Plasma-etching enhanced titanium oxynitride active phase with high oxygen content for ambient electrosynthesis of ammonia

Here we report that the plasma-etching processed commercial titanium nitride (TiN-PE, PE represents plasma-etching) that was first treated by ball-milling method (TiNBM, BM represents ball-milling) is highly electrochemically active for the nitrogen (N2) reduction reaction (NRR) to NH3. The results demonstrate that the TiN-PE as NRR electrocatalyst can deliver a yield rate of NH3 of 3.32 × 10−10 mol s−1 cm−2 (4.1 mg h−1 gcat.−1) with a Faradaic efficiency of 9.1% at −0.6 V (vs. RHE) in 0.1 M Na2SO4 solution (pH = 3.2). The X-ray photoelectron spectroscopy (XPS) analysis indicates that the titanium oxynitride (TiOxNy) with high oxygen content on TiN surface was significantly enhanced by this plasma-etching approach, which is electrocatalytically active species for NRR. The 15N isotopic labeling experimental results using 15N2 as the feeding gas verify that the syntheized NH3 product during NRR is composed of 15N in 15NH4+ (the enrichement of 64%) and 14N in 14NH4+ (the enrichment of 36%), indicating that the NRR process follows the Mars–van Krevelen mechanism. [Display omitted] •Commercial TiN was treated by a combined approach of ball-milling and plasma etching.•Titanium oxynitride (TiOxNy) with high oxygen content was obtained on TiN surface after plasma-etching treatment.•TiOxNy is the active phase of electrocatalytic N2 reduction reaction to ammonia.