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Temperature-programmed reduction of MoO/sub 3/ and MoO/sub 2/

Journal Article · · J. Phys. Chem.; (United States)
DOI:https://doi.org/10.1021/j100267a021· OSTI ID:6177537

The reduction of MoO/sub 3/ and MoO/sub 2/ is studied by temperature-programmed reduction (TPR). TPR patterns appear to be highly dependent on H/sub 2/O content of the reducing mixture, sample size, precalcination temperature, and heating rate. Activation energy values for reduction have been calculated from TPR series with various heating rates. A consistent interpretation of the complex TPR results is constructed, in which the extent of H/sub 2/ dissociation catalyzed by low-valent Mo atoms plays a central role. The formation of these Mo catalytic sites is found to depend on H/sub 2/O pressure, concentration of surface defects, and surface area. Reduction of MoO/sub 3/ to MoO/sub 2/ and of MoO/sub 2/ to Mo metal both can be catalyzed, in which case the rate-determining step is either H/sub 2/ dissociation, when the formation of catalytic sites is limited, or Mo-O bond breaking, when excess catalytic sites are present. Reduction of MoO/sub 3/ to MoO/sub 2/ can also take place noncatalyzed, with oxygen diffusion as rate-determining step. MoO/sub 2/ and Mo metal are also formed, as intermediates, in temperature-programmed sulfiding (TPS) of MoO/sub 3/. MoO/sub 2/ production is faster in H/sub 2//H/sub 2/S than in H/sub 2/ due to a different reduction mechanism involving H/sub 2/S as primary reactant. The formation of Mo metal is also faster, due to a higher porosity of the MoO/sub 2/ formed in situ. 48 references, 13 figures, 1 table.

Research Organization:
Univ. of Amsterdam, Netherlands
OSTI ID:
6177537
Journal Information:
J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 89:21; ISSN JPCHA
Country of Publication:
United States
Language:
English