Homogeneous electrocatalytic oxidation of ammonia to N2 under mild conditions

Habibzadeh, Faezeh; Miller, Susanne L.; Hamann, Thomas W.; Smith, III, Milton R.

doi:10.1073/pnas.1813368116

Homogeneous electrocatalytic oxidation of ammonia to N₂ under mild conditions

Journal Article · Thu Jan 17 00:00:00 EST 2019 · Proceedings of the National Academy of Sciences of the United States of America

DOI:https://doi.org/10.1073/pnas.1813368116· OSTI ID:1491265

Habibzadeh, Faezeh; Miller, Susanne L.; Hamann, Thomas W.;

We report that ruthenium polypyridyl complexes can catalyze ammonia oxidation to dinitrogen at room temperature and ambient pressure. During bulk electrolysis experiments, gas chromatography and mass spectrometry analysis of the headspace in the electrochemical cell showed that dinitrogen and dihydrogen are generated from ammonia with high faradaic efficiencies. A proposed mechanism where a hydrazine complex is the initial N–N bonded intermediate is supported by chemical and electrochemical experiments. This is a well-defined system for homogeneous electrocatalytic ammonia oxidation. This work establishes a platform for answering mechanistic questions relevant to using ammonia to store and distribute renewable energy.

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Research Organization:: Michigan State Univ., East Lansing, MI (United States)

Sponsoring Organization:: Camille Dreyfus Teacher-Scholar Awards Program; USDOE Office of Science (SC)

Grant/Contract Number:: SC0016604

OSTI ID:: 1491265

Alternate ID(s):: OSTI ID: 1612672

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: 8 Vol. 116; ISSN 0027-8424

Publisher:: National Academy of SciencesCopyright Statement

Country of Publication:: United States

Language:: English

References (30)

