Nitrogen reduction to ammonia at high efficiency and rates based on a phosphonium proton shuttle

Abstract

Ammonia (NH₃) is a globally important commodity for fertilizer production, but its synthesis by the Haber-Bosch process causes substantial emissions of carbon dioxide. Alternative, zero-carbon emission NH₃ synthesis methods being explored include the promising electrochemical lithium-mediated nitrogen reduction reaction, which has nonetheless required sacrificial sources of protons. In this study, a phosphonium salt is introduced as a proton shuttle to help resolve this limitation. The salt also provides additional ionic conductivity, enabling high NH₃ production rates of 53 ± 1 nanomoles per second per square centimeter at 69 ± 1% faradaic efficiency in 20-hour experiments under 0.5-bar hydrogen and 19.5-bar nitrogen. Continuous operation for more than 3 days is demonstrated.