Searching for the rules of electrochemical nitrogen fixation
File(s)
Author(s)
Type
Journal Article
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.
Date Issued
2023-11-17
Date Acceptance
2023-10-11
Citation
ACS Catalysis, 2023, 13 (22), pp.14513-14522
ISSN
2155-5435
Publisher
American Chemical Society
Start Page
14513
End Page
14522
Journal / Book Title
ACS Catalysis
Volume
13
Issue
22
Copyright Statement
© 2023 The Authors. Published by American Chemical Society. This publication is licensed under
CC-BY 4.0.
CC-BY 4.0.
License URL
Identifier
https://www.ncbi.nlm.nih.gov/pubmed/38026818
Publication Status
Published
Coverage Spatial
United States
Date Publish Online
2023-11-02