The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride
- 24 February 2013
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 135 (12), 4600-4603
- https://doi.org/10.1021/ja3115746
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 VVOPO4 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 O2 on the (VIVO)2P2O7 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 VV 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.Keywords
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