Elementary kinetics of nitrogen electroreduction on Fe surfaces

Sharad Maheshwari, Gholamreza Rostamikia, Michael J. Janik

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

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 the catalyst composition and structure to performance. Density functional theory (DFT) 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 (reversible hydrogen electrode) 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.

Original languageEnglish (US)
Article number041708
JournalJournal of Chemical Physics
Volume150
Issue number4
DOIs
StatePublished - Jan 28 2019

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Density functional theory
Nitrogen
nitrogen
Kinetics
kinetics
density functional theory
Electrodes
Catalysts
Ammonia
catalysts
Free energy
electrodes
Hydrogen
Chemical activation
ammonia
Molecules
Water
free energy
activation
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Maheshwari, Sharad ; Rostamikia, Gholamreza ; Janik, Michael J. / Elementary kinetics of nitrogen electroreduction on Fe surfaces. In: Journal of Chemical Physics. 2019 ; Vol. 150, No. 4.
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Elementary kinetics of nitrogen electroreduction on Fe surfaces. / Maheshwari, Sharad; Rostamikia, Gholamreza; Janik, Michael J.

In: Journal of Chemical Physics, Vol. 150, No. 4, 041708, 28.01.2019.

Research output: Contribution to journalArticle

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