Molybdenum Nitride and Oxide Layers Grown on Mo Foil for Supercapacitors

In this study, thin molybdenum nitride (MoN_x) layers were directly synthesized on molybdenum foil via thermal treatment under an NH₃ atmosphere, and their phase evolution, structural characteristics, and electrochemical performance were investigated. The thickness and morphology of the MoN_x layers were controlled by varying ammonolysis time and temperature, while subsequent annealing in N₂ converted the nitride layer into MoO₂. Meanwhile, oxidation in air yielded crystalline MoO₃ layers. X-ray diffraction and X-ray photoelectron spectroscopy confirmed progressive oxidation of molybdenum, with Mo 3d binding energies increasing in the sequence of Mo < MoN_x < MoO₂ < MoO₃, consistent with their nominal oxidation states. Electrochemical characterization revealed that both MoN_x/Mo and MoO₂/Mo electrodes exhibit notable pseudocapacitive behavior in 0.5 M H₂SO₄ electrolyte, with areal specific capacitances reaching up to 520 mF cm^-2 at 10 mV s^-1. Increasing layer thickness led to enhanced capacitance, likely due to an increase in the electrochemically accessible surface area and the extension of ion diffusion pathways. MoO₂-coated samples showed stronger faradaic contribution and superior rate capability compared to MoN_x counterparts, along with a gradual shift from predominantly electric double-layer capacitance toward hybrid pseudocapacitive charge storage mechanisms.