The role of ion solvation in lithium mediated nitrogen reduction

Westhead, Olivia; Spry, Matthew; Bagger, Alexander; Shen, Zukang; Yadegari, Hossein; Favero, Silvia; Tort, Romain; Titirici, Maria‐Magdalena; Ryan, Mary P.; Jervis, Rhodri; Katayama, Yu; Aguadero, Ainara; Regoutz, Anna; Grimaud, Alexis; Stephens, Ifan E. L.

doi:10.1039/d2ta07686a

Cited by 37 publications

(77 citation statements)

References 59 publications

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“…The lithium-mediated ammonia synthesis, initially proposed by Tsuneto et al, allows the splitting of the N 2 bond by direct dissociation on metallic Li; much evidence suggests that the selectivity is due to the formation of a solid electrolyte interphase over the active surface (Figure ). − Despite several breakthroughs in performance, − the current understanding of this system is still largely limited, notably by the nature of experimental setups. To date, researchers in the field have mostly been using Pt or Ag wires as pseudoreferences in conventional three-electrode systems. − However, these metals do not have a well-defined redox couple in this medium, and the equilibrium defining their redox potential is unknown .…”

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“…It therefore makes sense to use a material that can equilibrate with Li ions to meet criterion i. As much as the research community draws inspiration from Li-ion battery science to understand and optimize this reaction, ,, one can design a reference electrode accordingly. In this regard, battery intercalation materials such as lithium iron phosphate (LiFePO 4 ) and lithium titanate (Li 4 Ti 5 O 12 ) stand out.…”

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“…The as-assembled gastight cell was sequentially filled with test electrolytes containing 10 mM Ferrocene and was saturated with N 2 . For most of this work, LiNTf 2 1 M was chosen as a model electrolyte for its stable working electrode potential during electrolysis and for its high conductivity. , The Ferrocene–Ferrocenium redox couple acts as an internal reference redox system, with a defined one electron redox equilibrium (Figure a, insert). In every test condition, a cyclic voltammogram of the electrolyte was recorded within the Ferrocene–Ferrocenium redox voltage range, at a 50 mV·s –1 rate.…”

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Nonaqueous Li-Mediated Nitrogen Reduction: Taking Control of Potentials

et al. 2023

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The performance of the Li-mediated ammonia synthesis has progressed dramatically since its recent reintroduction. However, fundamental understanding of this reaction is slower paced, due to the many uncontrolled variables influencing it. To address this, we developed a true nonaqueous LiFePO4 reference electrode, providing both a redox anchor from which to measure potentials against and estimates of sources of energy efficiency loss. We demonstrate its stable electrochemical potential in operation using different N2- and H2-saturated electrolytes. Using this reference, we uncover the relation between partial current density and potentials. While the counter electrode potential increases linearly with current, the working electrode remains stable at lithium plating, suggesting it to be the only electrochemical step involved in this process. We also use the LiFePO4/Li+ equilibrium as a tool to probe Li-ion activity changes in situ. We hope to drive the field toward more defined systems to allow a holistic understanding of this reaction.

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Nonaqueous Li-Mediated Nitrogen Reduction: Taking Control of Potentials

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“…Other elements observed in trace amounts have been excluded. H cannot be detected by XPS so is also excluded but will be present in the SEI 23 . Data for dry samples is replotted from previous work 23 .…”

Section: And 1 M Liclo4 Electrolytes Under Dry (Red Line) Optimum Wat...mentioning

confidence: 99%

“…H cannot be detected by XPS so is also excluded but will be present in the SEI 23 . Data for dry samples is replotted from previous work 23 . All samples were gently rinsed in 0.1 ml of THF after the experiment to remove dried electrolyte from the surface.…”

Section: And 1 M Liclo4 Electrolytes Under Dry (Red Line) Optimum Wat...mentioning

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Water increases Faradaic selectivity of Li-mediated nitrogen reduction.

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et al. 2022

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The lithium-mediated system catalyses nitrogen to ammonia under ambient conditions. Herein we discover that trace amount of water - in contrast to prior reports from the literature – can effect a dramatic improvement in the Faradaic selectivity of N2 reduction to NH3. We report an optimal water concentration of 35.5 mM and LiClO4 salt concentration of 0.8 M allows a Faradaic efficiency up to 27.7% at ambient pressure. We attribute the increase in Faradaic efficiency to the incorporation of Li2O in the solid electrolyte interphase, as suggested by our X-ray photoelectron spectroscopy measurements. Our results highlight the extreme sensitivity of lithium mediated N2 reduction to small changes in the experimental conditions.

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Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

et al. 2023

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Natural nitrogen cycle has been severely disrupted by anthropogenic activities. The overuse of N‐containing fertilizers induces the increase of nitrate level in surface and ground waters, and substantial emission of nitrogen oxides causes heavy air pollution. Nitrogen gas, as the main component of air, has been used for mass ammonia production for over a century, providing enough nutrition for agriculture to support world population increase. In the last decade, researchers have made great efforts to develop ammonia processes under ambient conditions to combat the intensive energy consumption and high carbon emission associated with the Haber‐Bosch process. Among different techniques, electrochemical nitrate reduction reaction (NO3RR) can achieve nitrate removal and ammonia generation simultaneously using renewable electricity as the power, and there is an exponential growth of studies in this research direction. Here we provide a timely and comprehensive review on the important progresses of electrochemical NO3RR, covering the rational design of electrocatalysts, emerging C‐N coupling reactions, and advanced energy conversion and storage systems. Moreover, future perspectives are proposed to accelerate the industrialized NH3 production and green synthesis of chemicals, leading to a sustainable nitrogen cycle via prosperous N‐based electrochemistry.This article is protected by copyright. All rights reserved

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The role of ion solvation in lithium mediated nitrogen reduction

Abstract: Since its verification in 2019, there have been numerous high-profile papers reporting improved efficiency of lithium-mediated electrochemical nitrogen reduction to make ammonia. However, the literature lacks any coherent investigation systematically...

Cited by 37 publications

References 59 publications

Nonaqueous Li-Mediated Nitrogen Reduction: Taking Control of Potentials

Nonaqueous Li-Mediated Nitrogen Reduction: Taking Control of Potentials

Water increases Faradaic selectivity of Li-mediated nitrogen reduction.

Electrochemical Nitrate Reduction: Ammonia Synthesis and the Beyond

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