Kinetics and mechanism of oxidative dehydrogenation of propane on vanadium, molybdenum, and tungsten oxides

Journal Article · Thu Feb 17 04:00:00 EST 2000 · Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical

DOI:https://doi.org/10.1021/jp9933875· OSTI ID:20017544

Chen, K; Bell, A T; Iglesia, E

The effect of cation identity on oxidative dehydrogenation (ODH) pathways was examined using two-dimensional VO{sub x}, MoO{sub x}, and WO{sub x} structures supported on ZrO{sub 2}. The similar kinetic rate expressions obtained on MoO{sub x} and VO{sub x} catalysts confirmed that oxidative dehydrogenation of propane occurs via similar pathways, which involve rate-determining C-H bond activation steps using lattice oxygen atoms. The activation energies for propane dehydrogenation and for propene combustion increase in the sequence VO{sub x}/ZrO{sub 2} < MoO{sub x}/ZrO{sub 2} < WO{sub x}/ZrO{sub 2}; the corresponding reaction rates decrease in this sequence, suggesting that turnover rates reflect C-H bond cleavage activation energies, which are in turn influenced by the reducibility of these metal oxides. Propane ODH activation energies are higher than for propene combustion. This leads to an increase in maximum alkene yields and in the ratio of rate constants for propane ODH and propene combustion as temperature increases. This difference in activation energy (48--61 kJ/mol) between propane ODH and propene combustion is larger than between bond dissociation enthalpies for the weakest C-H bond in propane and propene (40 kJ/mol) and it increases in the sequence VO{sub x}/ZrO{sub 2} < MoO{sub x}/ZrO{sub 2} < WO{sub x}/ZrO{sub 2}. These results suggest that relative propane ODH and propene combustion rates depend not only on C-H bond energy differences but also on the absorption enthalpies for propene and propane, which reflect the Lewis acidity of cations involved in {pi} bonding of alkenes on oxide surfaces. The observed difference in activation energies between propane ODH and propene combustion increases at the Lewis acidity of the cations increases (V{sup 5+} < Mo{sup 6+} < W{sup 6+}).

• Research Organization: Univ. of California, Berkeley, CA (US)
• Sponsoring Organization: US Department of Energy
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 20017544
• Journal Information: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical, Journal Name: Journal of Physical Chemistry B: Materials, Surfaces, Interfaces, amp Biophysical Journal Issue: 6 Vol. 104; ISSN 1089-5647; ISSN JPCBFK
• Country of Publication: United States
• Language: English

Related Subjects

03 NATURAL GAS
10 SYNTHETIC FUELS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
COMBUSTION
DEHYDROGENATION
MOLYBDENUM OXIDES
PROPANE
PROPYLENE
TUNGSTEN OXIDES
VANADIUM OXIDES