Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Wang, Fei; Gerken, James B.; Bates, Desiree M.; Kim, Yeon Jung; Stahl, Shannon S.

doi:10.1021/jacs.0c04626

Electrochemical Strategy for Hydrazine Synthesis: Development and Overpotential Analysis of Methods for Oxidative N–N Coupling of an Ammonia Surrogate

Journal Article · Wed Jun 10 00:00:00 EDT 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c04626· OSTI ID:1647753

^[1]; Gerken, James B. ^[2]; Bates, Desiree M. ^[2]; Kim, Yeon Jung ^[2]; ^[2]

Univ. of Wisconsin, Madison, WI (United States); University of Wisconsin-Madison
Univ. of Wisconsin, Madison, WI (United States)

Hydrazine is an important industrial chemical and fuel that has attracted considerable attention for use in liquid fuel cells. Ideally, hydrazine could be prepared via direct oxidative coupling of ammonia, but thermodynamic and kinetic factors limit the viability of this approach. Here, the present study evaluates three different electrochemical strategies for the oxidative homocoupling of benzophenone imine, a readily accessible ammonia surrogate. Hydrolysis of the resulting benzophenone azine affords hydrazine and benzophenone, with the latter amenable to recycling. The three different electrochemical N–N coupling methods are (1) a proton-coupled electron-transfer process promoted by a phosphate base, (2) an iodine-mediated reaction involving intermediate N–I bond formation, and (3) a copper-catalyzed N–N coupling process. Analysis of the thermodynamic efficiencies for these electrochemical imine-to-azine oxidation reactions reveals low overpotentials (η) for the copper- and iodine-mediated processes (390 and 470 mV, respectively), but a much higher value for the proton-coupled pathway (η ≈ 1.6 V). A similar approach is used to assess molecular electrocatalytic methods for electrochemical oxidation of ammonia to dinitrogen.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-05ER15690

OSTI ID:: 1647753

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 28 Vol. 142; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (36)

