TY - JOUR
T1 - CO 2 adsorption in mono-, di- and trivalent cation-exchanged metal-organic frameworks: A molecular simulation study
AU - Chen, Yifei
AU - Nalaparaju, Anjaiah
AU - Eddaoudi, Mohamed
AU - JIANG, Jianwen
N1 - KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: This work is supported by the National Research Foundation of Singapore (R-279-000-261-281) and the National University of Singapore (R-279-000-297-112).
PY - 2012/2/14
Y1 - 2012/2/14
N2 - A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry's constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.
AB - A molecular simulation study is reported for CO 2 adsorption in rho zeolite-like metal-organic framework (rho-ZMOF) exchanged with a series of cations (Na +, K +, Rb +, Cs +, Mg 2+, Ca 2+, and Al 3+). The isosteric heat and Henry's constant at infinite dilution increase monotonically with increasing charge-to-diameter ratio of cation (Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ < Al 3+). At low pressures, cations act as preferential adsorption sites for CO 2 and the capacity follows the charge-to-diameter ratio. However, the free volume of framework becomes predominant with increasing pressure and Mg-rho-ZMOF appears to possess the highest saturation capacity. The equilibrium locations of cations are observed to shift slightly upon CO 2 adsorption. Furthermore, the adsorption selectivity of CO 2/H 2 mixture increases as Cs + < Rb + < K + < Na + < Ca 2+ < Mg 2+ ≈ Al 3+. At ambient conditions, the selectivity is in the range of 800-3000 and significantly higher than in other nanoporous materials. In the presence of 0.1% H 2O, the selectivity decreases drastically because of the competitive adsorption between H 2O and CO 2, and shows a similar value in all of the cation-exchanged rho-ZMOFs. This simulation study provides microscopic insight into the important role of cations in governing gas adsorption and separation, and suggests that the performance of ionic rho-ZMOF can be tailored by cations. © 2012 American Chemical Society.
UR - http://hdl.handle.net/10754/562100
UR - https://pubs.acs.org/doi/10.1021/la205152f
UR - http://www.scopus.com/inward/record.url?scp=84863298859&partnerID=8YFLogxK
U2 - 10.1021/la205152f
DO - 10.1021/la205152f
M3 - Article
SN - 0743-7463
VL - 28
SP - 3903
EP - 3910
JO - Langmuir
JF - Langmuir
IS - 8
ER -