Evaluating the Thermodynamics of Electrocatalytic N2 Reduction in Acetonitrile

Brian M. Lindley, Aaron M. Appel, Karsten Krogh-Jespersen, James M. Mayer, Alexander J.M. Miller

Research output: Contribution to journalArticlepeer-review

54 Citations (Scopus)


The development of a sustainable ammonia synthesis by proton-coupled electroreduction of dinitrogen (N2) requires knowledge of the thermodynamics described by standard reduction potentials. The first collection of N2 reduction standard potentials in an organic solvent are reported here. The potentials for reduction of N2 to ammonia (NH3), hydrazine (N2H4), and diazene (N2H2) in acetonitrile (MeCN) solution are derived using thermochemical cycles. Ammonia is thermodynamically favored, with a 0.43 V difference between NH3 and N2H4 and a 1.26 V difference between NH3 and N2H2. The thermodynamics for reduction of N2 to the protonated products ammonium (NH4 +) and hydrazinium (N2H5 +) under acidic conditions are also presented. Comparison with the H+/H2 potential in MeCN reveals a 63 mV thermodynamic preference for N2 reduction to NH3 over H2 production. Combined with knowledge of the kinetics of electrode-catalyzed H2 evolution, a wide working region is identified to guide future electrocatalytic studies.

Original languageEnglish
Pages (from-to)698-704
Number of pages7
JournalACS Energy Letters
Issue number4
Publication statusPublished - Oct 14 2016

ASJC Scopus subject areas

  • Chemistry (miscellaneous)
  • Renewable Energy, Sustainability and the Environment
  • Fuel Technology
  • Energy Engineering and Power Technology
  • Materials Chemistry

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