Analysis of high and selective uptake of CO2 in an oxamide-containing {Cu2(OOCR)4}-based metal-organic framework

Alsmail, Nada H. and Suyetin, Mikhail and Yan, Yong and Cabot, Rafel and Krap, Christina P. and Lü, Jian and Easun, Timothy L. and Biskoutskaia, Elena and Lewis, William and Blake, Alexander J. and Schröder, Martin (2014) Analysis of high and selective uptake of CO2 in an oxamide-containing {Cu2(OOCR)4}-based metal-organic framework. Chemistry - a European Journal, 20 (24). pp. 7317-7324. ISSN 0947-6539

[img]
Preview
PDF - Requires a PDF viewer such as GSview, Xpdf or Adobe Acrobat Reader
Download (1MB) | Preview

Abstract

The porous framework [Cu2(H2O)2L].4H2O.2DMA ((H¬4¬L = oxalylbis(azanediyl)diisophthalic acid; DMA = N,N-dimethylacetamide), denoted NOTT-125, is formed by connection of {Cu2(RCOO)4} paddlewheels with the isophthalate linkers in L4-. A single crystal structure determination reveals that NOTT-125 crystallises in monoclinic cell with a = 27.9161(6) Å, b = 18.6627(4) Å and c = 32.3643(8) Å, space group P2 (1)/c. The structure of this material shows fof topology, which can be viewed as the packing of two types of cages (Cage A and Cage B) in 3-dimensional space. Cage A is constructed by twelve {Cu2(OOCR)4} paddlewheels and six linkers to form an ellipsoid-shaped cavity approximately 24.0 Å along its long axis and 9.6 Å across the central diameter. Cage B consists of six {Cu2(OOCR)4} units and twelve linkers with a spherical diameter of 12.7 Å taking into account the van der Waals radii of the atoms. NOTT-125 incorporates oxamide functionality within the pore walls, and this, combined with high porosity in the desolvated NOTT-125a, is responsible for excellent CO2 uptake (40.1 wt% at 273 K and 1 bar) and selectivity for CO2 over CH4 or N2. Grand canonical Monte Carlo (GCMC) simulations show excellent agreement with the experimental gas isotherm data, and a computational study into the specific interactions and binding energies of both CO2 and CH4 with the linkers in NOTT-125 reveals a set of strong interactions between CO2 and the oxamide motif, which are not possible with a single amide.

Item Type: Article
Additional Information: This is the pre-peer reviewed version of the following article:Analysis of high and selective uptake of CO2 in an oxamide-containing {Cu2(OOCR)4}-based metal-organic framework / Alsmail, N.H., Suyetin, M., Yan, Y., Cabot, R., Krap, C.P., Lü, J., Easun, T.L., Bichoutskaia, E., Lewis, W., Blake, A. J. and Schröder, M. Chemistry : a European Journal (2014), 20: 7317–7324 which has been published in final form at http://onlinelibrary.wiley.com/doi/10.1002/chem.201304005/abstract
Keywords: Metal-organic framework, CO2, methane, copper, isophthalate, carboxylic acid, amide
Schools/Departments: University of Nottingham UK Campus > Faculty of Science > School of Chemistry
Identification Number: https://doi.org/10.1002/chem.201304005
Related URLs:
URLURL Type
http://www.interscience.wiley.comPublisher
Depositing User: Schroder, Martin
Date Deposited: 27 Aug 2015 08:58
Last Modified: 14 Sep 2016 15:48
URI: http://eprints.nottingham.ac.uk/id/eprint/29702

Actions (Archive Staff Only)

Edit View Edit View