Highly efficient metal-free borocarbonitride catalysts for electrochemical reduction of N2 to NH3.

ABSTRACT

The electrocatalytic nitrogen reduction reaction (NRR) for ammonia (NH3) under ambient conditions is emerging as a potentially sustainable alternative to the traditional, energy-intensive Haber-Bosch process for ammonia production. Currently, metal-based electrocatalysts constitute the majority of reported NRR catalysts. However, they often suffer from the shortcomings of competitive reactions of nitrogen adsorption/activation and hydrogen generation. Therefore, there is an urgent need to develop more environmentally friendly, low energy consumption, and non-polluting high-performance metal-free electrocatalysts. In this study, borocarbonitride (BCN) materials derived from boron imidazolate framework (BIF-20) were used to boost efficient electrochemical nitrogen conversion to ammonia under ambient conditions. The BCN catalyst demonstrated excellent performance in 0.1 M KOH, with an ammonia yield of 21.62 µg h-1 mgcat-1 and a Faradaic efficiency of 9.88% at -0.3 V (Reversible Hydrogen Electrode, RHE). This performance is superior to most metal-free catalysts and even some metal catalysts for NRR. The 15N2/14N2 isotope labeling experiments and density functional theory (DFT) calculations showed that N2 can be adsorbed and converted to NH3 on the surface of BCN, and that the energy barrier can be significantly reduced by structural design for BCN. This work highlights the important role played by the presence of Lewis acid-base pairs in metal-free catalysts for enhancing electrochemical NRR performance.