Insights into the Ring-Opening of Biomass-Derived Furanics over Carbon-Supported Ruthenium

Matthew J. Gilkey, Alexander V. Mironenko, Leerang Yang, Dionisios G. Vlachos, Bingjun Xu

Research output: Contribution to journalArticlepeer-review

Abstract

The selective ring-opening of cellulose-derived furanic molecules is a promising pathway for the production of industrially relevant linear oxygenates, such as 1,6-hexanediol. 2,5-Dimethylfuran (DMF) is employed as a model compound in a combined experimental and computational investigation to provide insights into the metal-catalyzed ring-opening. Ring-opening to 2-hexanol and 2-hexanone and ring-saturation to 2,5-dimethyltetrahydrofuran (DMTHF) are identified as two main parallel pathways. DFT calculations and microkinetic modeling indicate that DMF adsorbs on Ru in an open-ring configuration, which is potentially a common surface intermediate that leads to both ring-opening and ring-saturation products. Although the activation barriers for the two pathways are comparable, the formation of DMTHF is more thermodynamically favorable. In addition, steric interactions with co-adsorbed 2-propoxyl, derived from the solvent, and the oxophilic nature of Ru play key roles to determine the product distribution: the former favors less bulky, that is, ring-closed, intermediates, and the latter retards O−H bond formation. Finally, we show that the hydrodeoxygenation of oxygenated furanics, such as 5-methylfurfural and (5-methyl-2-furyl)methanol, on Ru occurs preferentially at oxygen-containing side groups to form DMF, followed by either ring-opening or ring-saturation.

Original languageEnglish (US)
Pages (from-to)3113-3121
Number of pages9
JournalChemSusChem
Volume9
Issue number21
DOIs
StatePublished - Nov 9 2016
Externally publishedYes

Keywords

  • biomass
  • hydrogenation
  • reaction mechanisms
  • ruthenium
  • supported catalysts

ASJC Scopus subject areas

  • Environmental Chemistry
  • Chemical Engineering(all)
  • Materials Science(all)
  • Energy(all)

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