Electrocatalytic Ammonia Oxidation Mediated by a Polypyridyl Iron Catalyst

Zott, Michael D.; Garrido-Barros, Pablo; Peters, Jonas C.

doi:10.1021/acscatal.9b03499

Title: Electrocatalytic Ammonia Oxidation Mediated by a Polypyridyl Iron Catalyst

Journal Article · Thu Sep 19 00:00:00 EDT 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b03499· OSTI ID:1708895

^[1];

^[1]

California Institute of Technology (CalTech), Pasadena, CA (United States). Division of Chemistry and Chemical Engineering

Electrocatalytic ammonia oxidation (AO) mediated by iron(II) tris(2-pyridylmethyl)amine (TPA) bis-ammine triflate, [(TPA)Fe(NH₃)₂]OTf₂, is reported. Interest in (electro)catalytic AO is growing rapidly, and this report adds a first-row transition metal (iron) complex to the known Ru catalysts recently reported. The featured system is well behaved and has been studied in detail by electrochemical methods. Cyclic voltammetry experiments in the presence of ammonia indicate an onset potential corresponding to ammonia oxidation at 0.7 V vs Fc/Fc⁺. Controlled potential coulometry (CPC) at an applied bias of 1.1 V confirms the generation of 16 equiv of N₂ with a Faradaic efficiency for N₂ of ~80%. Employing ¹⁵NH₃ yields exclusively ³⁰N₂, demonstrating the conversion of ammonia to N₂. A suite of electrochemical studies is consistent with an initial EC step that generates an Fe^III–NH₂ intermediate (at 0.4 V) followed by an anodically shifted catalytic wave. The data indicate a rate-determining step that is first order in both [Fe] and [NH₃] and point to a fast catalytic rate (k_obs) of ~10⁷ M^–1·s^–1 as computed by foot of the wave analysis (FOWA).

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); Gordon and Betty Moore Foundation (GBMF); California Institute of Technology (CalTech)

Grant/Contract Number:: SC0019136

OSTI ID:: 1708895

Journal Information:: ACS Catalysis, Vol. 9, Issue 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (61)

