Saving the Energy Loss in Lithium‐Mediated Nitrogen Fixation by Using a Highly Reactive Li₃N Intermediate for C−N Coupling Reactions

Abstract

Direct synthesis of N‐containing organic compounds from dinitrogen (N2) can make synthetic chemistry more sustainable. Previous bottlenecks in lithium‐mediated N2 fixation were resolved by loading Li‐metal anodes covered with the typical Li+ ion‐conducting solid electrolyte interface, which are subsequently allowed to react with N2. The developed strategy allowed us to reach high Faradaic efficiencies toward Li3N. These reactive Li3N were then contacted with acylchlorides. Surface nitride ions are more nucleophilic than amines which direct the two C−N coupling reactions toward formation of imides rather than amides, and an integrated current efficiency of 57–77 % could be realized. This study thereby not only provides a feasible electrochemical Li3N synthesis, but also delineates an economical and green synthesis of highly valuable N‐containing compounds from N2 under mild conditions, just using commercial spare parts and processes from the omnipresent Li battery technology.