Furfural hydrodeoxygenation (HDO) over silica-supported metal phosphides – the influence of metal - phosphorus stoichiometry on catalytic properties

X. Lan, Robert Pestman, Emiel J.M. Hensen, Thomas Weber (Corresponding author)

Research output: Contribution to journalArticleAcademicpeer-review

Abstract

The gas-phase hydrodeoxygenation (HDO) of furfural, a model compound for bio-based conversion, was investigated over transition metal phosphide catalysts. The HDO activity decreases in the order Ni 2P ≈ MoP > Co 2P ≈ WP ≫ Cu 3P > Fe 2P. Nickel phosphide phases (e.g., Ni 2P, Ni 12P 5, Ni 3P) are the most promising catalysts in the furfural HDO. Their selectivity to the gasoline additives 2-methylfuran and tetrahydro-2-methylfuran can be adjusted by varying the P/Ni ratio. The effect of P on catalyst properties as well as on the reaction mechanism of furfural HDO were investigated in depth for the first time. An increase of the P stoichiometry weakens the furan-ring/catalyst interaction, which contributes to a lower ring-opening and ring-hydrogenation activity. On the other hand, an increasing P content does lead to a stronger carbonyl/catalyst interaction, i.e., to a stronger η 2(C, O) adsorption configuration, which weakens the C1[sbnd]O1 bond (Scheme 1) in the carbonyl group and enhances the carbonyl conversion. Phosphorus species can also act as Brønsted acid sites promoting C1[sbnd]O1 (Scheme 1) hydrogenolysis of furfuryl alcohol, hence contributing to higher production of 2-methylfuran.

Original languageEnglish
JournalJournal of Catalysis
VolumeXX
Issue numberXX
DOIs
Publication statusAccepted/In press - 2021

Keywords

  • Biomass
  • Co P
  • Furfural
  • Hydrodeoxygenation
  • Infrared spectroscopy
  • Mechanism
  • Metal phosphide
  • Ni P

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