Divalent Oxidation State Ni as an Active Intermediate in Prussian Blue Analogues for Electrocatalytic Urea Oxidation

Urea degradation is one of the most crucial links in the natural nitrogen cycle. Exploring the real active species in the urea electro-oxidation process is of great significance for understanding the urea electro-oxidation mechanism and designing catalysts. A highly active and stable Prussian blue analogue catalyst (PBA@NiFe/NF) loaded on nickel foam was synthesized for electro-oxidation of urea. In situ Raman spectra revealed that Ni in PBA@NiFe/NF was able to maintain a stable divalent nickel (Ni(II)) state for up to 3.5 h during the initial urea oxidation process, which is rarely reported in previous research studies. In addition, with the participation of iron, the Ni-Fe bimetallic center significantly improves the electro-oxidation of urea. Our work provides a new idea for prolonging the Ni(II) activity in electrocatalytic oxidation of urea.

Automated summary

Urea degradation is crucial in the nitrogen cycle, and understanding the electro-oxidation mechanism and designing catalysts is significant. A stable and active catalyst (PBA@NiFe/NF) loaded on nickel foam was synthesized, and in situ Raman spectra showed the maintenance of stable Ni(II) state during urea oxidation. The participation of iron significantly improved the electro-oxidation of urea. This work provides new insights for prolonging Ni(II) activity in urea electrocatalytic oxidation.