Salting-out effect promoting highly efficient ambient ammonia synthesis

Abstract The electroreduction of nitrogen to ammonia offers a promising alternative to the energy-intensive Haber–Bosch process. Unfortunately, the reaction suffers from low activity and selectivity, owing to competing hydrogen evolution and the poor accessibility of nitrogen to the electrocatalyst. Here, we report that deliberately triggering a salting-out effect in a highly concentrated electrolyte can simultaneously tackle the above challenges and achieve highly efficient ammonia synthesis. The solute ions exhibit strong affinity for the surrounding H 2 O molecules, forming a hydration shell and limiting their efficacy as both proton sources and solvents. This not only effectively suppresses hydrogen evolution but also ensures considerable nitrogen flux at the reaction interface via heterogeneous nucleation of the precipitate, thus facilitating the subsequent reduction process in terms of both selectivity and activity. As expected, even when assembled with a metal-free electrocatalyst, a high Faradaic efficiency of 71 ± 1.9% is achieved with this proof-of-concept system.