The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride
- Creators
- Cheng, Mu-Jeng
- Goddard, William A., III
Abstract
We used density functional theory to study the mechanism of n-butane oxidation to maleic anhydride on the vanadium phosphorus oxide (VPO) surface. We found that O(1)═P on the V^(V)OPO_4 surface is the active center for initiating the VPO chemistry through extraction of H from alkane C–H bonds. This contrasts sharply with previous suggestions that the active center is either the V–O bonds or else a chemisorbed O_2 on the (V^(IV)O)_(2)P_(2)O_7 surface. The ability of O(1)═P to cleave alkane C–H bonds is due to its strong basicity coupled with large reduction potentials of nearby V^V ions. We examined several pathways for the subsequent functionalization of n-butane to maleic anhydride and found that the overall barrier does not exceed 21.7 kcal/mol.
Additional Information
© 2013 American Chemical Society. Received: November 26, 2012; Published: February 24, 2013. This work was initiated with support from the Center for Catalytic Hydrocarbon Functionalization, an Energy Frontier Research Center (DOE DE-SC0001298), and completed with support from Chevron USA Inc. and NSF (CHE-1214158).Attached Files
Published - ja3115746.pdf
Supplemental Material - ja3115746_si_001.pdf
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Additional details
- Eprint ID
- 38245
- Resolver ID
- CaltechAUTHORS:20130502-132101627
- DE-SC0001298
- Department of Energy (DOE)
- Chevron USA Inc.
- CHE-1214158
- NSF
- Created
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2013-05-03Created from EPrint's datestamp field
- Updated
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2021-11-09Created from EPrint's last_modified field