open access

https://hdl.handle.net/2115/94143

Nitrogen-Rich Molybdenum Nitride Synthesized in a Crucible under Air

英語

2024-03-18

American Chemical Society

Inorganic chemistry

63(11)

4989-4996

The triple bond in N-2 is significantly stronger than the double bond in O-2, meaning that synthesizing nitrogen-rich nitrides typically requires activated nitrogen precursors, such as ammonia, plasma-cracked atomic nitrogen, or high-pressure N-2. Here, we report a synthesis of nitrogen-rich nitrides under ambient pressure and atmosphere. Using Na2MoO4 and dicyandiamide precursors, we synthesized nitrogen-rich gamma-Mo2N3 in an alumina crucible under an ambient atmosphere, heated in a box furnace between 500 and 600 degrees 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 degrees 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.

学術雑誌論文

Accepted Manuscript

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/articlesonrequest/AOR-EHMYUAF3XNM5YDEGQXPE.

0020-1669