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

Yu, Yang; He, Teng; Wu, Anan; Pei, Qijun; Karkamkar, Abhijeet; Autrey, Tom; Chen, Ping

doi:10.1002/anie.201810945

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

Journal Article · 24 November 2018 · Angewandte Chemie (International Edition)

DOI: https://doi.org/10.1002/anie.201810945 · OSTI ID:1490385

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

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.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F); National Natural Science Foundation of China (NNSFC)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1490385

Alternate ID(s):: OSTI ID: 1506689

Report Number(s):: PNNL-SA--132154

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 10 Vol. 58; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Dendrimer-Stabilized Metal Nanoparticles as Efficient Catalysts for Reversible Dehydrogenation/Hydrogenation of N-Heterocycles Deraedt, Christophe; Ye, Rong; Ralston, Walter T. Journal of the American Chemical Society, Vol. 139, Issue 49 https://doi.org/10.1021/jacs.7b10768	journal	November 2017
A Molecular Iron Catalyst for the Acceptorless Dehydrogenation and Hydrogenation of N-Heterocycles Chakraborty, Sumit; Brennessel, William W.; Jones, William D. Journal of the American Chemical Society, Vol. 136, Issue 24 https://doi.org/10.1021/ja504523b	journal	June 2014
Hydrogen storage in liquid organic heterocycles Crabtree, Robert H. Energy & Environmental Science, Vol. 1, Issue 1 https://doi.org/10.1039/b805644g	journal	January 2008
Acceptorless Dehydrogenation of Nitrogen Heterocycles with a Versatile Iridium Catalyst Wu, Jianjun; Talwar, Dinesh; Johnston, Steven Angewandte Chemie, Vol. 125, Issue 27 https://doi.org/10.1002/ange.201300292	journal	May 2013
Ruthenium(0) Nanoclusters Stabilized by Nanozeolite Framework: Isolable, Reusable, and Green Catalyst for the Hydrogenation of Neat Aromatics under Mild Conditions with the Unprecedented Catalytic Activity and Lifetime Zahmakıran, Mehmet; Tonbul, Yalçın; Özkar, Saim Journal of the American Chemical Society, Vol. 132, Issue 29 https://doi.org/10.1021/ja103871s	journal	June 2010
Hydrogen-storage materials for mobile applications Schlapbach, Louis; Züttel, Andreas Nature, Vol. 414, Issue 6861 https://doi.org/10.1038/35104634	journal	November 2001
Ti-doped alkali metal aluminium hydrides as potential novel reversible hydrogen storage materials Bogdanović, Borislav; Schwickardi, Manfred Journal of Alloys and Compounds, Vol. 253-254, p. 1-9 https://doi.org/10.1016/S0925-8388(96)03049-6	journal	May 1997
Chemical and Physical Solutions for Hydrogen Storage Eberle, Ulrich; Felderhoff, Michael; Schüth, Ferdi Angewandte Chemie International Edition, Vol. 48, Issue 36 https://doi.org/10.1002/anie.200806293	journal	August 2009
Hydrogen Storage in Metal–Organic Frameworks Suh, Myunghyun Paik; Park, Hye Jeong; Prasad, Thazhe Kootteri Chemical Reviews, Vol. 112, Issue 2, p. 782-835 https://doi.org/10.1021/cr200274s	journal	September 2011
Acceptorless Dehydrogenation of Nitrogen Heterocycles with a Versatile Iridium Catalyst Wu, Jianjun; Talwar, Dinesh; Johnston, Steven Angewandte Chemie International Edition, Vol. 52, Issue 27 https://doi.org/10.1002/anie.201300292	journal	May 2013
High-capacity hydrogen storage in lithium and sodium amidoboranes Xiong, Zhitao; Yong, Chaw Keong; Wu, Guotao Nature Materials, Vol. 7, Issue 2 https://doi.org/10.1038/nmat2081	journal	December 2007
Ruthenium(0) Nanoclusters Stabilized by a Nanozeolite Framework: Isolable, Reusable, and Green Catalyst for the Hydrogenation of Neat Aromatics under Mild Conditions with the Unprecedented Catalytic Activity and Lifetime Zahmakıran, Mehmet; Tonbul, Yalçın; Özkar, Saim Journal of the American Chemical Society, Vol. 132, Issue 18 https://doi.org/10.1021/ja101602d	journal	May 2010
Dehydrogenation of N-ethyl perhydrocarbazole catalyzed by PCP pincer iridium complexes: Evaluation of a homogenous hydrogen storage system Wang, Zhaohui; Tonks, Ian; Belli, Jack Journal of Organometallic Chemistry, Vol. 694, Issue 17 https://doi.org/10.1016/j.jorganchem.2009.03.052	journal	August 2009
