Searching for the Rules of Electrochemical Nitrogen Fixation

Romain Tort, Alexander Bagger, Olivia Westhead, Yasuyuki Kondo, Artem Khobnya, Anna Winiwarter, Bethan J.V. Davies, Aron Walsh, Yu Katayama, Yuki Yamada, Mary P. Ryan, Maria Magdalena Titirici, Ifan E.L. Stephens

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Li-mediated ammonia synthesis is, thus far, the only electrochemical method for heterogeneous decentralized ammonia production. The unique selectivity of the solid electrode provides an alternative to one of the largest heterogeneous thermal catalytic processes. However, it is burdened with intrinsic energy losses, operating at a Li plating potential. In this work, we survey the periodic table to understand the fundamental features that make Li stand out. Through density functional theory calculations and experimentation on chemistries analogous to lithium (e.g., Na, Mg, Ca), we find that lithium is unique in several ways. It combines a stable nitride that readily decomposes to ammonia with an ideal solid electrolyte interphase, balancing reagents at the reactive interface. We propose descriptors based on simulated formation and binding energies of key intermediates and further on hard and soft acids and bases (HSAB principle) to generalize such features. The survey will help the community toward electrochemical systems beyond Li for nitrogen fixation.

Original languageEnglish
Pages (from-to)14513-14522
Number of pages10
JournalACS Catalysis
Volume13
Issue number22
DOIs
StatePublished - 17 Nov 2023

Bibliographical note

Publisher Copyright:
© 2023 The Authors. Published by American Chemical Society

Keywords

  • HSAB principle
  • ammonia synthesis
  • electrosynthesis
  • lithium-mediated
  • nitride
  • nitrogen fixation
  • nitrogen reduction
  • solid-electrolyte interphase

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