Mechanistic insights into the formation of acetaldehyde and diethyl ether from ethanol over support VO{sub x}, MoO{sub x}, and WO{sub x} catalysts.
- Chemical Sciences and Engineering Division
Catalytic pathways are described for reactions of ethanol to acetaldehyde by oxidative dehydrogenation and of ethanol to diethyl ether by condensation over VO{sub x}-Al{sub 2}O{sub 3}, MoO{sub x}-Al{sub 2}O{sub 3}, and WO{sub x}-Al{sub 2}O{sub 3}. Isotopic labeling shows that acetaldehyde formation occurs via rate-determining C-H bond cleavage of the CH{sub 2} group in an adsorbed alkoxide followed by removal of surface oxygen in a Mars and van Krevelen redox mechanism (as confirmed by in situ X-ray absorption, diffuse reflectance infra-red Fourier transform spectroscopy and UV-visible spectroscopy); diethyl ether formation occurs in parallel via coupling and condensation of two adjacent ethoxy species. Using a combination of in situ spectroscopic and kinetic analysis, catalyst properties influencing the formation of acetaldehyde and ether from the common adsorbed ethoxy intermediate are elucidated. X-ray absorption analysis during anaerobic ethanol titration is used to preclude the involvement of terminal MO bonds during the reaction. A study of the activity of catalysts with the same MoO{sub x} domain size on Al{sub 2}O{sub 3}, TiO{sub 2}, and CeO{sub 2} supports and binary oxides of MoO{sub x} and WO{sub x} on Al{sub 2}O{sub 3} are used to prove that the active redox oxygen for acetaldehyde formation is the oxygen atom linking the active metal oxide domain to the support oxide. Ether formation ability of the metal oxide is related to the electronegativity of the active metal atom.
- Research Organization:
- Argonne National Laboratory (ANL)
- Sponsoring Organization:
- SC
- DOE Contract Number:
- AC02-06CH11357
- OSTI ID:
- 1020688
- Report Number(s):
- ANL/CSE/JA-69599
- Journal Information:
- J. Catal., Journal Name: J. Catal. Journal Issue: 1 ; Apr. 1, 2011 Vol. 279; ISSN 0021-9517
- Country of Publication:
- United States
- Language:
- ENGLISH
Similar Records
Supported molybdenum oxides for the aldol condensation reaction of acetaldehyde
Structure and surface and catalytic properties of Mg-Al basic oxides