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Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction

Lazouski, Nikifar and Steinberg, Katherine J. and Gala, Michal L. and Krishnamurthy, Dilip and Viswanathan, Venkatasubramanian and Manthiram, Karthish (2022) Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction. ACS Catalysis, 12 (9). pp. 5197-5208. ISSN 2155-5435. doi:10.1021/acscatal.2c00389. https://resolver.caltech.edu/CaltechAUTHORS:20220419-936081000

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Abstract

Alternative approaches for producing ammonia are necessary to reduce the environmental impact of its production. The lithium-mediated electrochemical nitrogen reduction reaction (LM-NRR) is one attractive alternative method for producing ammonia at small scales in a distributed process. This process requires a proton donor in the electrolyte to produce ammonia from nitrogen, but the role of the proton donor in selective ammonia production is not well understood. In this work, we experimentally tested several classes of proton donors for the ability to promote LM-NRR. We found that a wide array of alcohols can promote nitrogen reduction and that n-butanol leads to the highest ammonia Faradaic efficiencies. Among the tested proton donors, even slight changes in the proton donor structure can significantly affect the yield of ammonia. In addition, most active proton donors exhibit a thresholding behavior as a function of their concentration, where the selectivity toward ammonia increases dramatically above a certain concentration of the proton donor. We found evidence to imply that these effects could be due to the proton-donor-induced changes in the properties of the solid electrolyte interphase (SEI), which lead to changes in the diffusion of relevant species through the SEI to the reactive electrode. By selectively allowing for diffusion of nitrogen over the proton donor to the electrode, the SEI can promote selective nitrogen reduction to ammonia. A coupled kinetic transport model of the process was proposed to explain the observed trends and to predict ammonia production as a function of operating conditions.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acscatal.2c00389DOIArticle
ORCID:
AuthorORCID
Lazouski, Nikifar0000-0002-4655-2041
Steinberg, Katherine J.0000-0002-8232-7714
Gala, Michal L.0000-0003-0676-5146
Krishnamurthy, Dilip0000-0001-8231-5492
Viswanathan, Venkatasubramanian0000-0003-1060-5495
Manthiram, Karthish0000-0001-9260-3391
Additional Information:© 2022 American Chemical Society. Received: January 21, 2022; Revised: March 30, 2022; Published: April 15, 2022. We thank Matt Wolski of Daramic for providing us with polyporous separator samples. This material was based on the work supported by the National Science Foundation under grant no. 2204756. N.L. and K.J.S. acknowledge the support by the National Science Foundation Graduate Research Fellowship under grant no. 1122374. D.K. and V.V. gratefully acknowledge the funding support from the National Science Foundation under the award CBET-1554273. V.V. acknowledges the support from the Scott Institute for Energy Innovation at Carnegie Mellon University. The authors declare no competing financial interest. Credit: Some of the data presented in the present work have been published previously in Lazouski, N. Development of a Lithium-Mediated Nitrogen Reduction Process and in ACS Cent. Sci. 2021, 7, 12, 2073–2082. Data availability: The data that support the plots within this paper and other findings of this study are available from the corresponding author upon request. Image processing software: Data were plotted in Origin 2018b (9.5). The plots obtained from Origin were compiled in Adobe Illustrator v 25.2. Diagrams were drawn in Adobe Illustrator.
Funders:
Funding AgencyGrant Number
NSFCBET-2204756
NSF Graduate Research FellowshipDGE-1122374
NSFCBET-1554273
Carnegie Mellon UniversityUNSPECIFIED
Subject Keywords:electrochemistry; ammonia synthesis; lithium-mediated; nonaqueous; solid electrolyte interphase; proton donor
Issue or Number:9
DOI:10.1021/acscatal.2c00389
Record Number:CaltechAUTHORS:20220419-936081000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220419-936081000
Official Citation:Proton Donors Induce a Differential Transport Effect for Selectivity toward Ammonia in Lithium-Mediated Nitrogen Reduction. Nikifar Lazouski, Katherine J. Steinberg, Michal L. Gala, Dilip Krishnamurthy, Venkatasubramanian Viswanathan, and Karthish Manthiram. ACS Catalysis 2022 12 (9), 5197-5208; DOI: 10.1021/acscatal.2c00389
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:114379
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:20 Apr 2022 14:20
Last Modified:17 May 2022 16:53

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