Reversible catalytic dehydrogenation of alcohols for energy storage

Bonitatibus, Jr., Peter J.; Chakraborty, Sumit; Doherty, Mark D.; Siclovan, Oltea; Jones, William D.; Soloveichik, Grigorii L.

doi:10.1073/pnas.1420199112

Reversible catalytic dehydrogenation of alcohols for energy storage

Journal Article · Tue Jan 13 23:00:00 EST 2015 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1420199112· OSTI ID:1235501

Bonitatibus, Jr., Peter J. ^[1]; Chakraborty, Sumit ^[2]; Doherty, Mark D. ^[1]; Siclovan, Oltea ^[1]; Jones, William D. ^[2]; Soloveichik, Grigorii L. ^[1]

Chemical &, Environmental Systems Organization, GE Global Research, Niskayuna, NY 12309, and
Department of Chemistry, University of Rochester, Rochester, NY 14627

Significance

Catalytic hydrogenation and dehydrogenation reactions are extremely important in organic chemistry and recently for energy storage in the form of chemical bonds. Although catalysts are known which catalyze both reactions, the rates and conditions required for the two are frequently very different due to the differences associated with the bonds to be activated (C–H/O–H/N–H and C = O/C = N/H–H). The use of a bifunctional catalyst would substantially simplify the design of processes related to energy storage. In this work, organometallic complexes of iron and iridium are shown to act as catalysts for reversible dehydrogenation of alcohols to carbonyl compounds. This finding opens a pathway to the development of catalysts for direct reversible electrochemical dehydrogenation of organic fuels in energy generation and storage reactions.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0001055

OSTI ID:: 1235501

Alternate ID(s):: OSTI ID: 1347970

Journal Information:: Proceedings of the National Academy of Sciences of the United States of America, Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Issue: 6 Vol. 112; ISSN 0027-8424

Publisher:: Proceedings of the National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (40)

