Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Post-synthetic modulation of the charge distribution in a metal-organic framework for optimal binding of carbon dioxide and sulfur dioxide. / Li, Lei; Da Silva, Ivan; Kolokolov, Daniil I. и др.
в: Chemical Science, Том 10, № 5, 07.02.2019, стр. 1472-1482.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
}
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
N1 - Publisher Copyright: © The Royal Society of Chemistry.
PY - 2019/2/7
Y1 - 2019/2/7
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.
KW - COORDINATION POLYMER
KW - IONIC LIQUIDS
KW - CO2 BINDING
KW - FLUE-GAS
KW - ADSORPTION
KW - DESULFURIZATION
KW - SELECTIVITY
KW - ABSORPTION
KW - CHEMISTRY
KW - SERIES
UR - http://www.scopus.com/inward/record.url?scp=85060862795&partnerID=8YFLogxK
U2 - 10.1039/c8sc01959b
DO - 10.1039/c8sc01959b
M3 - Article
C2 - 30842819
AN - SCOPUS:85060862795
VL - 10
SP - 1472
EP - 1482
JO - Chemical Science
JF - Chemical Science
SN - 2041-6520
IS - 5
ER -
ID: 18487529