Searching for the Rules of Electrochemical Nitrogen Fixation.
Romain TortAlexander BaggerOlivia WestheadYasuyuki KondoArtem KhobnyaAnna WiniwarterBethan J V DaviesAron WalshYu KatayamaYuki YamadaMary P RyanMaria-Magdalena TitirciIfan E L StephensPublished in: ACS catalysis (2023)
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.
Keyphrases
- density functional theory
- solid state
- ion batteries
- ionic liquid
- gold nanoparticles
- molecular dynamics
- room temperature
- molecularly imprinted
- anaerobic digestion
- minimally invasive
- cross sectional
- label free
- mental health
- healthcare
- binding protein
- molecular dynamics simulations
- transcription factor
- risk assessment
- climate change