Journal
JOURNAL OF PHYSICAL CHEMISTRY C
Volume 121, Issue 34, Pages 18746-18761Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.7b06369
Keywords
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Funding
- National Science Foundation [CBET-1159863]
- U.S. Department of Energy, Office of Basic Energy Sciences [DE-SC0007167]
- Office of Science of the U.S. Department of Energy [DE-AC02-05CH11231]
- Office of Biological and Environmental Research
- U.S. Department of Energy (DOE) [DE-SC0007167] Funding Source: U.S. Department of Energy (DOE)
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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 gamma-valerolactone (GVL) on a Ru(0001) model surface. Focusing on the importance of intramolecular esterification of LA to its stable derivative a-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.
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