{"title":"Samarium as a Catalytic Electron-Transfer Mediator in Electrocatalytic Nitrogen Reduction to Ammonia","authors":"Emily A. Boyd, Hoimin Jung, Jonas C. Peters","doi":"10.1021/jacs.4c14845","DOIUrl":null,"url":null,"abstract":"Samarium diiodide (SmI<sub>2</sub>) exhibits high selectivity for N<sub>2</sub>R catalyzed by molybdenum complexes; however, it has so far been employed only as a stoichiometric reagent (0.3 equiv of NH<sub>3</sub> per Sm) combined with coordinating proton sources (e.g., H<sub>2</sub>O, ROH). The latter inhibit catalytic turnover of Sm<sup>III</sup> owing to buildup of stable hydroxide/alkoxide sinks. Here, we report a tandem Sm/Mo-catalyzed <i>e</i>N<sub>2</sub>R system that achieves the lowest overpotential and highest Faradaic efficiency (82%) reported to date for nonaqueous <i>e</i>N<sub>2</sub>R at ambient pressure. Up to 8.4 equiv of NH<sub>3</sub> is produced per Sm, representing a 25-fold increase over N<sub>2</sub>R with stoichiometric SmI<sub>2</sub>. A noncoordinating proton source enables electrochemical SmI<sub>3</sub>/SmI<sub>2</sub> cycling at the applied potential of −1.45 V vs Fc<sup>+/0</sup>.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":"4 1","pages":""},"PeriodicalIF":14.4000,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c14845","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Samarium diiodide (SmI2) exhibits high selectivity for N2R catalyzed by molybdenum complexes; however, it has so far been employed only as a stoichiometric reagent (0.3 equiv of NH3 per Sm) combined with coordinating proton sources (e.g., H2O, ROH). The latter inhibit catalytic turnover of SmIII owing to buildup of stable hydroxide/alkoxide sinks. Here, we report a tandem Sm/Mo-catalyzed eN2R system that achieves the lowest overpotential and highest Faradaic efficiency (82%) reported to date for nonaqueous eN2R at ambient pressure. Up to 8.4 equiv of NH3 is produced per Sm, representing a 25-fold increase over N2R with stoichiometric SmI2. A noncoordinating proton source enables electrochemical SmI3/SmI2 cycling at the applied potential of −1.45 V vs Fc+/0.
期刊介绍：
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.
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