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Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation

Nature volume 495, pages 80–84 (2013)Cite this article

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Abstract

The energy costs associated with the separation and purification of industrial commodities, such as gases, fine chemicals and fresh water, currently represent around 15 per cent of global energy production, and the demand for such commodities is projected to triple by 2050 (ref. 1). The challenge of developing effective separation and purification technologies that have much smaller energy footprints is greater for carbon dioxide (CO2) than for other gases; in addition to its involvement in climate change, CO2 is an impurity in natural gas, biogas (natural gas produced from biomass), syngas (CO/H2, the main source of hydrogen in refineries) and many other gas streams. In the context of porous crystalline materials that can exploit both equilibrium and kinetic selectivity, size selectivity and targeted molecular recognition are attractive characteristics for CO2 separation and capture, as exemplified by zeolites 5A and 13X (ref. 2), as well as metal–organic materials (MOMs)3,4,5,6,7,8,9. Here we report that a crystal engineering7 or reticular chemistry5,9 strategy that controls pore functionality and size in a series of MOMs with coordinately saturated metal centres and periodically arrayed hexafluorosilicate (SiF62−) anions enables a ‘sweet spot’ of kinetics and thermodynamics that offers high volumetric uptake at low CO2 partial pressure (less than 0.15 bar). Most importantly, such MOMs offer an unprecedented CO2 sorption selectivity over N2, H2 and CH4, even in the presence of moisture. These MOMs are therefore relevant to CO2 separation in the context of post-combustion (flue gas, CO2/N2), pre-combustion (shifted synthesis gas stream, CO2/H2) and natural gas upgrading (natural gas clean-up, CO2/CH4).

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Figure 1: The variable pore size channel structures of SIFSIX-2-Cu, SIFSIX-2-Cu-i and SIFSIX-3-Zn.
Figure 2: Pure gas adsorption, modelling and gas mixture breakthrough studies of SIFSIX compounds.
Figure 3: Gas mixture selectivity of SIFSIX compounds and the stability study of SIFSIX-2-Cu-i.

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Acknowledgements

This publication is based on work supported by KAUST award number FIC/2010/06 (M.E. and M.J.Z.) and KAUST start up funds (M.E.). B.S. acknowledges computational resources made available by an XSEDE grant (number TG-DMR090028). Single-crystal diffraction experiments on SIFSIX-2-Cu-i were conducted at the Advanced Photon Source on beamline 15ID-B of ChemMatCARS Sector 15, which is principally supported by the National Science Foundation/Department of Energy under grant number NSF/CHE-0822838. Use of the Advanced Photon Source was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences under contract number DE-AC02-06CH11357.

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Author notes

  1. Patrick Nugent and Youssef Belmabkhout: These authors contributed equally to this work.

Authors and Affiliations

  1. Department of Chemistry, University of South Florida, 4202 East Fowler Avenue, Tampa, Florida 33620, USA,

    Patrick Nugent, Stephen D. Burd, Katherine Forrest, Tony Pham, Shengqian Ma, Brian Space, Lukasz Wojtas, Mohamed Eddaoudi & Michael J. Zaworotko

  2. Division of Physical Sciences and Engineering, Advanced Membranes and Porous Materials Center, 4700 King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia

    Youssef Belmabkhout, Amy J. Cairns, Ryan Luebke & Mohamed Eddaoudi

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Contributions

P.N., S.D.B. and M.J.Z. contributed to the conceptual approach to designing the materials synthetic experiments; P.N. and S.D.B. carried out the materials synthesis ; L.W. and R.L. conducted and interpreted the crystallographic experiments; P.N., S.D.B., Y.B., S.M., M.E. and A.J.C. conducted and interpreted low-pressure sorption experiments; Y.B. and M.E. contributed to the initial ideas, conceptualizing, designing, conducting (Y.B.) and interpreting sorption experiments for gas separation of various industrially relevant gas mixtures (high-pressure single and mixed gas sorption experiments, sorption kinetics and breakthrough experiments) and IAST calculations; K.F., T.P. and B.S. conducted electrostatic models of gas sorption; and M.E. and M.J.Z. wrote the manuscript.

Corresponding authors

Correspondence to Mohamed Eddaoudi or Michael J. Zaworotko.

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The authors declare no competing financial interests.

Additional information

Supplementary crystallographicdata for this manuscript has been deposited at the Cambridge Crystallographic Data Centre under deposition numbers CCDC 914600 and 914601. These data can be obtained free of charge from http://www.ccdc.cam.ac.uk/data_request/cif.

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Supplementary Information

This file contains Supplementary Text and Data, Supplementary Schemes 1-3, Supplementary Tables 1-4, Supplementary Figures 1-28 and Supplementary References. (PDF 6447 kb)

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Nugent, P., Belmabkhout, Y., Burd, S. et al. Porous materials with optimal adsorption thermodynamics and kinetics for CO2 separation. Nature 495, 80–84 (2013). https://doi.org/10.1038/nature11893

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