Efficient Electrocatalytic Nitrogen Reduction to Ammonia on Ultrafine Sn Nanoparticles

Electrocatalytic nitrogen reduction reaction (NRR) at ambient conditions is a promising route for ammonia (NH3) synthesis but still suffers from low activity and selectivity. Here, ultrafine Sn nanoparticles (NPs) grown on carbon blacks (SnSC/C) have been synthesized through a wet-chemical method using sodium citrate dehydrate as a stabilizing agent. Benefiting from the small sizes of Sn NPs, the SnSC/C catalyst exhibits excellent electrocatalytic performance for NRR with a high Faradaic efficiency of 22.76% and an NH3 yield rate of 17.28 μg h–1 mg–1 in the 0.1 M Na2SO4 electrolyte, outperforming many reported electrocatalysts for NRR under similar conditions. Density functional theory calculation results reveal that the potential-determining step on Sn NPs is the generation of NHNH* through simultaneous hydrogenation of N2* by a H* and a H+/e– pair via Langmuir–Hinshelwood plus Eley–Rideal mechanisms.