A Platinum-Free Zero-Carbon-Emission Easy Fuelling Direct Hydrazine Fuel Cell for Vehicles Asazawa, Koichiro; Yamada, Koji; Tanaka, Hirohisa Angewandte Chemie International Edition, Vol. 46, Issue 42 https://doi.org/10.1002/anie.200701334	journal	October 2007
Anode Catalysts for Direct Hydrazine Fuel Cells: From Laboratory Test to an Electric Vehicle Serov, Alexey; Padilla, Monica; Roy, Aaron J. Angewandte Chemie International Edition, Vol. 53, Issue 39 https://doi.org/10.1002/anie.201404734	journal	August 2014
Merging Photochemistry with Electrochemistry: Functional-Group Tolerant Electrochemical Amination of C(sp ³ )−H Bonds Wang, Fei; Stahl, Shannon S. Angewandte Chemie International Edition, Vol. 58, Issue 19 https://doi.org/10.1002/anie.201813960	journal	March 2019
Catalytic Ammonia Oxidation to Dinitrogen by Hydrogen Atom Abstraction Bhattacharya, Papri; Heiden, Zachariah M.; Chambers, Geoffrey M. Angewandte Chemie International Edition, Vol. 58, Issue 34 https://doi.org/10.1002/anie.201903221	journal	June 2019
Detection of the Elusive Nitrogen‐Centered Radicals from Catalytic Hofmann–Löffler Reactions Bosnidou, Alexandra E.; Duhamel, Thomas; Muñiz, Kilian European Journal of Organic Chemistry, Vol. 2020, Issue 40 https://doi.org/10.1002/ejoc.201900497	journal	May 2019
Electrochemistry during efficient copper recovery from complex electronic waste using ammonia based solutions Sun, Zhi; Cao, Hongbin; Venkatesan, Prakash Frontiers of Chemical Science and Engineering, Vol. 11, Issue 3 https://doi.org/10.1007/s11705-016-1587-x	journal	September 2016
Reactions of iodine in liquid ammonia Watt, G. W.; Foerster, D. R. Journal of Inorganic and Nuclear Chemistry, Vol. 13, Issue 3-4 https://doi.org/10.1016/0022-1902(60)80310-7	journal	May 1960
Ammonia—Hydrazine conversion processes Hayashi, Hiromu; Somei, Junichi; Okazaki, Tatsuya Applied Catalysis, Vol. 41 https://doi.org/10.1016/S0166-9834(00)80393-0	journal	July 1988
Direct hydrazine fuel cells: A review Serov, Alexey; Kwak, Chan Applied Catalysis B: Environmental, Vol. 98, Issue 1-2 https://doi.org/10.1016/j.apcatb.2010.05.005	journal	July 2010
Ammonia-fed fuel cells: a comprehensive review Afif, Ahmed; Radenahmad, Nikdalila; Cheok, Quentin Renewable and Sustainable Energy Reviews, Vol. 60 https://doi.org/10.1016/j.rser.2016.01.120	journal	July 2016
Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J. Inorganic Chemistry, Vol. 54, Issue 24 https://doi.org/10.1021/acs.inorgchem.5b02136	journal	December 2015
I ₂ /KI-Mediated Oxidative N–N Bond Formation for the Synthesis of 1,5-Fused 1,2,4-Triazoles from N -Aryl Amidines Song, Lina; Tian, Xianhai; Lv, Zhigang The Journal of Organic Chemistry, Vol. 80, Issue 14 https://doi.org/10.1021/acs.joc.5b01183	journal	July 2015
Electrocatalytic Ammonia Oxidation Mediated by a Polypyridyl Iron Catalyst Zott, Michael D.; Garrido-Barros, Pablo; Peters, Jonas C. ACS Catalysis, Vol. 9, Issue 11 https://doi.org/10.1021/acscatal.9b03499	journal	September 2019
Evaluating the Thermodynamics of Electrocatalytic N ₂ Reduction in Acetonitrile Lindley, Brian M.; Appel, Aaron M.; Krogh-Jespersen, Karsten ACS Energy Letters, Vol. 1, Issue 4 https://doi.org/10.1021/acsenergylett.6b00319	journal	September 2016
Hydrazine Production from Ammonia via Azine Hayashi, Hiromu; Kainoh, Akihiko; Katayama, Masayoshi Industrial & Engineering Chemistry Product Research and Development, Vol. 15, Issue 4 https://doi.org/10.1021/i360060a016	journal	December 1976
Dinitrogen Formation by Oxidative Intramolecular N---N Coupling in cis,cis- [(bpy) ₂ (NH ₃ )RuORu(NH ₃ )(bpy) ₂ ] ⁴⁺ Ishitani, Osamu; Ando, Emiko; Meyer, Thomas J. Inorganic Chemistry, Vol. 42, Issue 5 https://doi.org/10.1021/ic026096a	journal	March 2003
Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile Roberts, John A. S.; Bullock, R. Morris Inorganic Chemistry, Vol. 52, Issue 7 https://doi.org/10.1021/ic302461q	journal	June 2012
Formation of Dinitrogen by Oxidation of [(bpy) ₂ (NH ₃ )RuORu(NH ₃ )(bpy) ₂ ] ⁴⁺ Ishitani, Osamu; White, Peter S.; Meyer, Thomas J. Inorganic Chemistry, Vol. 35, Issue 8 https://doi.org/10.1021/ic9512643	journal	January 1996
