Cheng, Mu-Jeng and Goddard, William A., III (2013) The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride. Journal of the American Chemical Society, 135 (12). pp. 4600-4603. ISSN 0002-7863. doi:10.1021/ja3115746. https://resolver.caltech.edu/CaltechAUTHORS:20130502-132101627
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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.
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| 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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| Issue or Number: | 12 | |||||||||
| DOI: | 10.1021/ja3115746 | |||||||||
| Record Number: | CaltechAUTHORS:20130502-132101627 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20130502-132101627 | |||||||||
| Official Citation: | The Critical Role of Phosphate in Vanadium Phosphate Oxide for the Catalytic Activation and Functionalization of n-Butane to Maleic Anhydride Mu-Jeng Cheng and William A. Goddard, III Journal of the American Chemical Society 2013 135 (12), 4600-4603 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 38245 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Jason Perez | |||||||||
| Deposited On: | 03 May 2013 14:29 | |||||||||
| Last Modified: | 09 Nov 2021 23:36 |
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