Acceptorless and Base-Free Dehydrogenation of Alcohols and Amines using Ruthenium-Hydride Complexes Muthaiah, Senthilkumar; Hong, Soon Hyeok Advanced Synthesis & Catalysis, Vol. 354, Issue 16 https://doi.org/10.1002/adsc.201200532	journal	November 2012
Bifunctional Metal-Ligand Catalysis: Hydrogenations and New Reactions within the Metal-(Di)amine Scaffold Muñiz, Kilian Angewandte Chemie International Edition, Vol. 44, Issue 41 https://doi.org/10.1002/anie.200501787	journal	October 2005
Metalloenzyme-Inspired Catalysis: Selective Oxidation of Primary Alcohols with an Iridium–Aminyl-Radical Complex Königsmann, Martin; Donati, Nicola; Stein, Daniel Angewandte Chemie International Edition, Vol. 46, Issue 19 https://doi.org/10.1002/anie.200605170	journal	May 2007
Caprolactam from Renewable Resources: Catalytic Conversion of 5-Hydroxymethylfurfural into Caprolactone Buntara, Teddy; Noel, Sebastien; Phua, Pim Huat Angewandte Chemie International Edition, Vol. 50, Issue 31 https://doi.org/10.1002/anie.201102156	journal	June 2011
Selective Hydrogen Production from Methanol with a Defined Iron Pincer Catalyst under Mild Conditions Alberico, Elisabetta; Sponholz, Peter; Cordes, Christoph Angewandte Chemie International Edition, Vol. 52, Issue 52 https://doi.org/10.1002/anie.201307224	journal	December 2013
TROPDAD: A New Ligand for the Synthesis of Water-Stable Paramagnetic[16+1]-Electron Rhodium and Iridium Complexes Breher, Frank; Böhler, Carsten; Frison, Gilles Chemistry - A European Journal, Vol. 9, Issue 16 https://doi.org/10.1002/chem.200204700	journal	August 2003
Aerobic Lactonization of Diols by Biomimetic Oxidation Endo, Yoshinori; Bäckvall, Jan-E. Chemistry - A European Journal, Vol. 17, Issue 45 https://doi.org/10.1002/chem.201102168	journal	September 2011
A convenient lactonization of diols to γ- and δ-lactones catalysed by transition metal polyhydrides Lin, Yingrui; Zhu, Xianchao; Zhou, Yuefen Journal of Organometallic Chemistry, Vol. 429, Issue 2 https://doi.org/10.1016/0022-328X(92)83257-I	journal	May 1992
Transition metal complexes as electrocatalysts—Development and applications in electro-oxidation reactions Cheung, K.; Wong, W.; Ma, D. Coordination Chemistry Reviews, Vol. 251, Issue 17-20 https://doi.org/10.1016/j.ccr.2007.04.004	journal	September 2007
Iridium aminyl radical complexes as catalysts for the catalytic dehydrogenation of primary hydroxyl functions in natural products Donati, Nicola; Königsmann, Martin; Stein, Daniel Comptes Rendus Chimie, Vol. 10, Issue 8 https://doi.org/10.1016/j.crci.2007.03.017	journal	August 2007
A new type of electrochemical oxidation of alcohols mediated with a ruthenium–dioxolene–amine complex in neutral water Ozawa, Hironobu; Hino, Takami; Ohtsu, Hideki Inorganica Chimica Acta, Vol. 366, Issue 1 https://doi.org/10.1016/j.ica.2010.11.013	journal	January 2011
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
Efficient Catalyst for Acceptorless Alcohol Dehydrogenation: Interplay of Theoretical and Experimental Studies Zeng, Guixiang; Sakaki, Shigeyoshi; Fujita, Ken-ichi ACS Catalysis, Vol. 4, Issue 3 https://doi.org/10.1021/cs401101m	journal	January 2014
Fe-Catalyzed Acceptorless Dehydrogenation of Secondary Benzylic Alcohols Song, Hansoo; Kang, Byungjoon; Hong, Soon Hyeok ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs5007316	journal	July 2014
Catalytic Oxidation of Alcohol via Nickel Phosphine Complexes with Pendant Amines Weiss, Charles J.; Das, Parthapratim; Miller, Deanna L. ACS Catalysis, Vol. 4, Issue 9 https://doi.org/10.1021/cs500853f	journal	August 2014
Well-Defined Iron Catalysts for the Acceptorless Reversible Dehydrogenation-Hydrogenation of Alcohols and Ketones Chakraborty, Sumit; Lagaditis, Paraskevi O.; Förster, Moritz ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs5009656	journal	October 2014
Synthesis, Structure, and Redox and Catalytic Properties of a New Family of Ruthenium Complexes Containing the Tridentate bpea Ligand Rodríguez, Montserrat; Romero, Isabel; Llobet, Antoni Inorganic Chemistry, Vol. 40, Issue 17 https://doi.org/10.1021/ic010064q	journal	August 2001
Water Oxidation Intermediates Applied to Catalysis: Benzyl Alcohol Oxidation Vannucci, Aaron K.; Hull, Jonathan F.; Chen, Zuofeng Journal of the American Chemical Society, Vol. 134, Issue 9 https://doi.org/10.1021/ja210718u	journal	February 2012
Understanding the Mechanisms of Cobalt-Catalyzed Hydrogenation and Dehydrogenation Reactions Zhang, Guoqi; Vasudevan, Kalyan V.; Scott, Brian L. Journal of the American Chemical Society, Vol. 135, Issue 23 https://doi.org/10.1021/ja402679a	journal	May 2013
