Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model

Behtash, Sina; Lu, Jianmin; Walker, Eric; Mamun, Osman; Heyden, Andreas

doi:10.1016/j.jcat.2015.10.027

Solvent effects in the liquid phase hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst model

Journal Article · Sun Dec 06 00:00:00 EST 2015 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2015.10.027· OSTI ID:1656911

Behtash, Sina ^[1]; Lu, Jianmin ^[1]; Walker, Eric ^[1]; ^[1]; Heyden, Andreas ^[1]

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

Solvation effects of liquid water and 1,4-dioxane have been studied from first principles for the hydrodeoxygenation of methyl propionate over a Pd(1 1 1) catalyst surface model. Microkinetic reaction models have been developed for various reaction environments to study the effects of solvents on the reaction mechanism. Our models predict that in all reaction environments, decarbonylation pathways are favored over decarboxylation pathways. However, in the presence of liquid water the decarboxylation mechanism is facilitated due to solvent stabilization of the dehydrogenated derivatives of propionate. Altogether, the activity of Pd(1 1 1) is one order of magnitude lower in water than in 1,4-dioxane where we predict the activity to be very similar to the vapor phase. The decrease in Pd(1 1 1) activity due to liquid water can be traced back to the Pd surface being more crowded and propanoyl–methoxy type dissociations becoming more difficult. Propanoyl–methoxy type dissociations also become more rate controlling in liquid water than the dehydrogenation steps that are most rate controlling in 1,4-dioxane and in the vapor phase.

View Accepted Manuscript (DOE)

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

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

Grant/Contract Number:: AC02-05CH11231; SC0007167

OSTI ID:: 1656911

Alternate ID(s):: OSTI ID: 1422856
OSTI ID: 3001221

Journal Information:: Journal of Catalysis, Journal Name: Journal of Catalysis Journal Issue: C Vol. 333; ISSN 0021-9517

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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