Fundamental Limits of Dissociative Electrochemical Ammonia Synthesis via Electrodeposited Metals

Fuente: arXiv
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Main Authors: Azumah, Victor, Viswanathan, Venkatasubramanian
Format: Preprint
Published: 2025
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author Azumah, Victor
Viswanathan, Venkatasubramanian
author_facet Azumah, Victor
Viswanathan, Venkatasubramanian
contents Electrochemical ammonia synthesis via lithium-mediated nitrogen dissociation has demonstrated exceptional Faradaic efficiency at ambient conditions, but its viability is limited by a high energy cost of ~9.12 eV per NH3 via lithium electrodeposition. Here, we establish the thermodynamic limits for dissociative nitrogen reduction using elemental metals by decomposing the process into three steps: metal deposition, nitridation, and protonation. We derive energetic constraints that any viable mediator must satisfy and show that highly reducing metals impose significant energetic penalties. To reduce this cost, we explore solvent tuning and bimetallic alloy strategies that shift deposition potentials without compromising nitridation spontaneity. Our results offer design principles for lowering the energy input of dissociative nitrogen reduction while maintaining its selectivity advantage over associative routes.
format Preprint
id arxiv_https___arxiv_org_abs_2507_21121
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Fundamental Limits of Dissociative Electrochemical Ammonia Synthesis via Electrodeposited Metals
Azumah, Victor
Viswanathan, Venkatasubramanian
Chemical Physics
Materials Science
Electrochemical ammonia synthesis via lithium-mediated nitrogen dissociation has demonstrated exceptional Faradaic efficiency at ambient conditions, but its viability is limited by a high energy cost of ~9.12 eV per NH3 via lithium electrodeposition. Here, we establish the thermodynamic limits for dissociative nitrogen reduction using elemental metals by decomposing the process into three steps: metal deposition, nitridation, and protonation. We derive energetic constraints that any viable mediator must satisfy and show that highly reducing metals impose significant energetic penalties. To reduce this cost, we explore solvent tuning and bimetallic alloy strategies that shift deposition potentials without compromising nitridation spontaneity. Our results offer design principles for lowering the energy input of dissociative nitrogen reduction while maintaining its selectivity advantage over associative routes.
title Fundamental Limits of Dissociative Electrochemical Ammonia Synthesis via Electrodeposited Metals
topic Chemical Physics
Materials Science
url https://arxiv.org/abs/2507.21121