CONDENSATIONS BY SODIUM INSTEAD OF BY THE GRIGNARD REACTION. II. ¹ REACTION WITH BENZONITRILE. PREPARATION OF DIPHENYLKETAZINE Morton, Avery A.; Stevens, Joseph R. Journal of the American Chemical Society, Vol. 53, Issue 7 https://doi.org/10.1021/ja01358a050	journal	July 1931
Noble Metal-Free Hydrazine Fuel Cell Catalysts: EPOC Effect in Competing Chemical and Electrochemical Reaction Pathways Sanabria-Chinchilla, Jean; Asazawa, Koichiro; Sakamoto, Tomokazu Journal of the American Chemical Society, Vol. 133, Issue 14 https://doi.org/10.1021/ja111160r	journal	April 2011
Electrochemical Aminoxyl-Mediated α-Cyanation of Secondary Piperidines for Pharmaceutical Building Block Diversification Lennox, Alastair J. J.; Goes, Shannon L.; Webster, Matthew P. Journal of the American Chemical Society, Vol. 140, Issue 36 https://doi.org/10.1021/jacs.8b08145	journal	August 2018
Diversion of Catalytic C–N Bond Formation to Catalytic Oxidation of NH ₃ through Modification of the Hydrogen Atom Abstractor Dunn, Peter L.; Johnson, Samantha I.; Kaminsky, Werner Journal of the American Chemical Society, Vol. 142, Issue 7 https://doi.org/10.1021/jacs.9b13706	journal	January 2020
Extension of the Self-Consistent Spectrophotometric Basicity Scale in Acetonitrile to a Full Span of 28 p K _a Units: Unification of Different Basicity Scales Kaljurand, Ivari; Kütt, Agnes; Sooväli, Lilli The Journal of Organic Chemistry, Vol. 70, Issue 3 https://doi.org/10.1021/jo048252w	journal	February 2005
Copper-Catalyzed Oxidative Alkynylation of Diaryl Imines with Terminal Alkynes: A Facile Synthesis of Ynimines Laouiti, Anouar; Rammah, Mohamed M.; Rammah, Mohamed B. Organic Letters, Vol. 14, Issue 1 https://doi.org/10.1021/ol2032152	journal	December 2011
How a century of ammonia synthesis changed the world Erisman, Jan Willem; Sutton, Mark A.; Galloway, James Nature Geoscience, Vol. 1, Issue 10 https://doi.org/10.1038/ngeo325	journal	September 2008
Ruthenium-catalysed oxidative conversion of ammonia into dinitrogen Nakajima, Kazunari; Toda, Hiroki; Sakata, Ken Nature Chemistry, Vol. 11, Issue 8 https://doi.org/10.1038/s41557-019-0293-y	journal	July 2019
Ammonia as a possible element in an energy infrastructure: catalysts for ammonia decomposition Schüth, F.; Palkovits, R.; Schlögl, R. Energy Environ. Sci., Vol. 5, Issue 4 https://doi.org/10.1039/C2EE02865D	journal	January 2012
Recent advances in iodine mediated electrochemical oxidative cross-coupling Liu, Kun; Song, Chunlan; Lei, Aiwen Organic & Biomolecular Chemistry, Vol. 16, Issue 14 https://doi.org/10.1039/C8OB00063H	journal	January 2018
Mechanistic insights into copper-catalyzed aerobic oxidative coupling of N–N bonds Ryan, Michael C.; Kim, Yeon Jung; Gerken, James B. Chemical Science, Vol. 11, Issue 4 https://doi.org/10.1039/C9SC04305E	journal	January 2020
Kinetics of oxidation of nitrogen compounds by cerium(IV) Doherty, Anne M. M.; Radcliffe, Mark D.; Stedman, Geoffrey Journal of the Chemical Society, Dalton Transactions, Issue 18 https://doi.org/10.1039/a904080c	journal	January 1999
Ammonia for hydrogen storage: challenges and opportunities Klerke, Asbjørn; Christensen, Claus Hviid; Nørskov, Jens K. Journal of Materials Chemistry, Vol. 18, Issue 20 https://doi.org/10.1039/b720020j	journal	January 2008
Recent Advances in Nitrogen–Nitrogen Bond Formation Guo, Qihang; Lu, Zhan Synthesis, Vol. 49, Issue 17 https://doi.org/10.1055/s-0036-1588512	journal	August 2017
Homogeneous electrocatalytic oxidation of ammonia to N ₂ under mild conditions Habibzadeh, Faezeh; Miller, Susanne L.; Hamann, Thomas W. Proceedings of the National Academy of Sciences, Vol. 116, Issue 8 https://doi.org/10.1073/pnas.1813368116	journal	January 2019
Hydrazine Synthesis by a Catalytic Oxidation Process Hayashi, Hiromu Catalysis Reviews, Vol. 32, Issue 3 https://doi.org/10.1080/01614949009351352	journal	August 1990
Review—Ammonia Oxidation Electrocatalysis for Hydrogen Generation and Fuel Cells Adli, Nadia Mohd; Zhang, Hao; Mukherjee, Shreya Journal of The Electrochemical Society, Vol. 165, Issue 15 https://doi.org/10.1149/2.0191815jes	journal	January 2018
Ammonia as a Suitable Fuel for Fuel Cells Lan, Rong; Tao, Shanwen Frontiers in Energy Research, Vol. 2 https://doi.org/10.3389/fenrg.2014.00035	journal	August 2014

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