Galvanic Cell Studies on Ionic Carbide and Nitride Solutions in Molten Salts

Bonomi, Antonio; Hadate, M.; Gentaz, C.

doi:10.1149/1.2133513

Cited by 24 publications

(10 citation statements)

References 7 publications

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“…The electrolytic formation of nitrides from N 2 in molten alkali chlorides was reported prior to 1980. 337,338 Moreover, in 1998, Goto et al 339 reported that N 2 molecules can be electrochemically reduced to nitride ions (1/2N 2 + 3e − → N 3− ) in the molten eutectic mixture of LiCl−KCl (operating at 450 °C) at a nickel wire electrode. Since then, Murakami et al carried out a series of electrochemical ammonia synthesis experiments in the molten eutectic mixture of LiCl−KCl− CsCl containing 0.5 mol % Li 3 N, using hydrogen gas (H 2 ), 340,341 methane (CH 4 ), 342 hydrogen sulfide (H 2 S), 343 hydrogen chloride (HCl), 344 or water (H 2 O) 345,346 as the hydrogen source.…”

Section: N 2 Electroreduction In Molten Alkali Chloridesmentioning

confidence: 99%

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia

et al. 2020

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Global ammonia production reached 175 million metric tons in 2016, 90% of which is produced from high purity N2 and H2 gases at high temperatures and pressures via the Haber–Bosch process. Reliance on natural gas for H2 production results in large energy consumption and CO2 emissions. Concerns of human-induced climate change are spurring an international scientific effort to explore new approaches to ammonia production and reduce its carbon footprint. Electrocatalytic N2 reduction to ammonia is an attractive alternative that can potentially enable ammonia synthesis under milder conditions in small-scale, distributed, and on-site electrolysis cells powered by renewable electricity generated from solar or wind sources. This review provides a comprehensive account of theoretical and experimental studies on electrochemical nitrogen fixation with a focus on the low selectivity for reduction of N2 to ammonia versus protons to H2. A detailed introduction to ammonia detection methods and the execution of control experiments is given as they are crucial to the accurate reporting of experimental findings. The main part of this review focuses on theoretical and experimental progress that has been achieved under a range of conditions. Finally, comments on current challenges and potential opportunities in this field are provided.

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Section: N 2 Electroreduction In Molten Alkali Chloridesmentioning

confidence: 99%

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia

et al. 2020

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“…[7][8][9][10][11][12] In particular, it has been reported that molten LiCl, and related eutectics,p ossess the fascinating ability to stabilise the N 3À ion and establish the reversible N 2 /N 3À redox couple at ambient pressure. [13][14][15][16] Ito and co-workers proposed that this could be utilised in an ammonia synthesis process,by coupling the reduction of N 2 [Eq. (1)] at ac athode with its oxidation in the presence of H 2 [Eq.…”

Section: Introductionmentioning

confidence: 99%

The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl–KCl Eutectics

et al. 2019

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Molten LiCl and related eutectic electrolytes are known to permit direct electrochemical reduction of N2 to N3− with high efficiency. It had been proposed that this could be coupled with H2 oxidation in an electrolytic cell to produce NH3 at ambient pressure. Here, this proposal is tested in a LiCl–KCl–Li3N cell and is found not to be the case, as the previous assumption of the direct electrochemical oxidation of N3− to NH3 is grossly over‐simplified. We find that Li3N added to the molten electrolyte promotes the spontaneous and simultaneous chemical disproportionation of H2 (H oxidation state 0) into H− (H oxidation state −1) and H+ in the form of NH2−/NH2−/NH3 (H oxidation state +1) in the absence of applied current, resulting in non‐Faradaic release of NH3. It is further observed that NH2− and NH2− possess their own redox chemistry. However, these spontaneous reactions allow us to propose an alternative, truly catalytic cycle. By adding LiH, rather than Li3N, N2 can be reduced to N3− while stoichiometric amounts of H− are oxidised to H2. The H2 can then react spontaneously with N3− to form NH3, regenerating H− and closing the catalytic cycle. Initial tests show a peak NH3 synthesis rate of 2.4×10−8 mol cm−2 s−1 at a maximum current efficiency of 4.2 %. Isotopic labelling with 15N2 confirms the resulting NH3 is from catalytic N2 reduction.

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“…This results in the possibility of carbide‐based galvanic cells. Reported measurements of free energy and activity of ionic carbide allow a series of electrochemical applications for this molecule to be proposed. Electro‐oxidation of the acetylide ion in a molten LiCl–KCl–CaCl 2 –CaC 2 system leads to deposition of a carbon film on a copper substrate .…”

Section: Sustainable Access Usage and Recycling Of Calcium Carbidementioning

confidence: 99%

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

2019

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Calcium carbide, a stable solid compound composed of two atoms of carbon and one of calcium, has proven its effectiveness in chemical synthesis, due to the safety and convenience of handling the C≡C acetylenic units. The areas of CaC2 application are very diverse, and the development of calcium‐mediated approaches resolves several important challenges. This Review aims to discuss the laboratory chemistry of calcium carbide, and to go beyond its frontiers to organic synthesis, life sciences, materials and construction, carbon dioxide capturing, alloy manufacturing, and agriculture. The recyclability of calcium carbide and the availability of large‐scale industrial production facilities, as well as the future possibility of fossil‐resource‐independent manufacturing, position this compound as a key chemical platform for sustainable development. Easy regeneration and reuse of the carbide highlight calcium‐based sustainable chemical technologies as promising instruments for total carbon recycling.

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Galvanic Cell Studies on Ionic Carbide and Nitride Solutions in Molten Salts

Cited by 24 publications

References 7 publications

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia

The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl–KCl Eutectics

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

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Galvanic Cell Studies on Ionic Carbide and Nitride Solutions in Molten Salts

Cited by 24 publications

References 7 publications

Recent Advances and Challenges of Electrocatalytic N2Reduction to Ammonia

Recent Advances and Challenges of Electrocatalytic N2Reduction to Ammonia

The Feasibility of Electrochemical Ammonia Synthesis in Molten LiCl–KCl Eutectics

Calcium‐Based Sustainable Chemical Technologies for Total Carbon Recycling

Contact Info

Product

Resources

About

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia

Recent Advances and Challenges of Electrocatalytic N₂Reduction to Ammonia