Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

Jayanarasimhan, Ananthanarasimhan; Pierrard, Robert; Peyres, Sean M.; Yatom, Shurik; Curreli, Davide; Sankaran, R. Mohan

doi:10.1021/acssuschemeng.4c05771

Title: Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

Journal Article · 18 December 2024 · ACS Sustainable Chemistry & Engineering

DOI: https://doi.org/10.1021/acssuschemeng.4c05771 · OSTI ID:2526595

^[1]; Pierrard, Robert ^[1]; Peyres, Sean M. ^[1];

^[2]; Curreli, Davide ^[1];

^[1]

University of Illinois at Urbana-Champaign, IL (United States)
Princeton University, NJ (United States)

In this article, there is growing interest in reacting molecular nitrogen and water to sustainably synthesize fixed forms of nitrogen such as ammonia. In particular, low-temperature plasmas can activate these relatively inert feedstocks at or near room temperature without a catalyst. However, because of the enhanced reactivity and nonequilibrium chemistry, a diverse range of products is formed, and the underlying reaction mechanisms are exceedingly complex. In this work, we studied a simplified reactor consisting of a gaseous plasma containing controlled mixtures of nitrogen gas and water vapor. Densities of key chemical species such as N, H, OH, NH, and NO were measured by emission and laser-based spectroscopy as a function of the relative humidity. A global model was constructed and the reaction network was validated by comparing calculated species densities with experiments. We discover that N, a key initial intermediate for ammonia, strongly decreases in the presence of water vapor, and as a result, ammonia formation becomes limited at high relative humidity. This decrease is surprisingly not because N itself reacts, but because one of its main sources, an excited molecular nitrogen state, is reacted away. In addition, oxidation pathways for nitrogen, which lead to NO and related products, are found to be favored over reduction pathways because the corresponding reverse reactions are less significant. Together, this understanding helps explain previously reported observations of selectivity toward nitrogen oxides over ammonia, particularly at higher relative humidities.

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Research Organization:: Princeton Plasma Physics Laboratory (PPPL), Princeton, NJ (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Fusion Energy Sciences (FES)

Grant/Contract Number:: AC02-09CH11466; SC0023404

OSTI ID:: 2526595

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 1 Vol. 13; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ammonia
atmospheric-pressure plasma
chemical calculations
chemical reactions
humidity
laser-induced fluorescence
nitrogen
nitrogen fixation
plasma
plasma-liquid

Title: Insights into Sustainable Nitrogen Fixation by Gas-phase Spectroscopic Measurements and Global Modeling of Reaction Intermediates in Humid Nitrogen Plasma

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