Electronically Coupled SnO2 Quantum Dots and Graphene for Efficient Nitrogen Reduction Reaction.

Electrocatalytic N2 reduction reaction (NRR) provides an effective and renewable approach for artificial NH3 production, but still remains a grand challenge because of the low NH3 yield and Faradaic efficiency (FE). Herein, we reported that the SnO2 quantum dots (QDs) supported on reduced graphene oxide (RGO) could efficiently and stably catalyze NRR at ambient conditions. The NRR performance of resulting SnO2/RGO was studied by both experimental techniques and density functional theory calculations. It was found that the ultrasmall SnO2 QDs (2 nm) grown on RGO could provide abundant sites for efficient N2 adsorption. Significantly, the strongly electronically coupled SnO2 QDs and RGO brought about the enhanced conductivity and the decreased work function, which led to a considerably lowered energy barrier of *N2 → *N2H that was the rate-determining step of the NRR process. Meanwhile, the SnO2/RGO exhibited inferior hydrogen evolution reaction activity. As a result, the SnO2/RGO delivered a high NH3 yield of 25.6 μg h-1 mg-1 (5.1 μg cm-2h-1) and an FE of 7.1% in 0.1 M Na2SO4 at -0.5 V (vs RHE), together with the outstanding selectivity and stability, endowing it as a promising electrocatalyst for N2 fixation.