unsaturated metal centers, charge gradients, and phenolate nucleophilic sites in 2@KOH gives rise to a boosting of CO2 capture features with increased adsorption heat and adsorption capacity, as proven by the measurement of pulse gas chromatography and breakthrough curve measurements of simulated flue gas.
Keywords
metal-organic frameworks; carbon capture; gas separation; zeomimetic; green house gases
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