Ammonia—a renewable fuel made from sun, air, and water—could power the globe without carbon Service, Robert Science https://doi.org/10.1126/science.aau7489	journal	July 2018
Heterogeneous electrocatalysts design for nitrogen reduction reaction under ambient conditions Wan, Yuchi; Xu, Jichu; Lv, Ruitao Materials Today, Vol. 27 https://doi.org/10.1016/j.mattod.2019.03.002	journal	July 2019
Electrocatalytic Reduction of Nitrogen: From Haber-Bosch to Ammonia Artificial Leaf Martín, Antonio José; Shinagawa, Tatsuya; Pérez-Ramírez, Javier Chem, Vol. 5, Issue 2 https://doi.org/10.1016/j.chempr.2018.10.010	journal	February 2019
A Review of Electrocatalytic Reduction of Dinitrogen to Ammonia under Ambient Conditions Cui, Xiaoyang; Tang, Cheng; Zhang, Qiang Advanced Energy Materials, Vol. 8, Issue 22 https://doi.org/10.1002/aenm.201800369	journal	May 2018
Ammonia for power Valera-Medina, A.; Xiao, H.; Owen-Jones, M. Progress in Energy and Combustion Science, Vol. 69 https://doi.org/10.1016/j.pecs.2018.07.001	journal	November 2018
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–Oxygen Fuel Cell Cairns, E. J.; Simons, E. L.; Tevebaugh, A. D. Nature, Vol. 217, Issue 5130 https://doi.org/10.1038/217780a0	journal	February 1968
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
Recent advances in electrocatalysts for electro-oxidation of ammonia Zhong, C.; Hu, W. B.; Cheng, Y. F. J. Mater. Chem. A, Vol. 1, Issue 10 https://doi.org/10.1039/C2TA00607C	journal	January 2013
Selective Low Temperature NH3 Oxidation to N2 on Copper-Based Catalysts Gang, Lu; van Grondelle, J.; Anderson, B. G. Journal of Catalysis, Vol. 186, Issue 1 https://doi.org/10.1006/jcat.1999.2524	journal	August 1999
Fabrication of Hierarchically Porous RuO ₂ –CuO/Al–ZrO ₂ Composite as Highly Efficient Catalyst for Ammonia-Selective Catalytic Oxidation Cui, Xiangzhi; Chen, Lisong; Wang, Yongxia ACS Catalysis, Vol. 4, Issue 7 https://doi.org/10.1021/cs500421x	journal	May 2014
Selective catalytic oxidation of ammonia to nitrogen over CuO/CNTs: The promoting effect of the defects of CNTs on the catalytic activity and selectivity Song, Shaoqing; Jiang, Shujuan Applied Catalysis B: Environmental, Vol. 117-118 https://doi.org/10.1016/j.apcatb.2012.01.030	journal	May 2012
Evidence for Decoupled Electron and Proton Transfer in the Electrochemical Oxidation of Ammonia on Pt(100) Katsounaros, Ioannis; Chen, Ting; Gewirth, Andrew A. The Journal of Physical Chemistry Letters, Vol. 7, Issue 3 https://doi.org/10.1021/acs.jpclett.5b02556	journal	January 2016
A review on direct methanol fuel cells–In the perspective of energy and sustainability Joghee, Prabhuram; Malik, Jennifer Nekuda; Pylypenko, Svitlana MRS Energy & Sustainability, Vol. 2, Issue 1 https://doi.org/10.1557/mre.2015.4	journal	February 2015
Nitrogen Fixation Catalyzed by Transition Metal Complexes: Recent Developments: Nitrogen Fixation Catalyzed by Transition Metal Complexes: Recent Developments Stucke, Nadja; Flöser, Benedikt M.; Weyrich, Thomas European Journal of Inorganic Chemistry, Vol. 2018, Issue 12 https://doi.org/10.1002/ejic.201701326	journal	February 2018
Development of catalytic nitrogen fixation using transition metal–dinitrogen complexes under mild reaction conditions Nishibayashi, Yoshiaki Dalton Transactions, Vol. 47, Issue 33 https://doi.org/10.1039/C8DT02572J	journal	January 2018
Catalytic Reduction of Dinitrogen to Ammonia at a Single Molybdenum Center Yandulov, D. V. Science, Vol. 301, Issue 5629 https://doi.org/10.1126/science.1085326	journal	July 2003
Catalytic conversion of nitrogen to ammonia by an iron model complex Anderson, John S.; Rittle, Jonathan; Peters, Jonas C. Nature, Vol. 501, Issue 7465 https://doi.org/10.1038/nature12435	journal	September 2013
A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia Arashiba, Kazuya; Miyake, Yoshihiro; Nishibayashi, Yoshiaki Nature Chemistry, Vol. 3, Issue 2 https://doi.org/10.1038/nchem.906	journal	December 2010
Fe-Mediated Nitrogen Fixation with a Metallocene Mediator: Exploring p K _a Effects and Demonstrating Electrocatalysis Chalkley, Matthew J.; Del Castillo, Trevor J.; Matson, Benjamin D. Journal of the American Chemical Society, Vol. 140, Issue 19 https://doi.org/10.1021/jacs.8b02335	journal	April 2018
Molybdenum-catalysed ammonia production with samarium diiodide and alcohols or water Ashida, Yuya; Arashiba, Kazuya; Nakajima, Kazunari Nature, Vol. 568, Issue 7753 https://doi.org/10.1038/s41586-019-1134-2	journal	April 2019
Recent Developments in Nitrogen Reduction Catalysts: A Virtual Issue Minteer, Shelley D.; Christopher, Phillip; Linic, Suljo ACS Energy Letters, Vol. 4, Issue 1 https://doi.org/10.1021/acsenergylett.8b02197	journal	December 2018
Alternative Bioenergy: Updates to and Challenges in Nitrification Metalloenzymology Lancaster, Kyle M.; Caranto, Jonathan D.; Majer, Sean H. Joule, Vol. 2, Issue 3 https://doi.org/10.1016/j.joule.2018.01.018	journal	March 2018
Anammox Biochemistry: a Tale of Heme c Proteins Kartal, Boran; Keltjens, Jan T. Trends in Biochemical Sciences, Vol. 41, Issue 12 https://doi.org/10.1016/j.tibs.2016.08.015	journal	December 2016
Thermochemistry of Proton-Coupled Electron Transfer Reagents and its Implications Warren, Jeffrey J.; Tronic, Tristan A.; Mayer, James M. Chemical Reviews, Vol. 110, Issue 12 https://doi.org/10.1021/cr100085k	journal	December 2010
Oxidation of pentaamminecarbonylosmium(2+) to .mu.-dinitrogen-bis(cis-tetraamminecarbonylosmium)(4+) Buhr, John D.; Taube, H. Inorganic Chemistry, Vol. 18, Issue 8 https://doi.org/10.1021/ic50198a032	journal	August 1979
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
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
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
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
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
Highly Electrophilic (Salen)ruthenium(VI) Nitrido Complexes Man, Wai-Lun; Tang, Tsz-Man; Wong, Tsz-Wing Journal of the American Chemical Society, Vol. 126, Issue 2 https://doi.org/10.1021/ja037899f	journal	January 2004