Iron-Based Catalysts for the Hydrogenation of Esters to Alcohols Chakraborty, Sumit; Dai, Huiguang; Bhattacharya, Papri Journal of the American Chemical Society, Vol. 136, Issue 22 https://doi.org/10.1021/ja504034q	journal	May 2014
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
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
Ruthenium-catalyzed oxidative transformation of alcohols and aldehydes to esters and lactones Murahashi, Shunichi; Naota, Takeshi; Ito, Keiichiro The Journal of Organic Chemistry, Vol. 52, Issue 19 https://doi.org/10.1021/jo00228a032	journal	September 1987
Cobalt-Catalyzed Acceptorless Alcohol Dehydrogenation: Synthesis of Imines from Alcohols and Amines Zhang, Guoqi; Hanson, Susan K. Organic Letters, Vol. 15, Issue 3 https://doi.org/10.1021/ol303479f	journal	January 2013
Acceptorless, Neat, Ruthenium-Catalyzed Dehydrogenative Cyclization of Diols to Lactones Zhao, Jing; Hartwig, John F. Organometallics, Vol. 24, Issue 10 https://doi.org/10.1021/om048983m	journal	May 2005
Iron and Ruthenium Heterobimetallic Carbonyl Complexes as Electrocatalysts for Alcohol Oxidation: Electrochemical and Mechanistic Studies Serra, Daniel; Correia, Marie C.; McElwee-White, Lisa Organometallics, Vol. 30, Issue 21 https://doi.org/10.1021/om101070z	journal	November 2011
On the “Reverse Gear”Mechanism of the Reversible Dehydrogenation/Hydrogenation of a Nitrogen Heterocycle Catalyzed by a C _p *Ir Complex: A Computational Study Li, Haixia; Jiang, Jinliang; Lu, Gang Organometallics, Vol. 30, Issue 11 https://doi.org/10.1021/om200222j	journal	June 2011
Electron-Rich PNP- and PNN-Type Ruthenium(II) Hydrido Borohydride Pincer Complexes. Synthesis, Structure, and Catalytic Dehydrogenation of Alcohols and Hydrogenation of Esters Zhang, Jing; Balaraman, Ekambaram; Leitus, Gregory Organometallics, Vol. 30, Issue 21 https://doi.org/10.1021/om200595m	journal	November 2011
Base-Free, Acceptorless, and Chemoselective Alcohol Dehydrogenation Catalyzed by an Amide-Derived NNN -Ruthenium(II) Hydride Complex Tseng, Kuei-Nin T.; Kampf, Jeff W.; Szymczak, Nathaniel K. Organometallics, Vol. 32, Issue 7 https://doi.org/10.1021/om4000677	journal	March 2013
Reversible hydrogen storage using CO₂ and a proton-switchable iridium catalyst in aqueous media under mild temperatures and pressures Hull, Jonathan F.; Himeda, Yuichiro; Wang, Wan-Hui Nature Chemistry, Vol. 4, Issue 5, p. 383-388 https://doi.org/10.1038/nchem.1295	journal	March 2012
Effective dehydrogenation of 2-pyridylmethanol derivatives catalyzed by an iron complex Kamitani, Masahiro; Ito, Masaki; Itazaki, Masumi Chem. Commun., Vol. 50, Issue 59 https://doi.org/10.1039/C4CC01498G	journal	January 2014
Molecular catalysts for hydrogen production from alcohols Trincado, Monica; Banerjee, Dipshikha; Grützmacher, Hansjörg Energy Environ. Sci., Vol. 7, Issue 8 https://doi.org/10.1039/C4EE00389F	journal	January 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
Solid-state hydrogen storage for mobile applications: Quo Vadis? Weidenthaler, Claudia; Felderhoff, Michael Energy & Environmental Science, Vol. 4, Issue 7 https://doi.org/10.1039/c0ee00771d	journal	January 2011
A future energy supply based on Liquid Organic Hydrogen Carriers (LOHC) Teichmann, Daniel; Arlt, Wolfgang; Wasserscheid, Peter Energy & Environmental Science, Vol. 4, Issue 8 https://doi.org/10.1039/c1ee01454d	journal	January 2011
Electrocatalytic oxidation of alcohols by a carbon-supported Rh porphyrin Yamazaki, Shin-ichi; Yao, Masaru; Fujiwara, Naoko Chemical Communications, Vol. 48, Issue 36 https://doi.org/10.1039/c2cc30888f	journal	January 2012
Liquid-phase chemical hydrogen storage materials Yadav, Mahendra; Xu, Qiang Energy & Environmental Science, Vol. 5, Issue 12 https://doi.org/10.1039/c2ee22937d	journal	January 2012
Highly selective electrocatalytic dehydrogenation at low applied potential catalyzed by an Ir organometallic complex Bonitatibus, Peter J.; Rainka, Matthew P.; Peters, Andrea J. Chemical Communications, Vol. 49, Issue 90 https://doi.org/10.1039/c3cc46051g	journal	January 2013
Redox Behavior of New Ru–Dioxolene–Ammine Complexes and Catalytic Activity toward Electrochemical Oxidation of Alcohol under Mild Conditions Hino, Takami; Wada, Tohru; Fujihara, Tetsuaki Chemistry Letters, Vol. 33, Issue 12 https://doi.org/10.1246/cl.2004.1596	journal	December 2004
Organic liquid carriers for hydrogen storage Ichikawa, M. Solid-State Hydrogen Storage https://doi.org/10.1533/9781845694944.4.500	book	January 2008

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