Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites

Smith, Gemma L., Eyley, Jennifer E., Han, Xue, Zhang, Xinran, Li, Jiangnan, Jacques, Nicholas M., Godfrey, Harry G.W., Argent, Stephen P., McCormick McPherson, Laura J., Teat, Simon J., Cheng, Yongqiang, Frogley, Mark D., Cinque, Gianfelice, Day, Sarah J., Tang, Chiu C., Easun, Timothy L., Rudić, Svemir, Ramirez-Cuesta, Anibal J., Yang, Sihai and Schröder, Martin (2019) Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites. Nature Materials, 18 (12), 1358-1365. (doi:10.1038/s41563-019-0495-0).

Abstract

Emissions of SO₂ from flue gas and marine transport have detrimental impacts on the environment and human health, but SO₂ is also an important industrial feedstock if it can be recovered, stored and transported efficiently. Here we report the exceptional adsorption and separation of SO₂ in a porous material, [Cu₂(L)] (H₄L = 4′,4‴-(pyridine-3,5-diyl)bis([1,1′-biphenyl]-3,5-dicarboxylic acid)), MFM-170. MFM-170 exhibits fully reversible SO₂ uptake of 17.5 mmol g⁻¹ at 298 K and 1.0 bar, and the SO₂ binding domains for trapped molecules within MFM-170 have been determined. We report the reversible coordination of SO₂ to open Cu(ii) sites, which contributes to excellent adsorption thermodynamics and selectivities for SO₂ binding and facile regeneration of MFM-170 after desorption. MFM-170 is stable to water, acid and base and shows great promise for the dynamic separation of SO₂ from simulated flue gas mixtures, as confirmed by breakthrough experiments.

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Contributors

Author: Laura J. McCormick McPherson

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