Skip to main content

Research Repository

Advanced Search

Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions

Humby, Jack D.; Benson, Oguarabau; Smith, Gemma L.; Argent, Stephen P.; da Silva, Ivan; Cheng, Yongqiang; Rudić, Svemir; Manuel, Pascal; Frogley, Mark D.; Cinque, Gianfelice; Saunders, Lucy K.; Vitórica-Yrezábal, Iñigo J.; Whitehead, George F. S.; Easun, Timothy L.; Lewis, William; Blake, Alexander J.; Ramirez-Cuesta, Anibal J.; Yang, Sihai; Schröder, Martin

Authors

Jack D. Humby

Oguarabau Benson

Gemma L. Smith

Stephen P. Argent

Ivan da Silva

Yongqiang Cheng

Svemir Rudić

Pascal Manuel

Mark D. Frogley

Gianfelice Cinque

Lucy K. Saunders

Iñigo J. Vitórica-Yrezábal

George F. S. Whitehead

Timothy L. Easun

William Lewis

Alexander J. Blake

Anibal J. Ramirez-Cuesta

Sihai Yang

Martin Schröder



Abstract

In order to develop new porous materials for applications in gas separations such as natural gas upgrading, landfill gas processing and acetylene purification it is vital to gain understanding of host-substrate interactions at a molecular level. Herein we report a series of six isoreticular metal-organic frameworks (MOFs) for selective gas adsorption. These materials do not incorporate open metal sites and thus provide an excellent platform to investigate the effect of the incorporation of ligand functionality via amide and alkyne groups on substrate binding. By reducing the linker length of our previously reported MFM-136, we report much improved CO2/CH4 (50:50) and CO2/N2 (15:85) selectivity values of 20.2 and 65.4, respectively (1 bar and 273 K), in the new amide-decorated MOF, MFM-126. The CO2 separation performance of MFM-126 has been confirmed by dynamic breakthrough experiments. In situ inelastic neutron scattering and synchrotron FT-IR microspectroscopy were employed to elucidate dynamic interactions of adsorbed CO2 molecules within MFM-126. Upon changing the functionality to an alkyne group in MFM-127, the CO2 uptake decreases but the C2H2 uptake increases by 68%, leading to excellent C2H2/CO2 and C2H2/CH4 selectivities of 3.7 and 21.2, respectively. Neutron powder diffraction enabled the direct observation of the preferred binding domains in MFM-126 and MFM-127, and, to the best of our knowledge, we report the first example of acetylene binding to an alkyne moiety in a porous material, with over 50% of the acetylene observed within MFM-127 displaying interactions (less than 4 Å) with the alkyne functionality of the framework.

Journal Article Type Article
Publication Date Oct 12, 2018
Journal Chemical Science
Print ISSN 2041-6520
Electronic ISSN 2041-6539
Publisher Royal Society of Chemistry
Peer Reviewed Peer Reviewed
APA6 Citation Humby, J. D., Benson, O., Smith, G. L., Argent, S. P., da Silva, I., Cheng, Y., …Schröder, M. (2018). Host–guest selectivity in a series of isoreticular metal–organic frameworks: observation of acetylene-to-alkyne and carbon dioxide-to-amide interactions. Chemical Science, https://doi.org/10.1039/c8sc03622e
DOI https://doi.org/10.1039/c8sc03622e
Keywords General Chemistry
Publisher URL https://pubs.rsc.org/en/Content/ArticleLanding/2019/SC/C8SC03622E#!divAbstract

Files



You might also like



Downloadable Citations

;