Efficient Electrochemical Ammonia Synthesis from Nitric Oxide Using Highly Dispersed Cu₃P Nanoclusters Anchored on...

The electrochemical synthesis of green ammonia from NO has attracted great attention as an alternative strategy for the Haber-Bosch process. However, nitric oxide reduction reaction (NORR) has bottlenecks such as low selectivity toward NH₃ and poor stability of catalysts under corrosive reaction environment for efficient NH₃ production. Herein, highly dispersed copper phosphide nanocluster embedded in nitrogen-doped carbon nanorod (Cu₃P/NCNR) electrocatalysts are obtained by the simple electrospinning technique and calcination process. The Cu₃P/NCNR-2 synthesized at 800 °C achieved the highest Faradaic efficiency (FE_NH3) of 78.7 ± 0.7% with NH₃ yield rate of 26.4 ± 0.6 µmol cm^-2 h^-1 at -0.3 V (vs. RHE) in 0.1 м HCl electrolyte. The control experiments indicated that the Cu₃P is the active center in Cu₃P/NCNR-2. The synergistic effect of the highly dispersed Cu₃P nanoclusters on the N-doped carbon and the optimal Cu/P ratio enhanced NORR performance of Cu₃P/NCNR-2. The cycle stability and 24 h long-term durability test are carried out to verify the robustness of Cu₃P/NCNR-2 electrocatalyst. Furthermore, the Cu₃P/NCNR-2 catalyst is introduced as the cathode in the Zn-NO battery, which delivered a high-power density of 3.3 mW cm^-2 at a high current density of 2.5 mA cm^-2 while simultaneously producing an NH₃ yield of 250.9 µg cm^-2 h^-1 during the galvanostatic discharge.