eprintid: 10022699 rev_number: 33 eprint_status: archive userid: 608 dir: disk0/10/02/26/99 datestamp: 2017-10-05 11:57:44 lastmod: 2021-10-15 23:10:08 status_changed: 2019-01-31 14:20:46 type: article metadata_visibility: show creators_name: Manos, G creators_name: Dunne, LJ title: Statistical Mechanics of Binary Mixture Adsorption in Metal-Organic Frameworks in the Osmotic Ensemble ispublished: pub divisions: UCL divisions: B04 divisions: C05 divisions: F43 keywords: Metal–organic framework, mixture adsorption isotherms, transfer matrix, osmotic ensemble, binary and co-adsorption, mechanical pressure note: This version is the author accepted manuscript. For information on re-use, please refer to the publisher’s terms and conditions. © 2018 The Author(s) Published by the Royal Society. All rights reserved abstract: Although crucial for designing separation processes little is known experimentally about multi-component adsorption isotherms in comparison with pure single components. Very few binary mixture adsorption isotherms are to be found in the literature and information about isotherms over a wide range of gas-phase composition and mechanical pressures and temperature is lacking. Here, we present a quasi-one-dimensional statistical mechanical model of binary mixture adsorption in metal–organic frameworks (MOFs) treated exactly by a transfer matrix method in the osmotic ensemble. The experimental parameter space may be very complex and investigations into multi-component mixture adsorption may be guided by theoretical insights. The approach successfully models breathing structural transitions induced by adsorption giving a good account of the shape of adsorption isotherms of CO2 and CH4 adsorption in MIL-53(Al). Binary mixture isotherms and co-adsorption-phase diagrams are also calculated and found to give a good description of the experimental trends in these properties and because of the wide model parameter range which reproduces this behaviour suggests that this is generic to MOFs. Finally, a study is made of the influence of mechanical pressure on the shape of CO2 and CH4 adsorption isotherms in MIL-53(Al). Quite modest mechanical pressures can induce significant changes to isotherm shapes in MOFs with implications for binary mixture separation processes. date: 2018-03 date_type: published publisher: Royal Society, The official_url: http://doi.org/10.1098/rsta.2017.0151 oa_status: green full_text_type: other language: eng primo: open primo_central: open_green article_type_text: Article verified: verified_manual elements_id: 1426084 doi: 10.1098/rsta.2017.0151 lyricists_name: Manos, George lyricists_id: GMANO86 actors_name: Manos, George actors_id: GMANO86 actors_role: owner full_text_status: public publication: Philosophical Transactions of the Royal Society A volume: 376 number: 2115 article_number: 20170151 issn: 1364-503X citation: Manos, G; Dunne, LJ; (2018) Statistical Mechanics of Binary Mixture Adsorption in Metal-Organic Frameworks in the Osmotic Ensemble. Philosophical Transactions of the Royal Society A , 376 (2115) , Article 20170151. 10.1098/rsta.2017.0151 <https://doi.org/10.1098/rsta.2017.0151>. Green open access document_url: https://discovery.ucl.ac.uk/id/eprint/10022699/1/RSTA_2017_0151_MOFMix_RevisedSept19finalforsympletic.pdf