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Title: Importance of Angelica Lactone Formation in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over a Ru(0001) Model Surface

Abstract

Using mean-field microkinetic modeling with parameters derived from density functional theory calculations and harmonic transition state theory, we investigated the steady-state catalytic hydrodeoxygenation of levulinic acid (LA) to γ-valerolactone (GVL) on a Ru(0001) model surface. Focusing on the importance of intramolecular esterification of LA to its stable derivative α-angelica lactone (AGL) during the HDO to GVL, we studied various reaction pathways for GVL production that involve AGL and 4-hydroxypentanoic acid (HPA). We find that in a nonpolar reaction environment these pathways are not kinetically relevant but that GVL can be produced from LA by a single hydrogenation step, followed by ring closure and C–OH bond cleavage. However, AGL reaction pathways lead to surface poisoning at temperatures above 423 K when these pathways become kinetically accessible. As a result of surface poisoning—possibly at low temperatures by hydrogen and at high temperatures by AGL derivatives—we observe two different activity regimes characterized by significantly different activation barriers. Overall, simulation results agree well with experimental observations except at low temperatures of 323 K where our model significantly underestimates the turnover frequency, questioning whether Ru(0001) sites are active at these low temperatures.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]
  1. Department of Chemical Engineering, University of South Carolina, 301 Main Street, Columbia, South Carolina 29208, United States
  2. Department of Biomedical and Chemical Engineering, Syracuse University, Syracuse, New York 13244, United States
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
OSTI Identifier:
1480506
DOE Contract Number:  
SC0007167; AC02-05CH11231
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physical Chemistry. C; Journal Volume: 121; Journal Issue: 34
Country of Publication:
United States
Language:
English

Citation Formats

Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., and Heyden, Andreas. Importance of Angelica Lactone Formation in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over a Ru(0001) Model Surface. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b06369.
Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., & Heyden, Andreas. Importance of Angelica Lactone Formation in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over a Ru(0001) Model Surface. United States. doi:10.1021/acs.jpcc.7b06369.
Mamun, Osman, Saleheen, Mohammad, Bond, Jesse Q., and Heyden, Andreas. Thu . "Importance of Angelica Lactone Formation in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over a Ru(0001) Model Surface". United States. doi:10.1021/acs.jpcc.7b06369.
@article{osti_1480506,
title = {Importance of Angelica Lactone Formation in the Hydrodeoxygenation of Levulinic Acid to γ-Valerolactone over a Ru(0001) Model Surface},
author = {Mamun, Osman and Saleheen, Mohammad and Bond, Jesse Q. and Heyden, Andreas},
abstractNote = {Using mean-field microkinetic modeling with parameters derived from density functional theory calculations and harmonic transition state theory, we investigated the steady-state catalytic hydrodeoxygenation of levulinic acid (LA) to γ-valerolactone (GVL) on a Ru(0001) model surface. Focusing on the importance of intramolecular esterification of LA to its stable derivative α-angelica lactone (AGL) during the HDO to GVL, we studied various reaction pathways for GVL production that involve AGL and 4-hydroxypentanoic acid (HPA). We find that in a nonpolar reaction environment these pathways are not kinetically relevant but that GVL can be produced from LA by a single hydrogenation step, followed by ring closure and C–OH bond cleavage. However, AGL reaction pathways lead to surface poisoning at temperatures above 423 K when these pathways become kinetically accessible. As a result of surface poisoning—possibly at low temperatures by hydrogen and at high temperatures by AGL derivatives—we observe two different activity regimes characterized by significantly different activation barriers. Overall, simulation results agree well with experimental observations except at low temperatures of 323 K where our model significantly underestimates the turnover frequency, questioning whether Ru(0001) sites are active at these low temperatures.},
doi = {10.1021/acs.jpcc.7b06369},
journal = {Journal of Physical Chemistry. C},
number = 34,
volume = 121,
place = {United States},
year = {Thu Aug 17 00:00:00 EDT 2017},
month = {Thu Aug 17 00:00:00 EDT 2017}
}