Journal
GREEN CHEMISTRY
Volume 16, Issue 2, Pages 736-747Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c3gc41183d
Keywords
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Funding
- NSF-CDI I grant [CBET-940768]
- NSF
- Catalysis Center for Energy Innovation (CCEI), an Energy Frontier Research Center
- U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences [DE-SC0001004]
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The reaction energies and the corresponding energy barriers of hydrogenation and ring opening of furan on Pd(111) for the formation of tetrahydrofuran (THF), 1-butanol and small hydrocarbons were studied using density functional theory (DFT). THF forms via sequential hydrogenation of carbon atoms of the furan ring in the order of alpha-carbon, adjacent beta-carbon, second beta-carbon, and the remaining alpha-carbon. Upon hydrogenation of the alpha-carbon of furan, ring opening becomes facile. Thus, hydrofuran (HF) is a reactive intermediate in both hydrogenation and ring opening. The fate of HF determines the selectivity of the overall reaction. A simple kinetic analysis indicates that coverage effects are important and the hydrogen partial pressure is a key factor in controlling selectivity. Dihydrofuran (DHF) was found to be a stable intermediate, consistent with experimental findings. Once DHF is formed, ring opening is not favored due to the high energy barriers of ring opening of DHF, trihydrofuran (TriHF) and THF. 1-Butanol is a thermodynamically favored product, while THF is kinetically preferred. Our theoretical work agrees well with experimental observations that 1-butanol is a major product at high temperatures whereas THF is a major product at low temperatures. Insights gained into selectivity toward ring hydrogenation and ring opening can assist future studies in catalyst selection.
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