Elementary kinetics of nitrogen electroreduction on Fe surfaces

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

doi:10.1063/1.5048036

Elementary kinetics of nitrogen electroreduction on Fe surfaces

Journal Article · Wed Nov 28 23:00:00 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. ^[3]

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

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.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF) (United States)

Grant/Contract Number:: SC0016529

OSTI ID:: 1482070

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

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

Country of Publication:: United States

Language:: English

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