Mechanistic Studies of the Oxidation of Cyclohexene to 2-Cyclohexen-1-one over ALD Prepared Titania Supported Vanadia

Wu, Weiqiang; Kwon, Stephanie; McCarthy, James A.; Stair, Peter C.; Weitz, Eric

doi:10.1021/acs.jpcc.9b09603

Title: Mechanistic Studies of the Oxidation of Cyclohexene to 2-Cyclohexen-1-one over ALD Prepared Titania Supported Vanadia

Journal Article · Thu May 21 00:00:00 UTC 2020 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.9b09603 · OSTI ID:2480863

Wu, Weiqiang ^[1]; Kwon, Stephanie ^[1]; McCarthy, James A. ^[1];

^[1];

^[1]

Northwestern University, Evanston, IL (United States)

Selective oxidation of cyclohexene to 2-cyclohexen-1-one over titania supported vanadia (VO_x/TiO₂) has been studied using temperature dependent in-situ FTIR spectroscopy in both the presence and absence of oxygen. The VO_x/TiO₂ samples were prepared using one atomic layer deposition (ALD) cycle and characterized by Raman spectroscopy. In-situ FTIR data for the oxidation of cyclohexene and perdeuterocyclohexene allow for the formulation of a molecular level reaction mechanism, which is initiated by the transfer of an allyl hydrogen. Oxidation of perdeuterocyclohexene provides a direct probe of the formation of OD and HDO moieties that support the involvement of specific steps in the proposed mechanism. The presence of gas phase oxygen does not lead to a change in the products versus anaerobic conditions. However, gas phase oxygen is significantly incorporated in the CO₂ over-oxidation product above ~250 °C. Data were also obtained with cyclohexene epoxide as the reactant in an effort to determine whether there is a parallel reaction pathway, which is initiated by C=C activation in cyclohexene, that involves cyclohexene epoxide as an intermediate. Furthermore, though a minor pathway involving a cyclohexene epoxide intermediate cannot be ruled out, these data demonstrate that, under experimental conditions, the dominant pathway from cyclohexene to cyclohexene-1-one is initiated by an allyl-H activation step and does not involve an epoxide intermediate.

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Research Organization:: Northwestern University, Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)

Grant/Contract Number:: AC02-06CH11357; FG02-03ER15457

OSTI ID:: 2480863

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 22 Vol. 124; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Mechanistic Studies of the Oxidation of Cyclohexene to 2-Cyclohexen-1-one over ALD Prepared Titania Supported Vanadia

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