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dc.contributor.authorShetty, Manish
dc.contributor.authorBuesser, Beat
dc.contributor.authorRomán-Leshkov, Yuriy
dc.contributor.authorGreen, William H
dc.date.accessioned2021-10-27T20:10:14Z
dc.date.available2021-10-27T20:10:14Z
dc.date.issued2017
dc.identifier.urihttps://hdl.handle.net/1721.1/134999
dc.description.abstract© 2017 American Chemical Society. Density functional theory (DFT) calculations were performed on the multistep hydrodeoxygenation (HDO) of acetone (CH3COCH3) to propylene (CH3CHCH2) on a molybdenum oxide (α-MoO3) catalyst following an oxygen vacancy-driven pathway. First, a perfect O-terminated α-MoO3 (010) surface based on a 4 x 2 x 4 supercell is reduced by molecular hydrogen (H2) to generate a terminal oxygen (Ot) defect site. This process occurs via a dissociative chemisorption of H2 on adjacent surface oxygen atoms, followed by an H transfer to form a water molecule (H2O). Next, adsorption of CH3COCH3 on the oxygen-deficient Mo site forms an O-Mo bond and then the chemisorbed CH3COCH3 forms CH3COCH2 by transfer of an H atom to an adjacent Ot site. The surface bound hydroxyl (OH) then transfers the H atom to the immobilized O atom to form surface-bound enol, CH3CHOCH2. The next step releases CH3CHCH2 into the gas phase, while simultaneously oxidizes the surface back to a perfect O-terminated α-MoO3 (010) surface. The adsorption of H2, and the formation of a terminal oxygen (Ot) vacancy, moves the conduction band minimum (CBM) from 1.2 eV to 0 and 0.3 eV, respectively. Climbing image-nudged elastic band (CI-NEB) calculations using a Perdew-Burke-Ernzerhof (PBE) functional in combination with double-ζ valence (DZV) basis sets indicate that the dissociative adsorption of H2 is the rate-limiting step for the catalytic cycle with a barrier of 1.70 eV. Furthermore, the lower barrier for surface-mediated H transfer from primary-to-secondary carbon atom (0.63 eV) compared to that of a concerted direct H transfer to the secondary C atom with simultaneous desorption (2.02 eV) emphasizes the key role played by the surface in H transfer for effective deoxygenation. (Chemical Equation Presented).
dc.language.isoen
dc.publisherAmerican Chemical Society (ACS)
dc.relation.isversionof10.1021/ACS.JPCC.7B02942
dc.rightsArticle is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
dc.sourceOther repository
dc.titleComputational Investigation on Hydrodeoxygenation (HDO) of Acetone to Propylene on α-MoO 3 (010) Surface
dc.typeArticle
dc.relation.journalJournal of Physical Chemistry C
dc.eprint.versionAuthor's final manuscript
dc.type.urihttp://purl.org/eprint/type/JournalArticle
eprint.statushttp://purl.org/eprint/status/PeerReviewed
dc.date.updated2019-08-19T17:08:49Z
dspace.orderedauthorsShetty, M; Buesser, B; Román-Leshkov, Y; Green, WH
dspace.date.submission2019-08-19T17:08:50Z
mit.journal.volume121
mit.journal.issue33
mit.metadata.statusAuthority Work and Publication Information Needed


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