Details

Autor(en) / Beteiligte

• Lan, Xuefang
• Pestman, Robert
• Hensen, Emiel J.M.
• Weber, Thomas

Titel

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

Ist Teil von

• Journal of catalysis, 2021-11, Vol.403, p.181-193

Ort / Verlag

Elsevier Inc

Erscheinungsjahr

2021

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• Effect of phosphorus on the furfural HDO over nickel and nickel phosphide catalysts. [Display omitted] •Furfural HDO activity decreases in order: Ni2P ≈ MoP > Co2P > WP ≫ Cu3P > Fe2P.•More stable η2(C, O) adsorption on surfaces with increasing P/metal ratio.•More Brønsted acid sites with increasing P/metal ratio.•Furan-ring hydrogenation and ring opening suppressed with increasing P/metal content.•The carbonyl group conversion increased at higher P/metal ratio. 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 Ni2P ≈ MoP > Co2P ≈ WP ≫ Cu3P > Fe2P. Nickel phosphide phases (e.g., Ni2P, Ni12P5, Ni3P) 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 η2(C, O) adsorption configuration, which weakens the C1O1 bond (Scheme 1) in the carbonyl group and enhances the carbonyl conversion. Phosphorus species can also act as Brønsted acid sites promoting C1O1 (Scheme 1) hydrogenolysis of furfuryl alcohol, hence contributing to higher production of 2-methylfuran.