Post-Synthetic Modulation of the Charge Distribution in a Metal–Organic Framework for Optimal Binding of Carbon Dioxide and Sulfur Sioxide | Sciact - CRIS-система Института катализа

Post-Synthetic Modulation of the Charge Distribution in a Metal–Organic Framework for Optimal Binding of Carbon Dioxide and Sulfur Sioxide Научная публикация

Журнал

Chemical Science
ISSN: 2041-6520 , E-ISSN: 2041-6539

Вых. Данные

Год: 2019, Том: 10, Номер: 5, Страницы: 1472-1482 Страниц : 11 DOI: 10.1039/C8SC01959B

Ключевые слова

COORDINATION POLYMER; IONIC LIQUIDS; CO2 BINDING; FLUE-GAS; ADSORPTION; DESULFURIZATION; SELECTIVITY; ABSORPTION; CHEMISTRY; SERIES

Авторы

Li Lei ^1,2 , da Silva Ivan ³ , Kolokolov Daniil I. ^4,5 , Han Xue ¹ , Li Jiangnan ¹ , Smith Gemma ¹ , Cheng Yongqiang ⁶ , Daemen Luke L. ⁶ , Morris Christopher G. ^1,7 , Godfrey Harry G.W. ¹ , Jacques Nicholas M. ¹ , Zhang Xinran ¹ , Manuel Pascal ³ , Frogley Mark D. ⁷ , Murray Claire A. ⁷ , Ramirez-Cuesta Anibal J. ⁶ , Cinque Gianfelice ⁷ , Tang Chiu C. ⁷ , Stepanov Alexander G. ^4,5 , Yang Sihai ¹ , Schroder Martin ¹

Организации

1	School of Chemistry, University of Manchester, Oxford Road, Manchester, UK
2	Lehn Institute of Functional Materials, School of Chemistry, Sun Yat-Sen University, Guangzhou, China
3	ISIS Neutron Facility, STFC Rutherford Appleton Laboratory, Chilton, UK
4	Boreskov Institute of Catalysis, Siberian Branch of Russian Academy of Sciences
5	Novosibirsk State University, Novosibirsk 630090, Russia
6	The Chemical and Engineering Materials Division (CEMD), Neutron Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, USA
7	Diamond Light Source, Harwell Science Campus, UK

Информация о финансировании (6)

1	Engineering and Physical Sciences Research Council	EP/I011870
2	European Research Council	AdG 742041
3	Royal Society
4	Федеральное агентство научных организаций России	0303-2016-0003
5	University of Manchester
6	Oak Ridge National Laboratory

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.

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. , Yang S. , Schroder M.
Post-Synthetic Modulation of the Charge Distribution in a Metal–Organic Framework for Optimal Binding of Carbon Dioxide and Sulfur Sioxide

Chemical Science. 2019. V.10. N5. P.1472-1482. DOI: 10.1039/C8SC01959B WOS Scopus РИНЦ CAPlus PMID OpenAlex

Полный текст от издателя

Поступила в редакцию:	30 апр. 2018 г.
Принята к публикации:	30 окт. 2018 г.
Опубликована online:	31 окт. 2018 г.
Опубликована в печати:	7 февр. 2019 г.

Web of science:	WOS:000457448700022
Scopus:	2-s2.0-85060862795
РИНЦ:	38656532
Chemical Abstracts:	2018:2057201
PMID (PubMed):	30842819
OpenAlex:	W2898686944

БД	Цитирований
Scopus	64
Web of science	63
РИНЦ	61
OpenAlex	67