Is nitrogen the next carbon?: IS NITROGEN THE NEXT CARBON? Battye, William; Aneja, Viney P.; Schlesinger, William H. Earth's Future, Vol. 5, Issue 9 https://doi.org/10.1002/2017EF000592	journal	September 2017
Towards Catalytic Ammonia Oxidation to Dinitrogen: A Synthetic Cycle by Using a Simple Manganese Complex Keener, Megan; Peterson, Madeline; Hernández Sánchez, Raúl Chemistry - A European Journal, Vol. 23, Issue 48 https://doi.org/10.1002/chem.201703153	journal	August 2017
The bioenergetic role of dioxygen and the terminal oxidase(s) in cyanobacteria Paumann, Martina; Regelsberger, Günther; Obinger, Christian Biochimica et Biophysica Acta (BBA) - Bioenergetics, Vol. 1707, Issue 2-3 https://doi.org/10.1016/j.bbabio.2004.12.007	journal	April 2005
Alternatives to Electricity for Transmission, Firming Storage, and Supply Integration for Diverse, Stranded, Renewable Energy Resources: Gaseous Hydrogen and Anhydrous Ammonia Fuels via Underground Pipelines Leighty, William C.; Holbrook, John H. Energy Procedia, Vol. 29 https://doi.org/10.1016/j.egypro.2012.09.040	journal	January 2012
Optimization of Pt–Ir on carbon fiber paper for the electro-oxidation of ammonia in alkaline media Boggs, Bryan K.; Botte, Gerardine G. Electrochimica Acta, Vol. 55, Issue 19 https://doi.org/10.1016/j.electacta.2010.04.040	journal	July 2010
Why the optimal ammonia synthesis catalyst is not the optimal ammonia decomposition catalyst Boisen, A.; Dahl, S.; Norskov, J. Journal of Catalysis, Vol. 230, Issue 2 https://doi.org/10.1016/j.jcat.2004.12.013	journal	March 2005
Preparation and reactivity of osmium(II) hydride complexes with phosphites and polypyridyls Albertin, Gabriele; Antoniutti, Stefano; Pizzol, Sonia Journal of Organometallic Chemistry, Vol. 689, Issue 9 https://doi.org/10.1016/j.jorganchem.2004.02.019	journal	May 2004
Interplay between Theory and Experiment for Ammonia Synthesis Catalyzed by Transition Metal Complexes Tanaka, Hiromasa; Nishibayashi, Yoshiaki; Yoshizawa, Kazunari Accounts of Chemical Research, Vol. 49, Issue 5 https://doi.org/10.1021/acs.accounts.6b00033	journal	April 2016
Homolytic N–H Activation of Ammonia: Hydrogen Transfer of Parent Iridium Ammine, Amide, Imide, and Nitride Species Scheibel, Markus G.; Abbenseth, Josh; Kinauer, Markus Inorganic Chemistry, Vol. 54, Issue 19 https://doi.org/10.1021/acs.inorgchem.5b00829	journal	July 2015
As Precious as Platinum: Iron Nitride for Electrocatalytic Oxidation of Liquid Ammonia Little, Daniel J.; Edwards, Dillon O.; Smith, Milton R. ACS Applied Materials & Interfaces, Vol. 9, Issue 19 https://doi.org/10.1021/acsami.7b02639	journal	May 2017
Solar Energy Supply and Storage for the Legacy and Nonlegacy Worlds Cook, Timothy R.; Dogutan, Dilek K.; Reece, Steven Y. Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr100246c	journal	November 2010
Mechanism of Nitrogen Fixation by Nitrogenase: The Next Stage Hoffman, Brian M.; Lukoyanov, Dmitriy; Yang, Zhi-Yong Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr400641x	journal	January 2014
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
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry Rountree, Eric S.; McCarthy, Brian D.; Eisenhart, Thomas T. Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic500658x	journal	September 2014
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
Osmium Hydrazido and Dinitrogen Complexes Coia, George M.; Devenney, Martin; White, Peter S. Inorganic Chemistry, Vol. 36, Issue 11 https://doi.org/10.1021/ic961025v	journal	May 1997
Reduced nitrogen hydride complexes of a cofacial metallodiporphyrin and their oxidative interconversion. An analysis of ammonia oxidation and prospects for a dinitrogen electroreduction catalyst based on cofacial metallodiporphyrins Collman, James P.; Hutchison, James E.; Ennis, Matthew S. Journal of the American Chemical Society, Vol. 114, Issue 21 https://doi.org/10.1021/ja00047a016	journal	October 1992
Syntheses and reactions of hydrazine and diazene complexes of tungsten. The first example of monodentate coordination of diazene Smith, Milton R.; Cheng, Tan Yun; Hillhouse, Gregory L. Journal of the American Chemical Society, Vol. 115, Issue 19 https://doi.org/10.1021/ja00072a017	journal	September 1993
Preparation of Osmium Hydrazido Complexes by Interception of an Osmium(IV) Imido Intermediate Coia, George M.; White, Peter S.; Meyer, Thomas J. Journal of the American Chemical Society, Vol. 116, Issue 8 https://doi.org/10.1021/ja00087a081	journal	April 1994
Oxidation of coordinated ammonia to nitrate Thompson, Mark S.; Meyer, Thomas J. Journal of the American Chemical Society, Vol. 103, Issue 18 https://doi.org/10.1021/ja00408a054	journal	September 1981
Hydrogen Production from Ammonia Using Sodium Amide David, William I. F.; Makepeace, Joshua W.; Callear, Samantha K. Journal of the American Chemical Society, Vol. 136, Issue 38 https://doi.org/10.1021/ja5042836	journal	June 2014
Ammonia Oxidation by Abstraction of Three Hydrogen Atoms from a Mo–NH ₃ Complex Bhattacharya, Papri; Heiden, Zachariah M.; Wiedner, Eric S. Journal of the American Chemical Society, Vol. 139, Issue 8 https://doi.org/10.1021/jacs.7b00002	journal	February 2017
Ammonia Activation, H ₂ Evolution and Nitride Formation from a Molybdenum Complex with a Chemically and Redox Noninnocent Ligand Margulieux, Grant W.; Bezdek, Máté J.; Turner, Zoë R. Journal of the American Chemical Society, Vol. 139, Issue 17 https://doi.org/10.1021/jacs.7b03070	journal	April 2017
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
Challenges in reduction of dinitrogen by proton and electron transfer van der Ham, Cornelis J. M.; Koper, Marc T. M.; Hetterscheid, Dennis G. H. Chem. Soc. Rev., Vol. 43, Issue 15 https://doi.org/10.1039/C4CS00085D	journal	January 2014
Electrolysis of liquid ammonia for hydrogen generation Little, Daniel J.; Smith, III, Milton R.; Hamann, Thomas W. Energy & Environmental Science, Vol. 8, Issue 9 https://doi.org/10.1039/C5EE01840D	journal	January 2015
Carbon-free energy: a review of ammonia- and hydrazine-based electrochemical fuel cells Rees, Neil V.; Compton, Richard G. Energy & Environmental Science, Vol. 4, Issue 4 https://doi.org/10.1039/c0ee00809e	journal	January 2011
Fuel Power Density Ahlgren, William Journal of Pressure Vessel Technology, Vol. 134, Issue 5 https://doi.org/10.1115/1.4006906	journal	September 2012
Carbon-free H ₂ production from ammonia triggered at room temperature with an acidic RuO ₂ /γ-Al ₂ O ₃ catalyst Nagaoka, Katsutoshi; Eboshi, Takaaki; Takeishi, Yuma Science Advances, Vol. 3, Issue 4 https://doi.org/10.1126/sciadv.1602747	journal	April 2017
Coordination-induced weakening of ammonia, water, and hydrazine X–H bonds in a molybdenum complex Bezdek, Máté J.; Guo, Sheng; Chirik, Paul J. Science, Vol. 354, Issue 6313 https://doi.org/10.1126/science.aag0246	journal	November 2016

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Homogeneous electrocatalytic oxidation of ammonia to N2 under mild conditions

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