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Updated: May 30, 2025

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Samarium as a Catalytic Electron-Transfer Mediator in Electrocatalytic Nitrogen Reduction to Ammonia
Emily A Boyd1, Hoimin Jung1, Jonas C Peters1
1Division of Chemistry and Chemical Engineering, California Institute of Technology (Caltech), Pasadena, California 91125, United States.
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.
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