Synthesis and Reactivity of a Transient, Terminal Nitrido Complex of Rhodium Scheibel, Markus G.; Wu, Yanlin; Stückl, A. Claudia Journal of the American Chemical Society, Vol. 135, Issue 47 https://doi.org/10.1021/ja409764j	journal	November 2013
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
Coupling of terminal iridium nitrido complexes Abbenseth, Josh; Finger, Markus; Würtele, Christian Inorganic Chemistry Frontiers, Vol. 3, Issue 4 https://doi.org/10.1039/C5QI00267B	journal	January 2016
Tuning Electronic Structure To Control Manganese Nitride Activation Clarke, Ryan M.; Storr, Tim Journal of the American Chemical Society, Vol. 138, Issue 47 https://doi.org/10.1021/jacs.6b09576	journal	November 2016
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
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
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
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
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
Efficient water oxidation catalysts based on readily available iron coordination complexes Fillol, Julio Lloret; Codolà, Zoel; Garcia-Bosch, Isaac Nature Chemistry, Vol. 3, Issue 10 https://doi.org/10.1038/nchem.1140	journal	September 2011
Homogeneous Oxidation of Water by Iron Complexes with Macrocyclic Ligands Zhang, Biaobiao; Li, Fei; Yu, Fengshou Chemistry - An Asian Journal, Vol. 9, Issue 6 https://doi.org/10.1002/asia.201400066	journal	April 2014
Water oxidation catalysed by iron complex of N,N′-dimethyl-2,11-diaza[3,3](2,6)pyridinophane. Spectroscopy of iron–oxo intermediates and density functional theory calculations To, Wai-Pong; Wai-Shan Chow, Toby; Tse, Chun-Wai Chemical Science, Vol. 6, Issue 10 https://doi.org/10.1039/C5SC01680K	journal	January 2015
Iron Pentapyridyl Complexes as Molecular Water Oxidation Catalysts: Strong Influence of a Chloride Ligand and pH in Altering the Mechanism Das, Biswanath; Orthaber, Andreas; Ott, Sascha ChemSusChem, Vol. 9, Issue 10 https://doi.org/10.1002/cssc.201600052	journal	April 2016
Electrocatalytic Water Oxidation by a Monomeric Amidate-Ligated Fe(III)–Aqua Complex Coggins, Michael K.; Zhang, Ming-Tian; Vannucci, Aaron K. Journal of the American Chemical Society, Vol. 136, Issue 15 https://doi.org/10.1021/ja412822u	journal	April 2014
Iron Complexes of Square Planar Tetradentate Polypyridyl-Type Ligands as Catalysts for Water Oxidation Wickramasinghe, Lanka D.; Zhou, Rongwei; Zong, Ruifa Journal of the American Chemical Society, Vol. 137, Issue 41 https://doi.org/10.1021/jacs.5b08856	journal	October 2015
Iron(II) Polyamine Chemistry: Variation of Spin State and Coordination Number in Solid State and Solution with Iron(II) Tris(2-pyridylmethyl)amine Complexes Diebold, Alain; Hagen, Karl S. Inorganic Chemistry, Vol. 37, Issue 2 https://doi.org/10.1021/ic971105e	journal	January 1998
On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation Lee, Katherine J.; McCarthy, Brian D.; Dempsey, Jillian L. Chemical Society Reviews, Vol. 48, Issue 11 https://doi.org/10.1039/C8CS00851E	journal	January 2019
Electrochemically Driven Water-Oxidation Catalysis Beginning with Six Exemplary Cobalt Polyoxometalates: Is It Molecular, Homogeneous Catalysis or Electrode-Bound, Heterogeneous CoO _x Catalysis? Folkman, Scott J.; Soriano-Lopez, Joaquin; Galán-Mascarós, José Ramón Journal of the American Chemical Society, Vol. 140, Issue 38 https://doi.org/10.1021/jacs.8b06303	journal	September 2018
Magnetostructural Relationship in the Spin-Crossover Complex t-{Fe(abpt) ₂ [N(CN) ₂ ] ₂ }: Polymorphism and Disorder Phenomenon Sheu, Chou-Fu; Pillet, Sébastien; Lin, Yen-Chen Inorganic Chemistry, Vol. 47, Issue 23 https://doi.org/10.1021/ic800879c	journal	December 2008
The commensurate modulated structure of the metastable state in spin crossover complex [Fe(abpt)2(NCS)2] Sheu, Chou-Fu; Chen, Szu-Miao; Wang, Shih-Chi Chemical Communications, Issue 48 https://doi.org/10.1039/b910378c	journal	January 2009
Solvent-exchange kinetics in iron(II) solution of N,N-dimethylformamide and dimethyl sulfoxide studies by nuclear magnetic resonance line broadening Funahashi, S.; Jordon, R. B. Inorganic Chemistry, Vol. 16, Issue 6 https://doi.org/10.1021/ic50172a010	journal	June 1977
Potential-sweep voltammetry: General theory of chemical polarization Savéant, J. M.; Vianello, E. Electrochimica Acta, Vol. 12, Issue 6 https://doi.org/10.1016/0013-4686(67)85031-X	journal	June 1967
Synthesis of a First-Row Transition Metal Parent Amido Complex and Carbon Monoxide Insertion into the Amide N−H Bond Fox, Daniel J.; Bergman, Robert G. Journal of the American Chemical Society, Vol. 125, Issue 30 https://doi.org/10.1021/ja035707a	journal	July 2003
Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts Costentin, Cyrille; Savéant, Jean-Michel ChemElectroChem, Vol. 1, Issue 7 https://doi.org/10.1002/celc.201300263	journal	June 2014
Homogeneous redox catalysis of electrochemical reactions Andrieux, C. P.; Blocman, C.; Dumas-Bouchiat, J. M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 113, Issue 1 https://doi.org/10.1016/S0022-0728(80)80508-0	journal	October 1980
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
Foot of the Wave Analysis for Mechanistic Elucidation and Benchmarking Applications in Molecular Water Oxidation Catalysis Matheu, Roc; Neudeck, Sven; Meyer, Franc ChemSusChem, Vol. 9, Issue 23 https://doi.org/10.1002/cssc.201601286	journal	November 2016
Interpreting the Electrocatalytic Voltammetry of Homogeneous Catalysts by the Foot of the Wave Analysis and Its Wider Implications Wang, Vincent C. -C.; Johnson, Ben A. ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b00850	journal	June 2019
A Local Proton Source Enhances CO ₂ Electroreduction to CO by a Molecular Fe Catalyst Costentin, Cyrille; Drouet, Samuel; Robert, Marc Science, Vol. 338, Issue 6103 https://doi.org/10.1126/science.1224581	journal	October 2012

