Accelerating lithium-mediated nitrogen reduction through an integrated palladium membrane hydrogenation reactor

Lithium-mediated N₂ reduction reaction (LiNRR) is regarded as the most robust route towards electrifying NH₃ synthesis. However, in this reaction geometry, hydrogen atoms typically supplied through electrolyte degradation, via H₂ oxidation or a combination of both, hampering the efficiency of the process. In this work we provide an alternative H-source by merging a Pd Membrane reactor (PMR) with a LiNRR reactor in a unique dual-reactor setup. Specifically, use a Pd membrane that extracts H atoms directly from H₂O and transfers them across the membrane to an electrodeposited Li layer operating under non-aqueous LiNRR conditions. We show that these H₂O-derived H-atoms are used directly to synthesize NH₃ in the presence of N₂ and electrodeposited Li, thereby opening orthogonal reaction pathways within the metal-mediated nitrogen reduction concept.