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Analysis of High and Selective Uptake of CO2 in an Oxamide-Containing {Cu2(OOCR)4}-Based Metal–Organic Framework

DOI: 10.1002/chem.201304005 DOI Help
PMID: 24806046 PMID Help

Authors: Nada H. Alsmail (School of Chemistry, University of Nottingham, U.K.) , Mikhail Suyetin (School of Chemistry, University of Nottingham, U.K.) , Yong Yan (School of Chemistry, University of Nottingham, U.K.) , Rafel Cabot (School of Chemistry, University of Nottingham, U.K.) , Cristina Perez Krap (University of Nottingham) , Jian Lü (School of Chemistry, University of Nottingham, U.K.) , Timothy Easun (University of Nottingham) , Elena Bichoutskaia (School of Chemistry, University of Nottingham, U.K.) , William Lewis , Alexander J. Blake (University of Nottingham) , Martin Schröder (School of Chemistry, University of Nottingham, U.K.)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry - A European Journal , VOL 20 (24) , PAGES 7317 - 7324

State: Published (Approved)
Published: June 2014
Diamond Proposal Number(s): 8618

Abstract: The porous framework [Cu2(H2O)2L].4H2O.2DMA (H4L=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 unit cell with a=27.9161(6), b=18.6627(4) and c=32.3643(8)Å, beta=112.655(3)°, space group P21/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 three-dimensional space. Cage A is constructed from twelve {Cu2(OOCR)4} paddlewheels and six linkers to form an ellipsoid-shaped cavity approximately 24.0Å along its long axis and 9.6Å across its central diameter. Cage B consists of six {Cu2(OOCR)4} units and twelve linkers and has a spherical diameter of 12.7Å 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 desolvated NOTT-125a, is responsible for excellent CO2 uptake (40.1 wt % at 273K 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 of 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 that are not possible with a single amide.

Subject Areas: Chemistry, Materials, Energy

Instruments: I19-Small Molecule Single Crystal Diffraction

Other Facilities: No