Work

Steam-Assisted Ammonolysis of MoO2 as a Synthetic Pathway to Oxygenated δ-MoN

Year: 2025

Type: article

Abstract: A common route for the synthesis of molybdenum nitrides is through the temperature-programmed reaction of molybdenum oxides with NH3, or ammonolysis. In this work, the role of precursor phase, gas phase chemistry (impact of H2O), and temperature profile on the reaction outcome (700 °C) was examined, which resulted in varying amounts of MoO2, H2MoO5, and the nitride phases—cubic γ (nominally Mo2N) and hexagonal δ (nominally MoN). The phase fraction of the δ phase increased with precursor in the sequence MoO2 > MoO3 > H2MoO5. Steam in the reaction gas also favored the production of δ over γ, but with too much steam, MoO2 was obtained in the product. Synthesis conditions for obtaining nearly phase-pure δ were identified: MoO2 as the precursor, 2% H2O in the gas stream, and a moderate heating rate (3 °C/min). In situ X-ray diffraction provided insights into the reaction pathway. Extensive physico-chemical analysis of the δ phase, including synchrotron X-ray and neutron diffraction, electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and prompt gamma activation analysis, revealed its stoichiometry to be MoO0.108(8)N0.892(8)H0.012(5), indicating non-trivial oxygen incorporation. The presence of N/O ordering and an impurity phase Mo5N6 were also revealed, detectable only by neutron diffraction. Notably, a computationally predicted MoON phase (doi: 10.1103/PhysRevLett.123.236402), of interest due to its potential to display a metal-insulator transition, did not appear under any reaction condition examined.

Source: Materials

DOI: 10.3390/ma18102340