Influence of Gaseous Oxygen Species on Liquid-Phase, Fixed Nitrogen Products in Aqueous Plasma-Based Electrochemical Processes

IF 2.5 3区物理与天体物理 Q3 ENGINEERING, CHEMICAL

Plasma Chemistry and Plasma Processing Pub Date : 2025-05-28 DOI:10.1007/s11090-025-10571-2

Brandon Kamiyama, Mohammad Ali Eslamisaray, Emily Gillmore, R. Mohan Sankaran

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Abstract

Electrified, small-scale, remote approaches are needed as an alternative to conventional centralized methods for nitrogen fixation in order to reduce our reliance on fossil fuels and ensure global food security. Plasma-based electrolytic processes offer a promising solution by directly reacting molecular nitrogen and water under mild conditions. However, the complex non-equilibrium chemistry results in a diverse range of gas-phase and liquid-phase reactions, which impacts selectivity toward desired products. In this study, we investigate the influence of feed gas composition, specifically the presence of molecular oxygen at minute quantities, on the liquid-phase nitrogen products. Specifically, oxygen gas concentrations as low as 0.1% in the gas feed are found to substantially affect the selectivity towards ammonium ions. We additionally show that the total gas flow rate has an indiscriminate effect on both ammonium and nitrate/nitrite ion yields because of the presence of water vapor. By carefully controlling these process parameters, a production rate for ammonium ions exceeding 1 mg/h with a molar selectivity of ~ 14 is achieved. Our results highlight the importance of gas-phase chemistry in plasma-based electrolytic nitrogen fixation.

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水溶液等离子体电化学过程中气态氧对液相固定氮产物的影响

为了减少我们对化石燃料的依赖，确保全球粮食安全，需要电气化、小规模、远程的方法来替代传统的集中固氮方法。等离子体电解工艺通过在温和条件下直接反应分子氮和水，提供了一种很有前途的解决方案。然而，复杂的非平衡化学反应导致气相和液相反应的多样性，这影响了对所需产物的选择性。在本研究中，我们研究了原料气组成，特别是微量分子氧的存在对液相氮产物的影响。具体地说，进料中低至0.1%的氧气浓度会显著影响对铵离子的选择性。我们还表明，由于水蒸气的存在，总气体流量对铵离子和硝酸盐/亚硝酸盐离子的产率都有不加区分的影响。通过仔细控制这些工艺参数，实现了超过1 mg/h的铵离子收率，摩尔选择性为~ 14。我们的研究结果强调了气相化学在等离子体电解固氮中的重要性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Plasma Chemistry and Plasma Processing 工程技术-工程：化工

CiteScore

5.90

自引率

8.30%

发文量

审稿时长

6-12 weeks

期刊介绍： Publishing original papers on fundamental and applied research in plasma chemistry and plasma processing, the scope of this journal includes processing plasmas ranging from non-thermal plasmas to thermal plasmas, and fundamental plasma studies as well as studies of specific plasma applications. Such applications include but are not limited to plasma catalysis, environmental processing including treatment of liquids and gases, biological applications of plasmas including plasma medicine and agriculture, surface modification and deposition, powder and nanostructure synthesis, energy applications including plasma combustion and reforming, resource recovery, coupling of plasmas and electrochemistry, and plasma etching. Studies of chemical kinetics in plasmas, and the interactions of plasmas with surfaces are also solicited. It is essential that submissions include substantial consideration of the role of the plasma, for example, the relevant plasma chemistry, plasma physics or plasma–surface interactions; manuscripts that consider solely the properties of materials or substances processed using a plasma are not within the journal’s scope.