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

Mamun, Osman; Saleheen, Mohammad; Bond, Jesse Q.; Heyden, Andreas

doi:10.1021/acs.jpcc.7b06369

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

Journal Article · 03 August 2017 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.7b06369 · OSTI ID:1480506

^[1]; Saleheen, Mohammad ^[1]; Bond, Jesse Q. ^[2];

^[1]

Univ. of South Carolina, Columbia, SC (United States). Dept. of Chemical Engineering
Syracuse Univ., NY (United States). Dept. of Biomedical and Chemical Engineering

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. Finally, 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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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0007167; AC02-05CH11231

OSTI ID:: 1480506

Alternate ID(s):: OSTI ID: 1656916

Journal Information:: Journal of Physical Chemistry. C, Vol. 121, Issue 34; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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