Reversed I 1 Cu 4 Single-Atom Sites for Superior Neutral Ammonia Electrosynthesis with Nitrate

Electrochemical ammonia (NH 3 ) synthesis from nitrate reduction (NITRR) offers an appealing solution for addressing environmental concerns and the energy crisis. However, most of the developed electrocatalysts reduce NO 3 − to NH 3 via a hydrogen (H*)-mediated reduction mechanism, which suffers from undesired H*-H* dimerization to H 2 , resulting in unsatisfactory NH 3 yields. Herein, we demonstrate that reversed I 1 Cu 4 single-atom sites, prepared by anchoring iodine single atoms on the Cu surface, realized superior NITRR with a superior ammonia yield rate of 4.36 mg h −1 cm −2 and a Faradaic efficiency of 98.5% under neutral conditions via a proton-coupled electron transfer (PCET) mechanism, far beyond those of traditional Cu sites (NH 3 yield rate of 0.082 mg h −1 cm −2 and Faradaic efficiency of 36.5%) and most of H*-mediated NITRR electrocatalysts. Theoretical calculations revealed that I single atoms can regulate the local electronic structures of adjacent Cu sites in favor of stronger O-end-bidentate NO 3 − adsorption with dual electron transfer channels and suppress the H* formation from the H 2 O dissociation, thus switching the NITRR mechanism from H*-mediated reduction to PCET. By integrating the monolithic I 1 Cu 4 single-atom electrode into a flow-through device for continuous NITRR and in situ ammonia recovery, an industrial-level current density of 1 A cm −2 was achieved along with a NH 3 yield rate of 69.4 mg h −1 cm −2 . This study offers reversed single-atom sites for electrochemical ammonia synthesis with nitrate wastewater and sheds light on the importance of switching catalytic mechanisms in improving the performance of electrochemical reactions.