Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S

Handle URI:
http://hdl.handle.net/10754/623867
Title:
Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S
Authors:
Belmabkhout, Youssef ( 0000-0001-9952-5007 ) ; Pillai, Renjith S.; Alezi, Dalal ( 0000-0002-3462-1193 ) ; Shekhah, Osama ( 0000-0003-1861-9226 ) ; Bhatt, Prashant; Chen, Zhijie; Adil, Karim ( 0000-0002-3804-1065 ) ; Vaesen, Sebastien ( 0000-0002-0823-9564 ) ; De Weireld, Guy; Pang, Maolin; Suetin, Mikhail ( 0000-0002-4570-8905 ) ; Cairns, Amy; Solovyeva, Vera ( 0000-0003-1671-6794 ) ; Shkurenko, Aleksander ( 0000-0001-7136-2277 ) ; El Tall, Omar; Maurin, Guillaume; Eddaoudi, Mohamed ( 0000-0003-1916-9837 )
Abstract:
A cooperative experimental/modeling strategy was used to unveil the structure/gas separation performance relationship for a series of isostructural metal-organic frameworks (MOFs) with soc-topology (square-octahedral) hosting different extra-framework counter ions (NO3-, Cl- and Br-). In3+-, Fe3+-, Ga3+-and the newly isolated Al(III)-based isostructural soc-MOF were extensively studied and evaluated for the separation-based production of high-quality fuels (i.e., CH4, C3H8 and n-C4H10) and olefins. The structural/chemical fine-tuning of the soc-MOF platform promoted equilibrium-based selectivity toward C2+ (C2H6, C2H4, C3H6 C3H8 and n-C4H10) and conferred the desired chemical stability toward H2S. The noted dual chemical stability and gas/vapor selectivity, which have rarely been reported for equilibrium-based separation agents, are essential for the production of high-purity H-2, CH4 and C2+ fractions in high yields. Interestingly, the evaluated soc-MOF analogues exhibited high selectivity for C2H4, C3H6 and n-C4H10. In particular, the Fe, Ga and Al analogues presented relatively enhanced C2+/CH4 adsorption selectivities. Notably, the Ga and Al analogues were found to be technically preferable because their structural integrities and separation performances were maintained upon exposure to H2S, indicating that these materials are highly tolerant to H2S. Therefore, the Ga-soc-MOF was further examined for the selective adsorption of H2S in the presence of CO2-and CH4-containing streams, such as refinery-off gases (ROG) and natural gas (NG). Grand canonical Monte Carlo (GCMC) simulations based on a specific force field describing the interactions between the guest molecules and the Ga sites supported and confirmed the considerably higher affinity of the Ga-soc-MOF for C2+ (as exemplified by n-C4H10) than for CH4. The careful selection of an appropriate metal for the trinuclear inorganic molecular building block (MBB), i. e., a Ga metal center, imbues the soc-MOF platform with the requisite hydrolytic stability, H2S stability, and exceptional gas selectivity for ROG and NG upgrading. Finally, the soc-MOF was deployed as a continuous film on a porous support, and its gas permeation properties as a membrane were evaluated.
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Analytical Core Lab
Citation:
Belmabkhout Y, Pillai RS, Alezi D, Shekhah O, Bhatt PM, et al. (2017) Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S. J Mater Chem A 5: 3293–3303. Available: http://dx.doi.org/10.1039/c6ta09406f.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
J. Mater. Chem. A
KAUST Grant Number:
FCC/1/1972-8-01; 146040
Issue Date:
6-Jan-2017
DOI:
10.1039/c6ta09406f
Type:
Article
ISSN:
2050-7488; 2050-7496
Sponsors:
The authors gratefully acknowledge Internal KAUST FUND FCC/1/1972-8-01. Y. B., P. M. B. and M. E. thank the Aramco-sponsored research fund (contract. 66600024505). R. S. P. and G. M. thank KAUST for providing funding (contract 146040). We would like to acknowledge Dr Hamad Feras from Aramco R&D for his help in performing the initial evaluation of the H<INF>2</INF>S/CO<INF>2</INF>/CH<INF>4</INF> mixtures.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2017/TA/C6TA09406F#!divAbstract
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Analytical Core Lab; Physical Sciences and Engineering (PSE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorBelmabkhout, Youssefen
dc.contributor.authorPillai, Renjith S.en
dc.contributor.authorAlezi, Dalalen
dc.contributor.authorShekhah, Osamaen
dc.contributor.authorBhatt, Prashanten
dc.contributor.authorChen, Zhijieen
dc.contributor.authorAdil, Karimen
dc.contributor.authorVaesen, Sebastienen
dc.contributor.authorDe Weireld, Guyen
dc.contributor.authorPang, Maolinen
dc.contributor.authorSuetin, Mikhailen
dc.contributor.authorCairns, Amyen
