Elementary kinetics of nitrogen electroreduction on Fe surfaces

Maheshwari, Sharad; Rostamikia, Gholamreza; Janik, Michael J.

doi:10.1063/1.5048036

Title: Elementary kinetics of nitrogen electroreduction on Fe surfaces

Journal Article · Thu Nov 29 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5048036· OSTI ID:1482070

Maheshwari, Sharad ^[1]; Rostamikia, Gholamreza ^[2]; Janik, Michael J. ^[1]

Pennsylvania State Univ., University Park, PA (United States). Dept. of Chemical Engineering
Univ. of North Carolina, Wilmington, NC (United States). Dept. of Chemistry and Biochemistry

Electrochemical ammonia synthesis could provide a sustainable and efficient alternative to the energy intensive Haber-Bosch process. Development of an active and selective N₂ electroreduction catalyst requires mechanism determination to aid in connecting catalyst composition and structure to performance. Density functional theory calculations are used to examine the elementary step energetics of associative N₂ reduction mechanisms on two low index Fe surfaces. Interfacial water molecules in the Heyrovsky-like mechanism help lower some of the elementary activation barriers. Electrode potential dependent barriers show that cathodic potentials below -1.5 V-RHE are necessary to give a significant rate of N₂ electroreduction. DFT barriers suggest a larger overpotential than expected based on elementary reaction free energies. Linear Brønsted-Evans-Polanyi relationships do not hold across N–H formation steps on these surfaces, further confirming that explicit barriers should be considered in DFT studies of the nitrogen reduction reaction.

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Research Organization:: Pennsylvania State Univ., University Park, PA (United States); University of North Carolina, Wilmington, NC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)

Grant/Contract Number:: SC0016529; ACI-1053575; DGE-1449785

OSTI ID:: 1482070

Journal Information:: Journal of Chemical Physics, Vol. 150, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 25 works

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References (27)