Cited By (1)

Triple hydrogen atom abstraction from Mn–NH 3 complexes results in cyclophosphazenium cations Cook, Brian J.; Johnson, Samantha I.; Chambers, Geoffrey M. Chemical Communications, Vol. 55, Issue 93 https://doi.org/10.1039/c9cc06915a	journal	January 2019

Similar Records

Synthesis and reactions of monomeric hydrazine and hydrazido complexes that contain the Cp*MoMe[sub 3] core

Journal Article · Wed Jun 09 00:00:00 EDT 1993 · Inorganic Chemistry; (United States) · OSTI ID:1708895

Vale, M G; Schrock, R R

Electrocatalytic Alcohol Oxidation with Iron-Based Acceptorless Alcohol Dehydrogenation Catalyst

Journal Article · Mon Dec 30 00:00:00 EST 2019 · Inorganic Chemistry · OSTI ID:1708895

McLoughlin, Elizabeth A.; Matson, Benjamin D.; Sarangi, Ritimukta; +1 more

Porous Two-dimensional Iron-Cyano Nanosheets for High-rate Electrochemical Nitrate Reduction

Journal Article · Fri Dec 17 00:00:00 EST 2021 · ACS Nano · OSTI ID:1708895

Fang, Zhiwei; Jin, Zhaoyu; Tang, Sishuang; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia oxidation
iron catalysis
solar fuels
electrocatalysis
low-carbon fuels

Title: Electrocatalytic Ammonia Oxidation Mediated by a Polypyridyl Iron Catalyst

Citation Formats

References (61)

Cited By (1)

Linked Research (1)

Similar Records

Related Subjects