dc.contributor.authorSolovyeva, Veraen
dc.contributor.authorShkurenko, Aleksanderen
dc.contributor.authorEl Tall, Omaren
dc.contributor.authorMaurin, Guillaumeen
dc.contributor.authorEddaoudi, Mohameden
dc.date.accessioned2017-05-31T11:23:10Z-
dc.date.available2017-05-31T11:23:10Z-
dc.date.issued2017-01-06en
dc.identifier.citationBelmabkhout Y, Pillai RS, Alezi D, Shekhah O, Bhatt PM, et al. (2017) Metal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2S. J Mater Chem A 5: 3293–3303. Available: http://dx.doi.org/10.1039/c6ta09406f.en
dc.identifier.issn2050-7488en
dc.identifier.issn2050-7496en
dc.identifier.doi10.1039/c6ta09406fen
dc.identifier.urihttp://hdl.handle.net/10754/623867-
dc.description.abstractA cooperative experimental/modeling strategy was used to unveil the structure/gas separation performance relationship for a series of isostructural metal-organic frameworks (MOFs) with soc-topology (square-octahedral) hosting different extra-framework counter ions (NO3-, Cl- and Br-). In3+-, Fe3+-, Ga3+-and the newly isolated Al(III)-based isostructural soc-MOF were extensively studied and evaluated for the separation-based production of high-quality fuels (i.e., CH4, C3H8 and n-C4H10) and olefins. The structural/chemical fine-tuning of the soc-MOF platform promoted equilibrium-based selectivity toward C2+ (C2H6, C2H4, C3H6 C3H8 and n-C4H10) and conferred the desired chemical stability toward H2S. The noted dual chemical stability and gas/vapor selectivity, which have rarely been reported for equilibrium-based separation agents, are essential for the production of high-purity H-2, CH4 and C2+ fractions in high yields. Interestingly, the evaluated soc-MOF analogues exhibited high selectivity for C2H4, C3H6 and n-C4H10. In particular, the Fe, Ga and Al analogues presented relatively enhanced C2+/CH4 adsorption selectivities. Notably, the Ga and Al analogues were found to be technically preferable because their structural integrities and separation performances were maintained upon exposure to H2S, indicating that these materials are highly tolerant to H2S. Therefore, the Ga-soc-MOF was further examined for the selective adsorption of H2S in the presence of CO2-and CH4-containing streams, such as refinery-off gases (ROG) and natural gas (NG). Grand canonical Monte Carlo (GCMC) simulations based on a specific force field describing the interactions between the guest molecules and the Ga sites supported and confirmed the considerably higher affinity of the Ga-soc-MOF for C2+ (as exemplified by n-C4H10) than for CH4. The careful selection of an appropriate metal for the trinuclear inorganic molecular building block (MBB), i. e., a Ga metal center, imbues the soc-MOF platform with the requisite hydrolytic stability, H2S stability, and exceptional gas selectivity for ROG and NG upgrading. Finally, the soc-MOF was deployed as a continuous film on a porous support, and its gas permeation properties as a membrane were evaluated.en
dc.description.sponsorshipThe authors gratefully acknowledge Internal KAUST FUND FCC/1/1972-8-01. Y. B., P. M. B. and M. E. thank the Aramco-sponsored research fund (contract. 66600024505). R. S. P. and G. M. thank KAUST for providing funding (contract 146040). We would like to acknowledge Dr Hamad Feras from Aramco R&D for his help in performing the initial evaluation of the H<INF>2</INF>S/CO<INF>2</INF>/CH<INF>4</INF> mixtures.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2017/TA/C6TA09406F#!divAbstracten
dc.titleMetal–organic frameworks to satisfy gas upgrading demands: fine-tuning the soc-MOF platform for the operative removal of H2Sen
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentAnalytical Core Laben
dc.identifier.journalJ. Mater. Chem. Aen
dc.contributor.institutionInstitut Charles Gerhardt Montpellier UMR 5253 CNRS, Université Montpellier, Place E. Bataillon, Montpellier cedex 05, 34095, Franceen
dc.contributor.institutionThermodynamics Department, Faculty of Engineering, University of Mons, 20, Place du Parc, Mons, 7000, Belgiumen
kaust.authorBelmabkhout, Youssefen
kaust.authorAlezi, Dalalen
kaust.authorShekhah, Osamaen
kaust.authorBhatt, Prashanten
kaust.authorChen, Zhijieen
kaust.authorAdil, Karimen
kaust.authorPang, Maolinen
kaust.authorSuetin, Mikhailen
kaust.authorCairns, Amyen
kaust.authorSolovyeva, Veraen
kaust.authorShkurenko, Aleksanderen
kaust.authorEl Tall, Omaren
kaust.authorEddaoudi, Mohameden
kaust.grant.numberFCC/1/1972-8-01en
kaust.grant.number146040en
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