Theoretical investigations of CO₂ and CH₄ sorption in an interpenetrated diamondoid metal-organic material.

Handle URI:
http://hdl.handle.net/10754/596848
Title:
Theoretical investigations of CO₂ and CH₄ sorption in an interpenetrated diamondoid metal-organic material.
Authors:
Pham, Tony; Forrest, Katherine A; Tudor, Brant; Elsaidi, Sameh K; Mohamed, Mona H; McLaughlin, Keith; Cioce, Christian R; Zaworotko, Michael J; Space, Brian
Abstract:
Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal-organic material (MOM) consisting of a 7-fold interpenetrated net of Co(2+) ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels-this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM's high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity.
Citation:
Pham T, Forrest KA, Tudor B, Elsaidi SK, Mohamed MH, et al. (2014) Theoretical Investigations of CO 2 and CH 4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material . Langmuir 30: 6454–6462. Available: http://dx.doi.org/10.1021/la500967w.
Publisher:
American Chemical Society (ACS)
Journal:
Langmuir
KAUST Grant Number:
FIC/2010/06
Issue Date:
29-May-2014
DOI:
10.1021/la500967w
PubMed ID:
24835550
PubMed Central ID:
PMC4055056
Type:
Article
ISSN:
0743-7463; 1520-5827
Sponsors:
This work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors acknowledge the use of the services provided by Research Computing at the University of South Florida. M.H.M. acknowledges support from the Schlumberger Foundation and its Faculty for the Future Fellowship program. Lastly, the authors thank Professor David S. Sholl for his assistance on the ideal adsorbed solution theory (LAST) calculations.
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Full metadata record

DC FieldValue Language
dc.contributor.authorPham, Tonyen
dc.contributor.authorForrest, Katherine Aen
dc.contributor.authorTudor, Branten
dc.contributor.authorElsaidi, Sameh Ken
dc.contributor.authorMohamed, Mona Hen
dc.contributor.authorMcLaughlin, Keithen
dc.contributor.authorCioce, Christian Ren
dc.contributor.authorZaworotko, Michael Jen
dc.contributor.authorSpace, Brianen
dc.date.accessioned2016-02-21T09:35:20Zen
dc.date.available2016-02-21T09:35:20Zen
dc.date.issued2014-05-29en
dc.identifier.citationPham T, Forrest KA, Tudor B, Elsaidi SK, Mohamed MH, et al. (2014) Theoretical Investigations of CO 2 and CH 4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material . Langmuir 30: 6454–6462. Available: http://dx.doi.org/10.1021/la500967w.en
dc.identifier.issn0743-7463en
dc.identifier.issn1520-5827en
dc.identifier.pmid24835550en
dc.identifier.doi10.1021/la500967wen
dc.identifier.urihttp://hdl.handle.net/10754/596848en
dc.description.abstractGrand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal-organic material (MOM) consisting of a 7-fold interpenetrated net of Co(2+) ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels-this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM's high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity.en
dc.description.sponsorshipThis work was supported by the National Science Foundation (Award No. CHE-1152362). Computations were performed under a XSEDE Grant (No. TG-DMR090028) to B.S. This publication is also based on work supported by Award No. FIC/2010/06, made by King Abdullah University of Science and Technology (KAUST). The authors also thank the Space Foundation (Basic and Applied Research) for partial support. The authors acknowledge the use of the services provided by Research Computing at the University of South Florida. M.H.M. acknowledges support from the Schlumberger Foundation and its Faculty for the Future Fellowship program. Lastly, the authors thank Professor David S. Sholl for his assistance on the ideal adsorbed solution theory (LAST) calculations.en
dc.publisherAmerican Chemical Society (ACS)en
dc.rightsThis is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.en
dc.rights.urihttp://pubs.acs.org/page/policy/authorchoice_termsofuse.htmlen
dc.titleTheoretical investigations of CO₂ and CH₄ sorption in an interpenetrated diamondoid metal-organic material.en
dc.typeArticleen
dc.identifier.journalLangmuiren
dc.identifier.pmcidPMC4055056en
dc.contributor.institutionDepartment of Chemistry, University of South Florida , 4202 East Fowler Avenue CHE205, Tampa, Florida 33620-5250, United States.en
kaust.grant.numberFIC/2010/06en

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