Hybrid Catalysis Enabling Room-Temperature Hydrogen Gas Release from N -Heterocycles and Tetrahydronaphthalenes Kato, Shota; Saga, Yutaka; Kojima, Masahiro Journal of the American Chemical Society, Vol. 139, Issue 6 https://doi.org/10.1021/jacs.7b00253	journal	February 2017
Electrochemical Acceptorless Dehydrogenation of N-Heterocycles Utilizing TEMPO as Organo-Electrocatalyst Wu, Yong; Yi, Hong; Lei, Aiwen ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b04137	journal	January 2018
Metal-Free Dehydrogenation of N-Heterocycles by Ternary h -BCN Nanosheets with Visible Light Zheng, Meifang; Shi, Jiale; Yuan, Tao Angewandte Chemie, Vol. 130, Issue 19 https://doi.org/10.1002/ange.201800319	journal	March 2018
Metal hydrazinoborane LiN2H3BH3 and LiN2H3BH3·2N2H4BH3: crystal structures and high-extent dehydrogenation Wu, Hui; Zhou, Wei; Pinkerton, Frederick E. Energy & Environmental Science, Vol. 5, Issue 6 https://doi.org/10.1039/c2ee21508j	journal	January 2012
High capacity hydrogenstorage materials: attributes for automotive applications and techniques for materials discovery Yang, Jun; Sudik, Andrea; Wolverton, Christopher Chem. Soc. Rev., Vol. 39, Issue 2 https://doi.org/10.1039/B802882F	journal	January 2010
Interaction of hydrogen with metal nitrides and imides Chen, Ping; Xiong, Zhitao; Luo, Jizhong Nature, Vol. 420, Issue 6913, p. 302-304 https://doi.org/10.1038/nature01210	journal	November 2002
Hydrogen delivery through liquid organic hydrides: Considerations for a potential technology Shukla, Anshu; Karmakar, Shilpi; Biniwale, Rajesh B. International Journal of Hydrogen Energy, Vol. 37, Issue 4 https://doi.org/10.1016/j.ijhydene.2011.04.107	journal	February 2012
Complex Hydrides for Hydrogen Storage Orimo, Shin-ichi; Nakamori, Yuko; Eliseo, Jennifer R. ChemInform, Vol. 38, Issue 51 https://doi.org/10.1002/chin.200751221	journal	December 2007
Complex Hydrides for Hydrogen Storage Orimo, Shin-ichi; Nakamori, Yuko; Eliseo, Jennifer R. Chemical Reviews, Vol. 107, Issue 10 https://doi.org/10.1021/cr0501846	journal	October 2007
Lithiated Primary Amine-A New Material for Hydrogen Storage Chen, Juner; Wu, Hui; Wu, Guotao Chemistry - A European Journal, Vol. 20, Issue 22 https://doi.org/10.1002/chem.201402543	journal	April 2014
Hydrogen Storage in Microporous Metal-Organic Frameworks Rosi, Nathaniel L.; Eckert, Juergen; Eddaoudi, Mohamed Science, Vol. 300, Issue 5622, p. 1127-1129 https://doi.org/10.1126/science.1083440	journal	May 2003
Hydrogen carriers He, Teng; Pachfule, Pradip; Wu, Hui Nature Reviews Materials, Vol. 1, Issue 12 https://doi.org/10.1038/natrevmats.2016.59	journal	October 2016
Photokatalyse ermöglicht die akzeptorfreie Dehydrierung von benzanellierten gesättigten Ringen bei Raumtemperatur Yin, Qin; Oestreich, Martin Angewandte Chemie, Vol. 129, Issue 27 https://doi.org/10.1002/ange.201703536	journal	May 2017
The X1s Method for Accurate Bond Dissociation Energies Wu, Jianming; Ying Zhang, Igor; Xu, Xin ChemPhysChem, Vol. 11, Issue 12 https://doi.org/10.1002/cphc.201000273	journal	July 2010
Liquid Organic Hydrogen Carriers (LOHCs): Toward a Hydrogen-free Hydrogen Economy Preuster, Patrick; Papp, Christian; Wasserscheid, Peter Accounts of Chemical Research, Vol. 50, Issue 1 https://doi.org/10.1021/acs.accounts.6b00474	journal	December 2016
The effect of substitution on the utility of piperidines and octahydroindoles for reversible hydrogen storage Cui, Yi; Kwok, Samantha; Bucholtz, Andrew New Journal of Chemistry, Vol. 32, Issue 6 https://doi.org/10.1039/b718209k	journal	January 2008
Liquid organic and inorganic chemical hydrides for high-capacity hydrogen storage Zhu, Qi-Long; Xu, Qiang Energy & Environmental Science, Vol. 8, Issue 2 https://doi.org/10.1039/C4EE03690E	journal	January 2015
Computational structure–activity relationships in H ₂ storage: how placement of N atoms affects release temperatures in organic liquid storage materials Clot, Eric; Eisenstein, Odile; Crabtree, Robert H. Chem. Commun., Issue 22 https://doi.org/10.1039/B705037B	journal	January 2007
Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis He, Ke-Han; Tan, Fang-Fang; Zhou, Chao-Zheng Angewandte Chemie, Vol. 129, Issue 11 https://doi.org/10.1002/ange.201612486	journal	February 2017
