New routes to transition metal nitrides: and characterization of new phases

Abstract

Transition metal nitrides form a class of materials with unique physical properties which give them varied applications, as high temperature ceramics, magnetic materials, superconductors or catalysts. They are commonly prepared by high temperature conventional processes, but alternative synthetic approaches have also been explored, more recently, which utilize moderate-temperature conditions. For example, high surface area γ-Mo₂N nitride powders (fcc phase) are prepared from commercial oxide MoO₃ through a topotactic transformation process. Of prime importance is the nature of the precursor, because it may yield new nitride phases unattainable by other synthetic routes. A novel promising method to nitride synthesis has been developed using sulfides as starting materials. The ammonolysis reaction has been applied first to the preparation of two binary molybdenum nitrides: Mo₅N₆ (filled 2H-MoS₂ structure) and δ-MoN (NiAs-type structure) from MoS₂, and then extended to other metals such as W, Cr or Ti, as well as molybdenum- and tantalum-based ternary systems. Fine reactive molybdenum sulfide precursor powders (S_g ≥200 m² g^–1) have been synthesized in thiocyanate melt. On the other hand, alkali metal ternary oxides offer potential as nitridation precursors. For example, a binary nitride Nb₄N₅ (defect NaCl-type structure) results from ammonolysis of sodium or potassium niobates whereas LiNb₃O₈ is transformed into a mixed valent ternary nitride LiNb₃N₄ (filled 2H-MoS₂ structure). Another illustration of the Li⁺ inductive effect is given in the direct synthesis of LiMN₂ from Li₂MO₄ (M=Mo, W). The nitrides Mo₅N₆, δ-MoN and Nb₄N₅ show superconducting behavior at T<12 K.

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