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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

Journal Article · · Journal of Catalysis
 [1];  [2];  [1];  [1]
  1. University of South Carolina, Columbia, SC (United States)
  2. University of South Carolina, Columbia, SC (United States); University of Engineering & Technology, Lahore (Pakistan)
+ Show Author Affiliations

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.

Research Organization:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
SC0007167; CHE-1153012; FG02-11ER16268; TG-CTS090100
OSTI ID:
1656913
Alternate ID(s):
OSTI ID: 1430764
Journal Information:
Journal of Catalysis, Vol. 324; ISSN 0021-9517
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 38 works
Citation information provided by
Web of Science

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Cited By (4)

Kinetics study of the Ru/C-catalysed hydrogenolysis of polyols – insight into the interactions with the metal surface journal January 2017
Molecular mechanism comparison of decarbonylation with deoxygenation and hydrogenation of 5-hydroxymethylfurfural catalyzed by palladium acetate journal January 2019
Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups journal January 2018
Valorization of Biomass‐derived Small Oxygenates: Kinetics, Mechanisms and Site Requirements of H 2 ‐involved Hydrogenation and Deoxygenation Pathways over Heterogeneous Catalysts journal February 2019

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Ruthenium
Density functional theory
Microkinetic model
Deoxygenation
Hydrodeoxygenation
Organic acid