Temperature controlled three-stage catalytic dehydrogenation and cycle performance of perhydro-9-ethylcarbazole Yang, Ming; Han, Chaoqun; Ni, Gang International Journal of Hydrogen Energy, Vol. 37, Issue 17 https://doi.org/10.1016/j.ijhydene.2012.05.092	journal	September 2012
Chemische und physikalische Lösungen für die Speicherung von Wasserstoff Eberle, Ulrich; Felderhoff, Michael; Schüth, Ferdi Angewandte Chemie, Vol. 121, Issue 36 https://doi.org/10.1002/ange.200806293	journal	August 2009
Chemical utilization of hydrogen from fluctuating energy sources – Catalytic transfer hydrogenation from charged Liquid Organic Hydrogen Carrier systems Geburtig, Denise; Preuster, Patrick; Bösmann, Andreas International Journal of Hydrogen Energy, Vol. 41, Issue 2 https://doi.org/10.1016/j.ijhydene.2015.10.013	journal	January 2016
A thermodynamic and kinetic study of the heterolytic activation of hydrogen by frustrated borane–amine Lewis pairs Karkamkar, Abhi; Parab, Kshitij; Camaioni, Donald M. Dalton Trans., Vol. 42, Issue 3 https://doi.org/10.1039/C2DT31628E	journal	January 2013
Ironing Out Hydrogen Storage Ott, S. Science, Vol. 333, Issue 6050 https://doi.org/10.1126/science.1211021	journal	September 2011
Simple and Efficient System for Combined Solar Energy Harvesting and Reversible Hydrogen Storage Li, Lu; Mu, Xiaoyue; Liu, Wenbo Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03505	journal	June 2015
Hydrogen-storage materials for mobile applications Schlapbach, Louis; Züttel, Andreas Materials for Sustainable Energy https://doi.org/10.1142/9789814317665_0038	book	October 2010
Catalytic condensation for the formation of polycyclic heteroaromatic compounds Forberg, Daniel; Schwob, Tobias; Kempe, Rhett Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04143-6	journal	May 2018
Acceptorless Dehydrogenation of N-Heterocycles by Merging Visible-Light Photoredox Catalysis and Cobalt Catalysis He, Ke-Han; Tan, Fang-Fang; Zhou, Chao-Zheng Angewandte Chemie International Edition, Vol. 56, Issue 11 https://doi.org/10.1002/anie.201612486	journal	February 2017
Homogeneous Catalytic System for Reversible Dehydrogenation−Hydrogenation Reactions of Nitrogen Heterocycles with Reversible Interconversion of Catalytic Species Yamaguchi, Ryohei; Ikeda, Chikako; Takahashi, Yoshinori Journal of the American Chemical Society, Vol. 131, Issue 24 https://doi.org/10.1021/ja9022623	journal	June 2009
A high-performance hydrogen generation system: Transition metal-catalyzed dissociation and hydrolysis of ammonia–borane Chandra, Manish; Xu, Qiang Journal of Power Sources, Vol. 156, Issue 2 https://doi.org/10.1016/j.jpowsour.2005.05.043	journal	June 2006
A survey of Hammett substituent constants and resonance and field parameters Hansch, Corwin.; Leo, A.; Taft, R. W. Chemical Reviews, Vol. 91, Issue 2 https://doi.org/10.1021/cr00002a004	journal	March 1991
Hydrogen storage using a hot pressure swing reactor Jorschick, H.; Preuster, P.; Dürr, S. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE00476A	journal	January 2017
Photocatalysis Enabling Acceptorless Dehydrogenation of Benzofused Saturated Rings at Room Temperature Yin, Qin; Oestreich, Martin Angewandte Chemie International Edition, Vol. 56, Issue 27 https://doi.org/10.1002/anie.201703536	journal	May 2017
Energy storage in residential and commercial buildings via Liquid Organic Hydrogen Carriers (LOHC) Teichmann, Daniel; Stark, Katharina; Müller, Karsten Energy & Environmental Science, Vol. 5, Issue 10 https://doi.org/10.1039/c2ee22070a	journal	January 2012
Chemical hydrides: A solution to high capacity hydrogen storage and supply Biniwale, R.; Rayalu, S.; Devotta, S. International Journal of Hydrogen Energy, Vol. 33, Issue 1 https://doi.org/10.1016/j.ijhydene.2007.07.028	journal	January 2008
Metal-Free Dehydrogenation of N-Heterocycles by Ternary h -BCN Nanosheets with Visible Light Zheng, Meifang; Shi, Jiale; Yuan, Tao Angewandte Chemie International Edition, Vol. 57, Issue 19 https://doi.org/10.1002/anie.201800319	journal	March 2018

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