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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.

Ammonia is a critical component in fertilizers, pharmaceuticals, and fine chemicals and is an ideal, carbon-free fuel. Recently, lithium-mediated nitrogen reduction has proven to be a promising route for electrochemical ammonia synthesis at ambient conditions. In this work, we report a continuous-flow electrolyzer equipped with 25–square centimeter–effective area gas diffusion electrodes wherein nitrogen reduction is coupled with hydrogen oxidation. We show that the classical catalyst platinum is not stable for hydrogen oxidation in the organic electrolyte, but a platinum-gold alloy lowers the anode potential and avoids the decremental decomposition of the organic electrolyte. At optimal operating conditions, we achieve, at 1 bar, a faradaic efficiency for ammonia production of up to 61 ± 1% and an energy efficiency of 13 ± 1% at a current density of −6 milliamperes per square centimeter.

The industrial Haber-Bosch process to produce ammonia (NH3) from dinitrogen (N2) is crucial for modern society. However, N2 activation is inherently challenging and the Haber-Bosch process has significant drawbacks, as it is highly energy intensive, not sustainable due to substantial CO2 emissions primarily from the generation of H2 and requires large-centralized facilities. New strategies of sustainable N2 activation, such as low-temperature thermochemical catalysis and (photo)electrocatalysis, have been pursued, but progress has been hindered by the lack of rigor and reproducibility in the collection and analysis of results.In this Primer, we provide a holistic step-by-step protocol, applicable to all nitrogen-transformation reactions, focused on verifying genuine N2 activation by accounting for all contamination sources. We compare state-of-the-art results from different catalytic reactions following the protocol's framework, and discuss necessary reporting metrics and ways to interpret both experimental and density functional theory results. This Primer covers various common pitfalls in the field, best practices to improve reproducibility and cost-efficient methods to carry out rigorous experimentation. The future of nitrogen catalysis will require an increase in rigorous experimentation and standardization to prevent false positives from appearing in the literature, which can enable advancing towards practical technologies for the activation of N2.

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 Users may download and print one copy of any publication from the public portal for the purpose of private study or research.  You may not further distribute the material or use it for any profit-making activity or commercial gain  You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim.