Artificial Frustrated Lewis Pairs for Ampere-Level Ammonia Synthesis and High-Power-Density Zinc-Nitrate Battery

Cu-based electrocatalysts exhibit superior reduction kinetics in the electrochemical nitrate reduction reaction (NO₃RR) and suppress competing hydrogen evolution reaction, making NO₃RR an alternative to the traditional Haber-Bosch process in NH₃ production. However, the NO₃RR in NH₃ production involves a nine-proton and eight-electron process, and its performance is constrained by the poor capacity to generate protons. In this study, frustrated Lewis pairs (FLPs) were introduced into Cu-based catalysts to create La-doped Cu₂O, in which the FLPs [Cu-O-La-O_v] (where v denotes vacancy) formed by the Lewis acidic sites O_v and Lewis basic sites O in the Cu-O-La motif served as active sites. These active sites facilitated H₂O dissociation, providing ample protons for the NO₃RR hydrogenation. The La₉-CuO_<i>x</i> catalyst exhibited an ultralow NH₃ production overpotential of only 290 mV, achieving an NH₃ current density of 1.76 A cm^-2 at -0.4 V vs the reversible hydrogen electrode, with an NH₃ yield rate of 139.5 mg h^-1 cm^-2 and Faradaic efficiency of 98.9%. Due to the superior NO₃RR performance of La₉-CuO_<i>x</i>, a La₉-CuO_<i>x</i>-based Zn-NO₃^- battery achieved a remarkable power density of 80.6 mW cm^-2, with an NH₃ yield rate of 21.4 mg h^-1 cm^-2. This study clarifies the role of FLPs in facilitating the NO₃RR and achieves an efficient Zn-NO₃^- battery to accomplish electricity generation and NH₃ production simultaneously.