Catalysts for nitrogen reduction to ammonia Foster, Shelby L.; Bakovic, Sergio I. Perez; Duda, Royce D. Nature Catalysis, Vol. 1, Issue 7 https://doi.org/10.1038/s41929-018-0092-7	journal	July 2018
Electron transfer, bond breaking, and bond formation Saveant, Jean Michel Accounts of Chemical Research, Vol. 26, Issue 9 https://doi.org/10.1021/ar00033a001	journal	September 1993
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
Structural, electronic, and magnetic properties of bcc iron surfaces Błoński, P.; Kiejna, A. Surface Science, Vol. 601, Issue 1 https://doi.org/10.1016/j.susc.2006.09.013	journal	January 2007
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Ozone Oxidation of Single Walled Carbon Nanotubes from Density Functional Theory Yim, Wai-Leung; Johnson, J. Karl The Journal of Physical Chemistry C, Vol. 113, Issue 41 https://doi.org/10.1021/jp908089c	journal	September 2009
Electrocatalytic Synthesis of Ammonia at Room Temperature and Atmospheric Pressure from Water and Nitrogen on a Carbon-Nanotube-Based Electrocatalyst Chen, Shiming; Perathoner, Siglinda; Ampelli, Claudio Angewandte Chemie International Edition, Vol. 56, Issue 10 https://doi.org/10.1002/anie.201609533	journal	January 2017
Electrochemical Acceleration of Ammonia Synthesis on Fe-Based Alkali-Promoted Electrocatalyst with Proton Conducting Solid Electrolyte Kosaka, Fumihiko; Nakamura, Takehisa; Oikawa, Akio ACS Sustainable Chemistry & Engineering, Vol. 5, Issue 11 https://doi.org/10.1021/acssuschemeng.7b02469	journal	October 2017
Selectivity of CO ₂ Reduction on Copper Electrodes: The Role of the Kinetics of Elementary Steps Nie, Xiaowa; Esopi, Monica R.; Janik, Michael J. Angewandte Chemie International Edition, Vol. 52, Issue 9 https://doi.org/10.1002/anie.201208320	journal	January 2013
Superlinearly converging dimer method for transition state search Kästner, Johannes; Sherwood, Paul The Journal of Chemical Physics, Vol. 128, Issue 1 https://doi.org/10.1063/1.2815812	journal	January 2008
Activation of an Alkyl C−H Bond Geminal to an Agostic Interaction: An Unusual Mode of Base-Induced C−H Activation Häller, L. Jonas L.; Page, Michael J.; Macgregor, Stuart A. Journal of the American Chemical Society, Vol. 131, Issue 13 https://doi.org/10.1021/ja900953d	journal	April 2009
Surface Science and Catalysis—Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address Ertl, G. Catalysis Reviews, Vol. 21, Issue 2 https://doi.org/10.1080/03602458008067533	journal	January 1980
Hydrazine is a product of dinitrogen reduction by the vanadium-nitrogenase from Azotobacter chroococcum Dilworth, M. J.; Eady, R. R. Biochemical Journal, Vol. 277, Issue 2 https://doi.org/10.1042/bj2770465	journal	July 1991
First-principles based microkinetic modeling of borohydride oxidation on a Au(111) electrode Rostamikia, Gholamreza; Mendoza, Alfonso J.; Hickner, Michael A. Journal of Power Sources, Vol. 196, Issue 22 https://doi.org/10.1016/j.jpowsour.2011.07.042	journal	November 2011
The Challenge of Electrochemical Ammonia Synthesis: A New Perspective on the Role of Nitrogen Scaling Relations Montoya, Joseph H.; Tsai, Charlie; Vojvodic, Aleksandra ChemSusChem, Vol. 8, Issue 13 https://doi.org/10.1002/cssc.201500322	journal	June 2015
Universal transition state scaling relations for (de)hydrogenation over transition metals Wang, S.; Petzold, V.; Tripkovic, V. Physical Chemistry Chemical Physics, Vol. 13, Issue 46 https://doi.org/10.1039/c1cp20547a	journal	January 2011
Reaction mechanisms of CO2 electrochemical reduction on Cu(111) determined with density functional theory Nie, Xiaowa; Luo, Wenjia; Janik, Michael J. Journal of Catalysis, Vol. 312 https://doi.org/10.1016/j.jcat.2014.01.013	journal	April 2014
Catalyst Design by Interpolation in the Periodic Table: Bimetallic Ammonia Synthesis Catalysts Jacobsen, Claus J. H.; Dahl, Søren; Clausen, Bjerne S. Journal of the American Chemical Society, Vol. 123, Issue 34 https://doi.org/10.1021/ja010963d	journal	August 2001
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
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode Nørskov, J. K.; Rossmeisl, J.; Logadottir, A. The Journal of Physical Chemistry B, Vol. 108, Issue 46 https://doi.org/10.1021/jp047349j	journal	November 2004
Mechanism of Molybdenum Nitrogenase Burgess, Barbara K.; Lowe, David J. Chemical Reviews, Vol. 96, Issue 7 https://doi.org/10.1021/cr950055x	journal	January 1996
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Beyond fossil fuel–driven nitrogen transformations Chen, Jingguang G.; Crooks, Richard M.; Seefeldt, Lance C. Science, Vol. 360, Issue 6391 https://doi.org/10.1126/science.aar6611	journal	May 2018
Catalytic and electrocatalytic synthesis of NH3 in a H+ conducting cell by using an industrial Fe catalyst Ouzounidou, M.; Skodra, A.; Kokkofitis, C. Solid State Ionics, Vol. 178, Issue 1-2 https://doi.org/10.1016/j.ssi.2006.11.019	journal	January 2007
A simple method to approximate electrode potential-dependent activation energies using density functional theory Akhade, Sneha A.; Bernstein, Nicole J.; Esopi, Monica R. Catalysis Today, Vol. 288 https://doi.org/10.1016/j.cattod.2017.01.050	journal	June 2017
Mechanism of Mo-Dependent Nitrogenase Seefeldt, Lance C.; Hoffman, Brian M.; Dean, Dennis R. Annual Review of Biochemistry, Vol. 78, Issue 1 https://doi.org/10.1146/annurev.biochem.78.070907.103812	journal	June 2009

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