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

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja3115746DOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja3115746PublisherArticle
ORCID:
AuthorORCID
Cheng, Mu-Jeng0000-0002-8121-0485
Goddard, William A., III0000-0003-0097-5716
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).
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0001298
Chevron USA Inc.UNSPECIFIED
NSFCHE-1214158
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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