The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride
Mu-Jeng Cheng, William A. Goddard 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.
Group Members
Cheng, M. & III, W. A. G. (2013). The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride. *J. Am. Chem. Soc.*, *135*(12), 4600-4603. https://doi.org/10.1021/ja3115746