Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 10, Pages 3102-3107Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201810945
Keywords
hydrogen storage materials; metalation; organic hydrides; thermodynamic modification
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Funding
- National Natural Science Foundation of China [21875246, 51671178, 51472237]
- DICP [DICP ZZBS201616]
- Sino-Japanese Research Cooperative Program of the Ministry of Science and Technology [2016YFE0118300]
- National Science Foundation of China (NSFC) [21773193]
- Fundamental Research Funds for the Central Universities [20720160031]
- Hydrogen Materials-Advanced Research Consortium (HyMARC), as part of the Energy Materials Network under the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office
- U.S. Department of Energy [DE-AC05-76RL01830]
- iChEM2011
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Hydrogen uptake and release in arene-cycloalkane pairs provide an attractive opportunity for on-board and off-board hydrogen storage. However, the efficiency of arene-cycloalkane pairs currently is limited by unfavorable thermodynamics for hydrogen release. It is shown here that the thermodynamics can be optimized by replacement of H in the -OH group of cyclohexanol and phenol with alkali or alkaline earth metals. The enthalpy change upon dehydrogenation decreases substantially, which correlates with the delocalization of the oxygen electron to the benzene ring in phenoxides. Theoretical calculations reveal that replacement of H with a metal leads to a reduction of the HOMO-LUMO energy gap and elongation of the C-H bond in the alpha site in cyclohexanolate, which indicates that the cyclohexanol is activated upon metal substitution. The experimental results demonstrate that sodium phenoxide-cyclohexanolate, an air- and water-stable pair, can desorb hydrogen at ca. 413 K and 373 K in the solid form and in an aqueous solution, respectively. Hydrogenation, on the other hand, is accomplished at temperatures as low as 303 K.
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