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

doi:10.1002/anie.201810945

This content will become publicly available on November 25, 2019

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:

Yu, Yang ^[1]; He, Teng ^[1]; Wu, Anan ^[2]; Pei, Qijun ^[1]; Karkamkar, Abhijeet ^[3]; Autrey, Tom ^[3];

^[4]

Chinese Academy of Sciences (CAS), Dalian (China). Dalian Inst. of Chemical Physics
Xiamen Univ., Xiamen (China). Fujian Provincial Key Lab. of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
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:: 2018-11-25

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:: Accepted Manuscript

Journal Name:: Angewandte Chemie (International Edition)

Additional Journal Information:: Journal Name: Angewandte Chemie (International Edition); 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.

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                    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.

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                    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.

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@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)},

  number       = 10,

  volume       = 58,

  place        = {United States},

  year         = {2018},

  month        = {11}

}

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Works referenced in this record:

Hydrogen Storage in Metal�Organic Frameworks
journal, September 2011

Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri
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Interaction of hydrogen with metal nitrides and imides
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Chen, Ping; Xiong, Zhitao; Luo, Jizhong
Nature, Vol. 420, Issue 6913, p. 302-304
DOI: 10.1038/nature01210

Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials
journal, May 1997

Bogdanovi?, Borislav; Schwickardi, Manfred
Journal of Alloys and Compounds, Vol. 253-254, p. 1-9
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Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003

Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed
Science, Vol. 300, Issue 5622, p. 1127-1129
DOI: 10.1126/science.1083440

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Similar Records

This content will become publicly available on November 25, 2019

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

Abstract

Citation Formats

Hydrogen Storage in Metal�Organic Frameworks journal, September 2011

Interaction of hydrogen with metal nitrides and imides journal, November 2002

Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials journal, May 1997

Hydrogen Storage in Microporous Metal-Organic Frameworks journal, May 2003

Hydrogen Storage in Metal�Organic Frameworks
journal, September 2011

Interaction of hydrogen with metal nitrides and imides
journal, November 2002

Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials
journal, May 1997

Hydrogen Storage in Microporous Metal-Organic Frameworks
journal, May 2003