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Title: Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study

Abstract

Microkinetic models based on first principles calculations have been used to study the vapor and liquid phase hydrodeoxygenation of propionic acid on a Rh(111) surface. Calculations suggest that both decarboxylation and decarbonylation do not occur at an appreciable rate under all reaction environments. Propanol and propionaldehyde are the main products on this surface and they are produced at similar rates in both vapor and liquid phase environments. While a condensed phase can shift the reaction rate, the dominant pathways and selectivity towards the various products are hardly affected. At 473 K, the turnover frequency is increased by about a factor of 1.5 in liquid water relative to the gas phase. In liquid 1,4-dioxane, the turnover frequency is also slightly increased relative to the gas phase. Here, given the uncertainty in Rh cavity radius in the liquid phase calculations, computations with different cavity radii have been performed. With larger Rh cavity radius, the promotional effect of the solvents on the turnover frequency becomes more significant, while practically no changes are observed for a smaller cavity radius.

Authors:
 [1];  [1];  [1];  [2]; ORCiD logo [1]
  1. University of South Carolina, Columbia, SC (United States)
  2. Syracuse University, NY (United States)
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE
OSTI Identifier:
1656889
Alternate Identifier(s):
OSTI ID: 1657881
Grant/Contract Number:  
SC0007167; DMREF-1534260; TG-CTS090100
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 391; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Propionic acid; Hydrodeoxygenation mechanism; Propanol; Propionaldehyde; Microkinetic modeling; Solvent effect; Lateral interaction

Citation Formats

Yang, Wenqiang, Solomon, Rajadurai Vijay, Mamun, Osman, Bond, Jesse Q., and Heyden, Andreas. Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study. United States: N. p., 2020. Web. https://doi.org/10.1016/j.jcat.2020.08.015.
Yang, Wenqiang, Solomon, Rajadurai Vijay, Mamun, Osman, Bond, Jesse Q., & Heyden, Andreas. Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study. United States. https://doi.org/10.1016/j.jcat.2020.08.015
Yang, Wenqiang, Solomon, Rajadurai Vijay, Mamun, Osman, Bond, Jesse Q., and Heyden, Andreas. Fri . "Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study". United States. https://doi.org/10.1016/j.jcat.2020.08.015. https://www.osti.gov/servlets/purl/1656889.
@article{osti_1656889,
title = {Investigation of the reaction mechanism of the hydrodeoxygenation of propionic acid over a Rh(1 1 1) surface: A first principles study},
author = {Yang, Wenqiang and Solomon, Rajadurai Vijay and Mamun, Osman and Bond, Jesse Q. and Heyden, Andreas},
abstractNote = {Microkinetic models based on first principles calculations have been used to study the vapor and liquid phase hydrodeoxygenation of propionic acid on a Rh(111) surface. Calculations suggest that both decarboxylation and decarbonylation do not occur at an appreciable rate under all reaction environments. Propanol and propionaldehyde are the main products on this surface and they are produced at similar rates in both vapor and liquid phase environments. While a condensed phase can shift the reaction rate, the dominant pathways and selectivity towards the various products are hardly affected. At 473 K, the turnover frequency is increased by about a factor of 1.5 in liquid water relative to the gas phase. In liquid 1,4-dioxane, the turnover frequency is also slightly increased relative to the gas phase. Here, given the uncertainty in Rh cavity radius in the liquid phase calculations, computations with different cavity radii have been performed. With larger Rh cavity radius, the promotional effect of the solvents on the turnover frequency becomes more significant, while practically no changes are observed for a smaller cavity radius.},
doi = {10.1016/j.jcat.2020.08.015},
journal = {Journal of Catalysis},
number = ,
volume = 391,
place = {United States},
year = {2020},
month = {8}
}

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