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Lithium-mediated nitrogen reduction is a proven method to electrochemically synthesize ammonia; yet the process has so far been unstable, and the continuous deposition of lithium limits its practical applicability. One...

Boosting ammonia with a little oxygen Ammonia synthesis from nitrogen for fertilizer production is highly energy intensive. Chemists are therefore exploring electrochemical approaches that could draw power from renewable sources while generating less waste. One promising cycle involves the reduction of lithium ions at an electrode, with the resultant metal in turn reducing nitrogen and regenerating the ions. Li et al . report the counterintuitive result that small quantities of oxygen could enhance the efficiency of this process, which they attribute to diffusional effects that limit excessive lithium reduction. —JSY

Electrochemical processes for ammonia synthesis could potentially replace the high temperature and pressure conditions of the Haber-Bosch process, with voltage offering a pathway to distributed fertilizer production that leverages the rapidly decreasing cost of renewable electricity. However, nitrogen is an unreactive molecule and the hydrogen evolution reaction presents a major selectivity challenge. An electrode of electrodeposited lithium in tetrahydrofuran solvent overcomes both problems by providing a surface that easily reacts with nitrogen and by limiting the access of protons with a nonaqueous electrolyte. Under these conditions, we measure relatively high faradaic efficiencies (ca. 10 %) and rates (0.1 mA cm À 2 ) toward NH 3 . We observe the development of a solid electrolyte interface layer as well as the accumulation of lithium and lithium-containing species. Detailed DFT studies suggest lithium nitride and hydride to be catalytically active phases given their thermodynamic and kinetic stability relative to metallic lithium under reaction conditions and the fast diffusion of nitrogen in lithium.[a] Dr.