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Title: Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface

Abstract

The hydrodeoxygenation of organic acids is often found to be a rate-controlling process during upgrading of biomass feedstocks into fuels. We developed a microkinetic model based on data obtained from density functional theory calculations for the decarboxylation and decarbonylation mechanisms of propanoic acid (CH3CH2COOH) over a Ru(0 0 0 1) model surface. The model predicts that the decarbonylation mechanism is two orders of magnitude faster than the decarboxylation mechanism. The most favorable decarbonylation pathway proceeds via removal of the acid –OH group to produce propanoyl (CH3CH2CO) followed by C–CO bond scission of propanoyl to produce CH3CH2 and CO. Finally, CH3CH2 is hydrogenated to CH3CH3. Dehydrogenation reactions that have been observed to be important over Pd catalysts play no role over Ru(0 0 0 1), and a sensitivity analysis indicates that removal of the acid –OH group is the rate-controlling step in the deoxygenation. Altogether, our results suggest that to improve the Ru catalyst performance for the decarbonylation of organic acids, the free site coverage needs to be increased by, for example, adding a catalyst promoter that decreases the hydrogen and CO adsorption strength (without significantly affecting the C–OH bond scission rate), or by raising the reaction temperature and operating atmore » relatively low CO and H2 partial pressures.« less

Authors:
 [1];  [2];  [1];  [1]
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  1. University of South Carolina, Columbia, SC (United States)
  2. University of South Carolina, Columbia, SC (United States); University of Engineering & Technology, Lahore (Pakistan)
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1656913
Alternate Identifier(s):
OSTI ID: 1430764
Grant/Contract Number:  
SC0007167; CHE-1153012; FG02-11ER16268; TG-CTS090100
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 324; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ruthenium; Density functional theory; Microkinetic model; Deoxygenation; Hydrodeoxygenation; Organic acid

Citation Formats

Lu, Jianmin, Faheem, Muhammad, Behtash, Sina, and Heyden, Andreas. Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface. United States: N. p., 2015. Web. doi:10.1016/j.jcat.2015.01.005.
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Lu, Jianmin, Faheem, Muhammad, Behtash, Sina, & Heyden, Andreas. Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface. United States. https://doi.org/10.1016/j.jcat.2015.01.005
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Lu, Jianmin, Faheem, Muhammad, Behtash, Sina, and Heyden, Andreas. Mon . "Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface". United States. https://doi.org/10.1016/j.jcat.2015.01.005. https://www.osti.gov/servlets/purl/1656913.
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@article{osti_1656913,
title = {Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface},
author = {Lu, Jianmin and Faheem, Muhammad and Behtash, Sina and Heyden, Andreas},
abstractNote = {The hydrodeoxygenation of organic acids is often found to be a rate-controlling process during upgrading of biomass feedstocks into fuels. We developed a microkinetic model based on data obtained from density functional theory calculations for the decarboxylation and decarbonylation mechanisms of propanoic acid (CH3CH2COOH) over a Ru(0 0 0 1) model surface. The model predicts that the decarbonylation mechanism is two orders of magnitude faster than the decarboxylation mechanism. The most favorable decarbonylation pathway proceeds via removal of the acid –OH group to produce propanoyl (CH3CH2CO) followed by C–CO bond scission of propanoyl to produce CH3CH2 and CO. Finally, CH3CH2 is hydrogenated to CH3CH3. Dehydrogenation reactions that have been observed to be important over Pd catalysts play no role over Ru(0 0 0 1), and a sensitivity analysis indicates that removal of the acid –OH group is the rate-controlling step in the deoxygenation. Altogether, our results suggest that to improve the Ru catalyst performance for the decarbonylation of organic acids, the free site coverage needs to be increased by, for example, adding a catalyst promoter that decreases the hydrogen and CO adsorption strength (without significantly affecting the C–OH bond scission rate), or by raising the reaction temperature and operating at relatively low CO and H2 partial pressures.},
doi = {10.1016/j.jcat.2015.01.005},
journal = {Journal of Catalysis},
number = ,
volume = 324,
place = {United States},
year = {Mon Feb 02 00:00:00 EST 2015},
month = {Mon Feb 02 00:00:00 EST 2015}
}
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    Works referencing / citing this record:

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    Molecular mechanism comparison of decarbonylation with deoxygenation and hydrogenation of 5-hydroxymethylfurfural catalyzed by palladium acetate
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