Synthesis, characterisation and hydrogenation performance of ternary nitride catalysts

Noemie Perret, Anne-Marie Alexander, Stuart M. Hunter, Peter Chung, Justin S. J. Hargreaves, Russell F. Howe, Mark A. Keane*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

27 Citations (Scopus)


Synthesis of phase pure Co3Mo3N and Fe3Mo3N by temperature programmed ammonolysis has been established by XRD and elemental analysis. The ternary nitrides are characterised by a η-6 structure and low surface area (4–9 m2 g−1). Pseudomorphic transformation of cobalt molybdate prepared using cobalt nitrate generated rod-shaped crystals while the use of iron chloride resulted in Fe3Mo3N aggregates with irregular morphology and wide size distribution. XPS measurements have revealed surface N enrichment relative to the bulk where the passivated samples show a range of oxidation states; Co3Mo3N exhibited Mo2+ and Con+ (0 ≤ n ≤ 3) whereas Fe3Mo3N was characterised by higher oxidation states (Fe3+ and Mo3+). Temperature programmed reduction (TPR) to 823 K served to remove the passivation layer where subsequent H2 chemisorption and temperature programmed desorption (TPD) has demonstrated greater uptake on Fe3Mo3N relative to Co3Mo3N, resulting in a higher nitrobenzene hydrogenation rate (to aniline). Fe3Mo3N promoted selective reduction of –NO2 in p-chloronitrobenzene to generate p-chloroaniline as sole product whereas Co3Mo3N favoured C-Cl scission with the formation of nitrobenzene (in addition to p-chloroaniline). Hydrodechlorination properties were further established for Co3Mo3N in the conversion of chlorobenzene (to benzene) under conditions where Fe3Mo3N was inactive. A temporal deactivation of both nitrides is associated with Cl poisoning of Co3Mo3N and structural changes to Fe3Mo3N.

Original languageEnglish
Pages (from-to)128-137
Number of pages10
JournalApplied Catalysis A: General
Early online date28 Sept 2014
Publication statusPublished - Nov 2014


  • ternary nitrides
  • Co3Mo3N
  • Fe3Mo3N
  • selective hydrogenation
  • hydrodechlorination
  • cobalt-molybdenum nitride
  • temperature-programmed desorption
  • ammonia-synthesis activity
  • p-chloronitrobenzene
  • surface-area
  • phase hydrogenation
  • magnetic-properties
  • lattice nitrogen
  • thiophene HDS
  • gas


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