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Vanadium nitride catalysts were synthesized by the temperature-programmed reduction of vanadium oxide (V2O5) with pure NH3. The resulting materials contained VN or VN with a negligible amount of vanadium sesquioxide (V2O3) in the bulk after the nitrization of V oxides, indicating that the structural properties of these materials were strong functions of the heating rate and space velocity employed. The V nitrides proved to be active NH3 decomposition catalysts. Since the activity varied with changes in the surface area and particle size, ammonia decomposition over the V nitrides appeared to be structure-sensitive. While detailed relationships between the catalytic activity and surface composition could not be ascertained, there was a direct correlation between the activity, and the surface area and grain-boundary length. The most active catalyst, VN-c, which contained the δ-phase, had the greatest grain-boundary length. The catalytic properties of V nitrides were comparable or superior to those of a Ni/SiO2·Al2O3 catalyst. These results suggested that the characteristics of the active sites in the vanadium nitrides were similar to those in the Group 8—10 metal-based catalysts.

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