Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface

Lu, Jianmin; Heyden, Andreas

doi:10.1016/j.jcat.2014.11.003

Title: Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface

Journal Article · Mon Nov 24 00:00:00 EST 2014 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2014.11.003· OSTI ID:1656914

Lu, Jianmin ^[1]; Heyden, Andreas ^[1]

University of South Carolina, Columbia, SC (United States)

The reaction mechanism of the hydrodeoxygenation of guaiacol to aromatic products has been studied by density functional theory calculations and microkinetic modeling over a Ru(0 0 0 1) model surface. Our model suggests that the dominant hydrodeoxygenation pathway proceeds via O–H bond cleavage of guaiacol, C₆H₄(OH)(OCH₃), to C₆H₄(O)(OCH₃), followed by dehydrogenation of the methoxy group to C₆H₄(O)(OC), decarbonylation to C₆H₄O, and finally hydrogenation to phenol. At the adsorbed C₆H₄(O)(OCH) intermediate, a competitive deoxygenation pathway is identified, which involves methyne group removal to C₆H₄O₂, followed by hydrogenation to C₆H₄(OH)(O), dehydroxylation to C₆H₄O, and finally hydrogenation to phenol. In agreement with experimental results, phenol is predicted to be the major product and catechol is the most relevant minority side product. Further deoxygenation of phenol to benzene is found to be slow. Lastly, computations predict the last dehydrogenation step of the methoxy species in guaiacol to be at least partially rate controlling over Ru(0 0 0 1).

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Research Organization:: Univ. of South Carolina, Columbia, SC (United States)

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

Grant/Contract Number:: FG02-11ER16268; SC0007167; TG-CTS090100

OSTI ID:: 1656914

Alternate ID(s):: OSTI ID: 1244577

Journal Information:: Journal of Catalysis, Vol. 321, Issue C; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 92 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Title: Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface

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