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Title: Reversible Hydrogen Uptake/Release over a Sodium Phenoxide-Cyclohexanolate Pair

Abstract

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 α 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.

Authors:
 [1];  [1];  [2];  [1];  [3];  [3]; ORCiD logo [4]
  1. Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics
  2. Xiamen Univ., Xiamen (China). Fujian Provincial Key Lab. of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  4. Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics, State Key Lab.of Catalysis; Xiamen Univ., Fujian (China). Collaborative Innovation Centre of Chemistry for Energy Materials
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1490385
Report Number(s):
PNNL-SA-132154
Journal ID: ISSN 1433-7851
Grant/Contract Number:  
AC0576RL01830; 21875246, 51671178, 51472237; 21773193; 2016YFE0118300; 20720160031
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Angewandte Chemie (International Edition)
Additional Journal Information:
Journal Volume: 58; Journal Issue: 10; Journal ID: ISSN 1433-7851
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; hydrogen storage materials; metalation; organic hydrides; thermodynamic modification

Citation Formats

Yu, Yang, He, Teng, Wu, Anan, Pei, Qijun, Karkamkar, Abhijeet, Autrey, Tom, and Chen, Ping. Reversible Hydrogen Uptake/Release over a Sodium Phenoxide-Cyclohexanolate Pair. United States: N. p., 2018. Web. doi:10.1002/anie.201810945.
Yu, Yang, He, Teng, Wu, Anan, Pei, Qijun, Karkamkar, Abhijeet, Autrey, Tom, & Chen, Ping. Reversible Hydrogen Uptake/Release over a Sodium Phenoxide-Cyclohexanolate Pair. United States. doi:10.1002/anie.201810945.
Yu, Yang, He, Teng, Wu, Anan, Pei, Qijun, Karkamkar, Abhijeet, Autrey, Tom, and Chen, Ping. Sun . "Reversible Hydrogen Uptake/Release over a Sodium Phenoxide-Cyclohexanolate Pair". United States. doi:10.1002/anie.201810945.
@article{osti_1490385,
title = {Reversible Hydrogen Uptake/Release over a Sodium Phenoxide-Cyclohexanolate Pair},
author = {Yu, Yang and He, Teng and Wu, Anan and Pei, Qijun and Karkamkar, Abhijeet and Autrey, Tom and Chen, Ping},
abstractNote = {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 α 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.},
doi = {10.1002/anie.201810945},
journal = {Angewandte Chemie (International Edition)},
issn = {1433-7851},
number = 10,
volume = 58,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
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Works referenced in this record:

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