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Published March 27, 2013 | Supplemental Material + Published
Journal Article Open

The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride

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).

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Published - ja3115746.pdf

Supplemental Material - ja3115746_si_001.pdf

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