Abstract
A multiscale theoretical investigation has been performed to study the hydrogen and acetylene storage in Ca2+- and Mg2+-doped COFs (COF-105 and COF-108). The first-principles calculations show that the Ca2+ and Mg2+ can be immobilized at the COFs surfaces, and the doped Ca and Mg cations can adsorb five H2 molecules and three C2H2 molecules with ideal binding energies. The Grand Canonical Monte Carlo (GCMC) simulations were carried out to obtain the hydrogen and acetylene uptakes of Ca2+- and Mg2+-doped COFs at room temperature in the different pressure ranges. Our results demonstrate that, at T = 298 K and p = 100 bar, the total gravimetric uptakes of H2 in Ca2+-doped COF-105 and COF-108 reach 6.78 and 6.54 wt%, respectively, and a higher uptakes of 7.14 and 7.27 wt% have been reached for Mg2+-doped COF-105 and COF-108, respectively. At T = 298 K and p = 1 bar, the acetylene uptakes of Ca2+-doped COF-105, Ca2+-doped COF-108, Mg2+-doped COF-105, and Mg2+-doped COF-108 are 406.42, 366.24, 308.07, and 319.88 cm3/g (corresponding to the excess uptakes of 358.37, 316.38, 236.7109, and 245.42 cm3/g), respectively. The Ca2+-doped COF-105 displays a highest acetylene storage capacity among all materials reported. The Ca2+- and Mg2+-doped COFs can be very practical hydrogen or acetylene storage medium in the future.
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Acknowledgments
H. Zhang acknowledges financial support from the National Natural Science Foundation of China (NSFC. Grant No. 11074176 and NSAF. Grant No. 10976019) and the support from Research Fund for the Doctoral Program of Higher Education of China (Grant No. 20100181110080).
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Guo, JH., Zhang, H., Gong, M. et al. Ca2+- and Mg2+-doped covalent organic frameworks exhibiting high hydrogen and acetylene storage. Struct Chem 24, 691–703 (2013). https://doi.org/10.1007/s11224-012-0120-1
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DOI: https://doi.org/10.1007/s11224-012-0120-1