4.8 Article

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

期刊

ACS CATALYSIS
卷 12, 期 9, 页码 5197-5208

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acscatal.2c00389

关键词

electrochemistry; ammonia synthesis; lithium-mediated; nonaqueous; solid electrolyte interphase; proton donor

资金

  1. National Science Foundation [2204756, 1122374, CBET-1554273]
  2. Scott Institute for Energy Innovation at Carnegie Mellon University

向作者/读者索取更多资源

This study investigates the influence of proton donor selection and concentration on ammonia production in lithium-mediated electrochemical nitrogen reduction reaction (LM-NRR). The research finds that alcohols can promote nitrogen reduction, with n-butanol exhibiting the highest ammonia Faradaic efficiency. Additionally, slight changes in proton donor structure significantly affect ammonia yield, and there is a thresholding behavior regarding the selectivity of ammonia depending on proton donor concentration.
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 (SET), 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.

作者

我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。

评论

主要评分

4.8
评分不足

次要评分

新颖性
-
重要性
-
科学严谨性
-
评价这篇论文

推荐

暂无数据
暂无数据