Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide

Lei Li; Ivan Da Silva; Daniil I. Kolokolov; Xue Han; Jiangnan Li; Gemma Smith; Yongqiang Cheng; Luke L. Daemen; Christopher G. Morris; Harry G.W. Godfrey; Nicholas M. Jacques; Xinran Zhang; Pascal Manuel; Mark D. Frogley; Claire A. Murray; Anibal J. Ramirez-Cuesta; Gianfelice Cinque; Chiu C. Tang; Alexander G. Stepanov; Sihai Yang; Martin Schroder

doi:10.1039/c8sc01959b

Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide

Lei Li, Ivan Da Silva, Daniil I. Kolokolov, Xue Han, Jiangnan Li, Gemma Smith, Yongqiang Cheng, Luke L. Daemen, Christopher G. Morris, Harry G.W. Godfrey, Nicholas M. Jacques, Xinran Zhang, Pascal Manuel, Mark D. Frogley, Claire A. Murray, Anibal J. Ramirez-Cuesta, Gianfelice Cinque, Chiu C. Tang, Alexander G. Stepanov, Sihai YangMartin Schroder

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Abstract

Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH₃, [Al(OH)(L)]Cl, [(H₂L)Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH₃ shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO₂ and SO₂ in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and ²H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO₂ and SO₂ in these materials. CO₂ and SO₂ binding in MFM-305-CH₃ is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO₂. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO₂ and SO₂ more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.

Original language	English
Pages (from-to)	1472-1482
Number of pages	11
Journal	Chemical Science
Volume	10
Issue number	5
DOIs	https://doi.org/10.1039/c8sc01959b
State	Published - 2019

Funding

We thank EPSRC (EP/I011870 to MS), ERC (AdG 742041 to MS) and University of Manchester for funding. We are especially grateful to STFC and the ISIS Neutron Facility for access to the Beamlines TOSCA and WISH, to Diamond Light Source for access to Beamlines I11 and B22 and to ORNL for access to Beamline VISION. LL thanks for the International Postdoctoral Exchange Fellowship Program from China and the Sino-British Fellowship (Royal Society) for support. The computing resources were made available through the VirtuES and ICEMAN projects, funded by Laboratory Directed Research and Development program at ORNL. DIK and AGS acknowledge financial support within the framework of the budget project #AAAA-A17-117041710084-2 of the Boreskov Institute of Catalysis. We thank EPSRC (EP/I011870 to MS), ERC (AdG 742041 to MS) and University of Manchester for funding. We are especially grateful to STFC and the ISIS Neutron Facility for access to the Beamlines TOSCA and WISH, to Diamond Light Source for access to Beamlines I11 and B22 and to ORNL for access to Beamline VISION. LL thanks for the International Postdoctoral Exchange Fellowship Program from China and the Sino-British Fellowship (Royal Society) for support. The computing resources were made available through the VirtuES and ICEMAN projects, funded by Laboratory Directed Research and Development program at ORNL. DIK and AGS acknowledge nancial support within the framework of the budget project #AAAA-A17-117041710084-2 of the Boreskov Institute of Catalysis.

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10.1039/c8sc01959b

Cite this

Li, L., Da Silva, I., Kolokolov, D. I., Han, X., Li, J., Smith, G., Cheng, Y., Daemen, L. L., Morris, C. G., Godfrey, H. G. W., Jacques, N. M., Zhang, X., Manuel, P., Frogley, M. D., Murray, C. A., Ramirez-Cuesta, A. J., Cinque, G., Tang, C. C., Stepanov, A. G., ... Schroder, M. (2019). Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide. Chemical Science, 10(5), 1472-1482. https://doi.org/10.1039/c8sc01959b

