Mendoza-Cortés, José L. and Han, Sang Soo and Goddard, William A., III (2012) High H_2 Uptake in Li-, Na-, K-Metalated Covalent Organic Frameworks and Metal Organic Frameworks at 298 K. Journal of Physical Chemistry A, 116 (6). pp. 1621-1631. ISSN 1089-5639 http://resolver.caltech.edu/CaltechAUTHORS:20120314-131731977
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The Yaghi laboratory has developed porous covalent organic frameworks (COFs), COF102, COF103, and COF202, and metal–organic frameworks (MOFs), MOF177, MOF180, MOF200, MOF205, and MOF210, with ultrahigh porosity and outstanding H2 storage properties at 77 K. Using grand canonical Monte Carlo (GCMC) simulations with our recently developed first principles based force field (FF) from accurate quantum mechanics (QM), we calculated the molecular hydrogen (H2) uptake at 298 K for these systems, including the uptake for Li-, Na-, and K-metalated systems. We report the total, delivery and excess amount in gravimetric and volumetric units for all these compounds. For the gravimetric delivery amount from 1 to 100 bar, we find that eleven of these compounds reach the 2010 DOE target of 4.5 wt % at 298 K. The best of these compounds are MOF200-Li (6.34) and MOF200-Na (5.94), both reaching the 2015 DOE target of 5.5 wt % at 298 K. Among the undoped systems, we find that MOF200 gives a delivery amount as high as 3.24 wt % while MOF210 gives 2.90 wt % both from 1 to 100 bar and 298 K. However, none of these compounds reach the volumetric 2010 DOE target of 28 g H_2/L. The best volumetric performance is for COF102-Na (24.9), COF102-Li (23.8), COF103-Na (22.8), and COF103-Li (21.7), all using delivery g H_2/L units for 1–100 bar. These are the highest volumetric molecular hydrogen uptakes for a porous material under these thermodynamic conditions. Thus, one can obtain outstanding H_2 uptakes with Li, Na, and K doping of simple frameworks constructed from simple, cheap organic linkers. We present suggestions for strategies for synthesis of alkali metal-doped MOFs or COFs.
|Additional Information:||© 2012 American Chemical Society. Received: July 21, 2011. Revised: December 16, 2011. Published: December 21, 2011. J.L.M.-C. would like to acknowledge the Roberto Rocca Fellowship for support and Robert Nielsen for helpful discussions. S.S.H. acknowledges that this research was partially performed for the Hydrogen Enegy R&D Center, one of the 21st Century Frontier R&D programs, funded by the Ministry of Education, Science and Technology of Korea. We thank Professor Omar Yaghi (UCLA) and Dr. Hiroyasu Furukawa (UCLA) for helpful discussions. W.A.G. and J.L.M.-C. acknowledge the DOE (DE-F6-36-08G018141, Program Manager Rich Bechtold) for supporting this research.|
|Official Citation:||High H2 Uptake in Li-, Na-, K-Metalated Covalent Organic Frameworks and Metal Organic Frameworks at 298 K José L. Mendoza-Cortés, Sang Soo Han, and William A. Goddard, III The Journal of Physical Chemistry A2012116 (6), 1621-1631|
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|Deposited By:||Tony Diaz|
|Deposited On:||20 Mar 2012 22:07|
|Last Modified:||26 Dec 2012 14:57|
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