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The Dual-Phase Mechanism for the Catalytic Conversion of n-Butane to Maleic Anhydride by the Vanadyl Pyrophosphate Heterogeneous Catalyst

O'Leary, Willis C. and Goddard, William A., III and Cheng, Mu-Jeng (2017) The Dual-Phase Mechanism for the Catalytic Conversion of n-Butane to Maleic Anhydride by the Vanadyl Pyrophosphate Heterogeneous Catalyst. Journal of Physical Chemistry C, 121 (43). pp. 24069-24076. ISSN 1932-7447. https://resolver.caltech.edu/CaltechAUTHORS:20170919-081753764

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Abstract

Industrial production of maleic anhydride (MA) from n-butane relies on the vanadyl pyrophosphate (VPO) catalyst. Improving VPO’s selectivity and activity could have enormous economic and environmental impact, but efforts have been impeded by uncertainties regarding the active phases and atomistic mechanism of the VPO catalyst. We report here a plausible 15-step mechanism taking n-butane to MA with energetics computed using hybrid density functional theory calculations on periodic models of the surface layers. We find that the P═O group on the X1 phase is solely responsible for butane activation. The P═O group is made active by the reduction of a nearby vanadium atom, a so-called reduction-coupled oxo-activation. However, we show that a catalyst consisting only of the X1 phase would not be selective because of several highly exothermic steps. Instead, we show that the more stable α1 phase can catalyze the formation of MA after initial activation, thus proposing and validating a dual-phase mechanism that takes butane to MA. Our new mechanism inspires the development of a more selective VPO catalyst containing small X1 regions highly separated by α_1 surfaces.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpcc.7b07881DOIArticle
http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b07881PublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/acs.jpcc.7b07881PublisherSupporting Information
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Cheng, Mu-Jeng0000-0002-8121-0485
Additional Information:© 2017 American Chemical Society. Received: August 8, 2017; Published: September 18, 2017. This project was initiated with funding from NSF CHE-1214158 and finished with funding from NSF CBET 1512759. Additionally, a gift from Dr. Fredrick H. Shair contributed to the project by supporting a Summer Undergraduate Research Fellowship for W.C. O’Leary. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1214158
NSFCBET-1512759
Caltech Summer Undergraduate Research Fellowship (SURF)UNSPECIFIED
Issue or Number:43
Record Number:CaltechAUTHORS:20170919-081753764
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20170919-081753764
Official Citation:Dual-Phase Mechanism for the Catalytic Conversion of n-Butane to Maleic Anhydride by the Vanadyl Pyrophosphate Heterogeneous Catalyst. Willis C. O’Leary, William A. Goddard, III, and Mu-Jeng Cheng. The Journal of Physical Chemistry C 2017 121 (43), 24069-24076. DOI: 10.1021/acs.jpcc.7b07881
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:81556
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:19 Sep 2017 16:22
Last Modified:03 Oct 2019 18:44

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