@article{4df51c4371924c0ca2c36f235b0c57f9,

title = "Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide",

abstract = "Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L)Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and 2H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.",

author = "Lei Li and {Da Silva}, Ivan and Kolokolov, {Daniil I.} and Xue Han and Jiangnan Li and Gemma Smith and Yongqiang Cheng and Daemen, {Luke L.} and Morris, {Christopher G.} and Godfrey, {Harry G.W.} and Jacques, {Nicholas M.} and Xinran Zhang and Pascal Manuel and Frogley, {Mark D.} and Murray, {Claire A.} and Ramirez-Cuesta, {Anibal J.} and Gianfelice Cinque and Tang, {Chiu C.} and Stepanov, {Alexander G.} and Sihai Yang and Martin Schroder",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry.",

year = "2019",

doi = "10.1039/c8sc01959b",

language = "English",

volume = "10",

pages = "1472--1482",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "5",

}

Li, L, Da Silva, I, Kolokolov, DI, Han, X, Li, J, Smith, G, Cheng, Y, Daemen, LL, Morris, CG, Godfrey, HGW, Jacques, NM, Zhang, X, Manuel, P, Frogley, MD, Murray, CA, Ramirez-Cuesta, AJ, Cinque, G, Tang, CC, Stepanov, AG, Yang, S & Schroder, M 2019, 'Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide', Chemical Science, vol. 10, no. 5, pp. 1472-1482. https://doi.org/10.1039/c8sc01959b

TY - JOUR

T1 - Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide

AU - Li, Lei

AU - Da Silva, Ivan

AU - Kolokolov, Daniil I.

AU - Han, Xue

AU - Li, Jiangnan

AU - Smith, Gemma

AU - Cheng, Yongqiang

AU - Daemen, Luke L.

AU - Morris, Christopher G.

AU - Godfrey, Harry G.W.

AU - Jacques, Nicholas M.

AU - Zhang, Xinran

AU - Manuel, Pascal

AU - Frogley, Mark D.

AU - Murray, Claire A.

AU - Ramirez-Cuesta, Anibal J.

AU - Cinque, Gianfelice

AU - Tang, Chiu C.

AU - Stepanov, Alexander G.

AU - Yang, Sihai

AU - Schroder, Martin

PY - 2019

Y1 - 2019

N2 - Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L)Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and 2H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.

AB - Modulation of pore environment is an effective strategy to optimize guest binding in porous materials. We report the post-synthetic modification of the charge distribution in a charged metal-organic framework, MFM-305-CH3, [Al(OH)(L)]Cl, [(H2L)Cl = 3,5-dicarboxy-1-methylpyridinium chloride] and its effect on guest binding. MFM-305-CH3 shows a distribution of cationic (methylpyridinium) and anionic (chloride) centers and can be modified to release free pyridyl N-centres by thermal demethylation of the 1-methylpyridinium moiety to give the neutral isostructural MFM-305. This leads simultaneously to enhanced adsorption capacities and selectivities (two parameters that often change in opposite directions) for CO2 and SO2 in MFM-305. The host-guest binding has been comprehensively investigated by in situ synchrotron X-ray and neutron powder diffraction, inelastic neutron scattering, synchrotron infrared and 2H NMR spectroscopy and theoretical modelling to reveal the binding domains of CO2 and SO2 in these materials. CO2 and SO2 binding in MFM-305-CH3 is shown to occur via hydrogen bonding to the methyl and aromatic-CH groups, with a long range interaction to chloride for CO2. In MFM-305 the hydroxyl, pyridyl and aromatic C-H groups bind CO2 and SO2 more effectively via hydrogen bonds and dipole interactions. Post-synthetic modification via dealkylation of the as-synthesised metal-organic framework is a powerful route to the synthesis of materials incorporating active polar groups that cannot be prepared directly.

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U2 - 10.1039/c8sc01959b

DO - 10.1039/c8sc01959b

M3 - Article

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SN - 2041-6520

VL - 10

SP - 1472

EP - 1482

JO - Chemical Science

JF - Chemical Science

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ER -

Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide

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