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

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. In this paper, 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.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3]; ORCiD logo [3];  [4]; ORCiD logo [5];  [5];  [5];  [5]; ORCiD logo [6];  [7]; ORCiD logo [4]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Manchester, Manchester (United Kingdom)
  2. Univ. of Nottingham, Nottingham (United Kingdom)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. Diamond Light Source, Didcot (United Kingdom)
  6. Cardiff Univ., Cardiff (United Kingdom)
  7. STFC Rutherford Appleton Lab., Chilton (United Kingdom)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1580420
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 18; Journal Issue: 12; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

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. Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites. United States: N. p., 2019. Web. https://doi.org/10.1038/s41563-019-0495-0.
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, & Schröder, Martin. Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites. United States. https://doi.org/10.1038/s41563-019-0495-0
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. Mon . "Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites". United States. https://doi.org/10.1038/s41563-019-0495-0. https://www.osti.gov/servlets/purl/1580420.
@article{osti_1580420,
title = {Reversible coordinative binding and separation of sulfur dioxide in a robust metal–organic framework with open copper sites},
author = {Smith, Gemma L. and Eyley, Jennifer E. and Han, Xue and Zhang, Xinran and Li, Jiangnan and Jacques, Nicholas M. and Godfrey, Harry G. W. and Argent, Stephen P. and McCormick McPherson, Laura J. and Teat, Simon J. and Cheng, Yongqiang and Frogley, Mark D. and Cinque, Gianfelice and Day, Sarah J. and Tang, Chiu C. and Easun, Timothy L. and Rudić, Svemir and Ramirez-Cuesta, Anibal J. and Yang, Sihai and Schröder, Martin},
abstractNote = {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. In this paper, 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.},
doi = {10.1038/s41563-019-0495-0},
journal = {Nature Materials},
number = 12,
volume = 18,
place = {United States},
year = {2019},
month = {10}
}

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Figures / Tables:

Fig. 1 Fig. 1: Structure of MFM-170 solved from single crystal X-ray data. The metal cluster of MFM-170 consists of a Cu2(O2CR)4 paddlewheel with four isophthalate units occupying the equatorial sites and one pyridyl N-donor from the ligand coordinating to the axial site of one Cu atom. The axial position of themore » other Cu atom of the Cu2(O2CR)4 unit is occupied by a water molecule. The framework is constructed from Cu24(RC6H3(CO2)2)24 cuboctahedron, which acts as a 36-connected node, joined in a cubic array to six adjacent cuboctahedra by four ligands each. The overall framework can be visualised as this smaller cubic net which is connected to a secondary identical net via the 12 corners of the cuboctahedra via Cu-N bonds. Thus, each ligand is a 3-connected node, with two isophthalate moieties that each connect an edge of a cuboctahedron, and one pyridyl N atom which joins a corner of a cuboctahedron. Figure shows views of a) structure of H4L; b) the unit cell of MFM-170; c) the simplified structure showing the ‘smaller’ net of MFM-170; d) full structure resulting from connection of the two smaller nets; e) metal-ligand Cages A, B and C, observed in MFM-170.« less

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    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.