Lewis acid-dominated aqueous electrolyte acting as co-catalyst and overcoming N₂ activation issues on catalyst...

The growing demands for ammonia in agriculture and transportation fuel stimulate researchers to develop sustainable electrochemical methods to synthesize ammonia ambiently, to get past the energy-intensive Haber-Bosch process. However, the conventionally used aqueous electrolytes limit N₂ solubility, leading to insufficient reactant molecules in the vicinity of the catalyst during electrochemical nitrogen reduction reaction (NRR). This hampers the yield and production rate of ammonia, irrespective of how efficient the catalyst is. Herein, we introduce an aqueous electrolyte (NaBF₄), which not only acts as an N₂-carrier in the medium but also works as a full-fledged "co-catalyst" along with our active material MnN₄ to deliver a high yield of NH₃ (328.59 μg h^-1 mg_cat^-1) at 0.0 V versus reversible hydrogen electrode. BF₃-induced charge polarization shifts the metal d-band center of the MnN₄ unit close to the Fermi level, inviting N₂ adsorption facilely. The Lewis acidity of the free BF₃ molecules further propagates their importance in polarizing the N≡N bond of the adsorbed N₂ and its first protonation. This push-pull kind of electronic interaction has been confirmed from the change in d-band center values of the MnN₄ site as well as charge density distribution over our active model units, which turned out to be effective enough to lower the energy barrier of the potential determining steps of NRR. Consequently, a high production rate of NH₃ (2.45 × 10^-9 mol s^-1 cm^-2) was achieved, approaching the industrial scale where the source of NH₃ was thoroughly studied and confirmed to be chiefly from the electrochemical reduction of the purged N₂ gas.