Sandra Chouziera, Tivadar Czerib, Magalie Roy-Aubergerb, Christophe Pichonb, Christophe Geanteta, Michel Vrinata, Pavel Afanasieva, 
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| a | Institut de recherches sur la catalyse et l'environnement de Lyon UMR5256, CNRS-Université de Lyon 1, 2 avenue Albert Einstein, 69626 Villeurbanne cedex, France |
| b | IFP Energies nouvelles, BP 3, 69390 Vernaison, France |
Received 9 June 2011; revised 1 August 2011; Accepted 7 August 2011. Available online 11 August 2011.
Abstract
Decomposition of ammonium heptamolybdate–hexamethylentetramine (HMTA) complex (HMTA)2(NH4)4Mo7O24·2H2O was studied as a function of treatment conditions in the range 300–1173 K. The evolution of solid products during decomposition was studied by thermal analysis and in situ EXAFS. Depending on the nature of the gas used for treatment, single phases of highly dispersed nitrides Mo2N, carbide Mo2C, or oxide MoO2 can be obtained. The nature of the products obtained was explained by qualitative thermodynamical considerations. Morphology of the solids considerably depends on such preparation parameters as temperature and mass velocity of the gas flow. For the nitride-based materials, catalytic activity was evaluated in the model thiophene HDS reaction. It was demonstrated that NH3-treated samples showed better catalytic activity than N2-treated ones due to cleaner surface and better morphology. Transmission microscopy, XRD and XPS studies showed that MoS2 is formed on the surface during HDS reaction or sulfidation with H2S. Optimized nitride-derived catalysts showed mass activity several times higher than unsupported MoS2 or MoS2/Al2O3 reference catalyst.
Graphical Abstract
Depending on the conditions, decomposition of molybdate–HTMA complex yields highly dispersed molybdenum nitride, carbide or oxide.
