Ammonia Electrosynthesis with High Selectivity under Ambient Conditions via a Li⁺ Incorporation Strategy

We report the discovery of a dramatically enhanced N₂ electroreduction reaction (NRR) selectivity under ambient conditions via the Li⁺ incorporation into poly(N-ethyl-benzene-1,2,4,5-tetracarboxylic diimide) (PEBCD) as a catalyst. The detailed electrochemical evaluation and density functional theory calculations showed that Li⁺ association with the O atoms in the PEBCD matrix can retard the HER process and can facilitate the adsorption of N₂ to afford a high potential scope for the NRR process to proceed in the "[O-Li⁺]·N₂-Hx" alternating hydrogenation mode. This atomic-scale incorporation strategy provides new insight into the rational design of NRR catalysts with higher selectivity.