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Title: Mechanistic Insights into the Hydrogenolysis of Levoglucosanol over Bifunctional Platinum Silica–Alumina Catalysts

Journal Article · · ACS Catalysis
 [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States). Department of Chemical and Biological Engineering
  2. Argonne National Lab. (ANL), Lemont, IL (United States). Materials Science Division
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In this paper, we report on the hydrogenolysis of the biorenewable intermediate levoglucosanol (Lgol) over bifunctional platinum catalysts supported on silica–alumina in tetrahydrofuran solvent. 13C radiolabeling is used to confirm the ring rearrangement forming tetrahydrofurandimethanol. The reaction rate and product selectivity are comparable between 1.1 and 5.3 wt % Pt loadings, indicating that, at these metal loadings, the rate-limiting step is acid catalyzed. The measured zero-order dependence in hydrogen indicates that a non-rate-determining hydrogenation step follows an acid-catalyzed irreversible rate-determining step. The measured first-order dependence in Lgol indicates that the acid sites are not highly covered by Lgol. A physical mixture of Pt/SiO2 and SiAl catalysts displayed product selectivity similar to that of the Pt/SiAl catalyst, indicating that nanoscale proximity of metal and acid sites is not required to carry out Lgol hydrogenolysis selectively. As the Pt loading in Pt/SiAl catalysts is decreased, or when the bare SiAl support is separated from a Pt/SiO2 catalyst in a dual-layer configuration, the selectivity toward identified products decreases. These results suggest that degradation reactions are avoided when the reactive intermediates formed over acid sites are rapidly hydrogenated over metal sites. First-principles simulations are performed to investigate the energetics of the proposed reaction pathway. A detailed reaction mechanism for Lgol hydrogenolysis is proposed on the basis of a combination of the experimental and computational results. Our findings provide a fundamental understanding of the catalytic conversion of levoglucosanol over bifunctional metal–acid catalysts, facilitating rationally designed processes to produce renewable chemicals from biomass-derived levoglucosenone.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Energy Efficiency and Renewable Energy (EERE)
Contributing Organization:
University of Wisconsin-Madison Department of Chemistry; University of Wisconsin-Madison Department of Civil and Environmental Engineering; Consortium for Computational Physics and Chemistry (CCPC); Laboratory Computing Resource Center at Argonne National Laboratory
Grant/Contract Number:
EE0006878; AC02-06CH11357; AC02-05CH11231
OSTI ID:
1477855
Journal Information:
ACS Catalysis, Vol. 8, Issue 5; ISSN 2155-5435
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

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Cited By (3)

Catalytic production of hexane-1,2,5,6-tetrol from bio-renewable levoglucosanol in water: effect of metal and acid sites on (stereo)-selectivity journal January 2018
Tuning zirconia-supported metal catalysts for selective one-step hydrogenation of levoglucosenone journal January 2019
The Roles of H2O/Tetrahydrofuran System in Lignocellulose Valorization journal February 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
36 MATERIALS SCIENCE
bifunctional
biomass
catalysis
heterogeneous
kinetics
levoglucosenone
mechanism