Decomposition of molybdate–hexamethylenetetramine complex: One single source route for different catalytic materials

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 AbstractDepending on the conditions, decomposition of molybdate–HTMA complex yields highly dispersed molybdenum nitride, carbide or oxide. Figure optionsDownload as PowerPoint slideResearch highlights
► Decomposition of molybdate–HTMA complex yields highly dispersed Mo2N, Mo2C or MoO2.
► In situ EXAFS shows formation of common amorphous product MoCxNyOz at 673 K.
► Crystalline Mo2N with surface area near 200 m2/g was obtained at 823 K.
► High mass activity in thiophene HDS was observed.