Nitrogen-rich molybdenum nitride synthesized in a crucible under air

The triple bond in N2 is significantly stronger than the double bond in O2, meaning that synthesizing nitrogen-rich nitrides typically requires activated nitrogen precursors, such as ammonia, plasma-cracked atomic nitrogen, or high-pressure N2. Here, we report a synthesis of nitrogen-rich nitrides under ambient pressure and atmosphere. Using Na2MoO4 and dicyandiamide precursors, we synthesized nitrogen-rich γ-Mo2N3 in an alumina crucible under an ambient atmosphere, heated in a box furnace between 500 and 600 °C. Byproducts of this metathesis reaction include volatile gases and solid Na(OCN), which can be washed away with water. X-ray diffraction and neutron diffraction showed Mo2N3 with a rock salt structure having cation vacancies, with no oxygen incorporation, in contrast to the more common nitrogen-poor rock salt Mo2N with anion vacancies. Moreover, an increase in temperature to 700 °C resulted in molybdenum oxynitride, Mo0.84N0.72O0.27. This work illustrates the potential for dicyandiamide as an ambient-temperature metathesis precursor for an increased effective nitrogen chemical potential under ambient conditions. The classical experimental setting often used for solid-state oxide synthesis, therefore, has the potential to expand the nitride chemistry. © 2024 American Chemical Society.

Keywords

Nitrogen, Molybdenum, Nitrides, Synthesis, Crucibles, Air, Ammonia, Atmospheres, Neutron diffraction, Oxygen, Oxides, Chemistry, Diffraction, Salts

Citation

Demura, M., Nagao, M., Lee, C.-H., Goto, Y., Nambu, Y., Avdeev, M., Masubuchi, Y., Mitsudome, T., Sun, W., Tadanaga, K., & Miura, A. (2024). Nitrogen-rich molybdenum nitride synthesized in a crucible under air. Inorganic Chemistry, 63(11), 4989-4996. doi:10.1021/acs.inorgchem.3c04345

URI

https://doi.org/10.1021/acs.inorgchem.3c04345
https://apo.ansto.gov.au/handle/10238/15799

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