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The Mechanism of Propane Ammoxidation over the ab Plane of the Mo-V-Te-Nb-O M1 Phase Probed by Density Functional Theory

Yu, Junjun
http://orcid.org/0000-0001-9654-8246
http://rave.ohiolink.edu/etdc/view?acc_num=ucin1445342500

Abstract Details

2015, PhD, University of Cincinnati, Engineering and Applied Science: Chemical Engineering.
The selective ammoxidation of propane into acrylonitrile catalyzed by the bulk Mo-V-Te-Nb-O system received considerable attention because it is more environmentally benign than the current process of propylene ammoxidation and relies on a more abundant feedstock. This process consists of a series of elementary steps including propane oxidative dehydrogenation (ODH), ammonia and O2 activation, and N-insertion into C3 surface intermediates. However, the limited fundamental understanding of the reaction mechanism and the roles of the different cations have hindered the progress in further improving the activity and selectivity of these catalysts required for the commercial application. In this thesis, we present and discuss the results of the density functional theory (DFT) calculations performed to investigate the overall propane ammoxidation pathway employing the cluster models of the proposed selective and active sites present in the surface ab plane of the so-called M1 phase, which is the main catalytic phase present in the bulk mixed Mo-V-Te-Nb oxides. The activation energies for the oxidative dehydrogenation (ODH) of propane and sequentially formed intermediates (isopropyl, propene, and allyl) were calculated for different surface cation sites. Propane activation on V5+=O was found to be the rate-limiting step (Ea = 1.2 eV), consistent with the current proposed reaction mechanism for propane activation on the bulk mixed Mo-V-Te-Nb oxides and the current understanding of V5+ as the active site for alkane activation present in V-based mixed oxides. Furthermore, a linear relationship was established between the H adsorption energy and the activation energy for H abstraction from various C3 intermediates, which is highly useful for predicting the energy barriers of H abstraction from C3 species based solely on H adsorption energy. The energy barriers of ammonia activation on different surface sites and NH insertion into the allyl species were investigated and discussed in terms of the hypothetical reaction pathway reported in the literature. These elementary reaction steps were indicated to be energetically barrier-less. The formation of acrylonitrile over Te=O as the H abstraction site from the surface absorbed precursor was found to be a barrier-less step. The overall reaction pathway was then explored using micro-kinetic models to study the selectivity of propane ammoxidation to acrylonitrile on the Mo-V-Te-Nb-O M1 phase. The calculated coverages of surface intermediates on Mo and V active sites from the micro-kinetic model indicated that NH is the dominant species on the surface as compared to surface O species which may explain why the M1 phase is so selective in transforming the gas-phase p-allyl intermediate into acrylonitrile as opposed to combustion products. This thesis reports the very first theoretical study of a complete mechanism of propane ammoxidation over surface ab planes of bulk mixed Mo-V-Te-Nb-O M1 phase. Improved understanding of the surface structure – reactivity relationships for propane ammoxidation to acrylonitrile over this model mixed metal oxide system gained in this research offers a possibility of not only molecular engineering of such mixed metal oxide catalysts for propane (amm)oxidation, but also fundamentally advancing the field of selective alkane (amm)oxidation over bulk mixed metal oxides.
Vadim Guliants, Ph.D. (Committee Chair)
Ye Xu, Ph.D. (Committee Member)
Junhang Dong, Ph.D. (Committee Member)
Peter Panagiotis Smirniotis, Ph.D. (Committee Member)
163 p.
Chemical Engineering
propane ammoxidation; microkinetic modeling; density functional theory; Mixed metal oxide; Mo-V-Te-Nb-O

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Citations

  • Yu, J. (2015). The Mechanism of Propane Ammoxidation over the ab Plane of the Mo-V-Te-Nb-O M1 Phase Probed by Density Functional Theory [Doctoral dissertation, University of Cincinnati]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1445342500

    APA Style (7th edition)

  • Yu, Junjun. The Mechanism of Propane Ammoxidation over the ab Plane of the Mo-V-Te-Nb-O M1 Phase Probed by Density Functional Theory. 2015. University of Cincinnati, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=ucin1445342500.

    MLA Style (8th edition)

  • Yu, Junjun. "The Mechanism of Propane Ammoxidation over the ab Plane of the Mo-V-Te-Nb-O M1 Phase Probed by Density Functional Theory." Doctoral dissertation, University of Cincinnati, 2015. http://rave.ohiolink.edu/etdc/view?acc_num=ucin1445342500

    Chicago Manual of Style (17th edition)

ucin1445342500
766
© 2015, some rights reserved.Creative Commons License The Mechanism of Propane Ammoxidation over the ab Plane of the Mo-V-Te-Nb-O M1 Phase Probed by Density Functional Theory by Junjun Yu is licensed under a Creative Commons Attribution-NonCommercial-NoDerivs 3.0 Unported License. Based on a work at etd.ohiolink.edu.
This open access ETD is published by University of Cincinnati and OhioLINK.