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Title: Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks

Abstract

The study of the mobility/rotation of the organic linkers in porous metal-organic frameworks could provide a valuable information about the guest/framework interaction and the factors control the kinetics of adsorption. Here, we analyzed the dynamics of pyrazine ring rotation in a series of pillared square grid frameworks, namely SIFSIX-3-M (M = Fe, Ni). It was found that the rotation of pyrazine ring is influenced by the variation of metal cation, temperature and the guest molecule. The Fe-analogue, [Fe(pz)2(SiF6)2] (pz= Pyrazine), , showed no pronounced ring rotation and exhibited a high affinity toward Xe gas over Kr as exemplified by the sharp Xe uptake at low loading (~0.1 bar) and its high isosteric heat of adsorption (Qst~ 27.4 kJmol-1) compared to the current benchmark materials. The Ni analogue, on the contrary, showed a two-regime adsorption isotherm for Xe with a temperature-dependent inflection point. However, this behavior is not observed with the other gases such as CO2, N2, and Kr which showed one-step adsorption isotherms without any inflection. Using molecular models and simulations, we hypothesize that the inflection point is due to a disordered to ordered transition of the rotational configurations of the pz rings in SIFSIX-3-Ni. These results further support themore » impact of tuning the pore size and chemistry on the adsorption behavior of porous materials.« less

Authors:
; ; ; ORCiD logo; ; ; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1373592
DOE Contract Number:  
AC02-06CH11357
Resource Type:
Journal Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Elsaidi, Sameh K., Mohamed, Mona H., Simon, Cory M., Braun, Efrem, Pham, Tony, Forrest, Katherine A., Xu, Wenqian, Banerjee, Debasis, Space, Brian, Zaworotko, Michael J., and Thallapally, Praveen K. Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks. United States: N. p., 2017. Web. doi:10.1039/c6sc05012c.
Elsaidi, Sameh K., Mohamed, Mona H., Simon, Cory M., Braun, Efrem, Pham, Tony, Forrest, Katherine A., Xu, Wenqian, Banerjee, Debasis, Space, Brian, Zaworotko, Michael J., & Thallapally, Praveen K. Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks. United States. doi:10.1039/c6sc05012c.
Elsaidi, Sameh K., Mohamed, Mona H., Simon, Cory M., Braun, Efrem, Pham, Tony, Forrest, Katherine A., Xu, Wenqian, Banerjee, Debasis, Space, Brian, Zaworotko, Michael J., and Thallapally, Praveen K. Sun . "Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks". United States. doi:10.1039/c6sc05012c.
@article{osti_1373592,
title = {Effect of ring rotation upon gas adsorption in SIFSIX-3-M (M = Fe, Ni) pillared square grid networks},
author = {Elsaidi, Sameh K. and Mohamed, Mona H. and Simon, Cory M. and Braun, Efrem and Pham, Tony and Forrest, Katherine A. and Xu, Wenqian and Banerjee, Debasis and Space, Brian and Zaworotko, Michael J. and Thallapally, Praveen K.},
abstractNote = {The study of the mobility/rotation of the organic linkers in porous metal-organic frameworks could provide a valuable information about the guest/framework interaction and the factors control the kinetics of adsorption. Here, we analyzed the dynamics of pyrazine ring rotation in a series of pillared square grid frameworks, namely SIFSIX-3-M (M = Fe, Ni). It was found that the rotation of pyrazine ring is influenced by the variation of metal cation, temperature and the guest molecule. The Fe-analogue, [Fe(pz)2(SiF6)2] (pz= Pyrazine), , showed no pronounced ring rotation and exhibited a high affinity toward Xe gas over Kr as exemplified by the sharp Xe uptake at low loading (~0.1 bar) and its high isosteric heat of adsorption (Qst~ 27.4 kJmol-1) compared to the current benchmark materials. The Ni analogue, on the contrary, showed a two-regime adsorption isotherm for Xe with a temperature-dependent inflection point. However, this behavior is not observed with the other gases such as CO2, N2, and Kr which showed one-step adsorption isotherms without any inflection. Using molecular models and simulations, we hypothesize that the inflection point is due to a disordered to ordered transition of the rotational configurations of the pz rings in SIFSIX-3-Ni. These results further support the impact of tuning the pore size and chemistry on the adsorption behavior of porous materials.},
doi = {10.1039/c6sc05012c},
journal = {Chemical Science},
issn = {2041-6520},
number = 3,
volume = 8,
place = {United States},
year = {2017},
month = {1}
}

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