Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound

Phuong Bui, Juan Antonio Cecilia, S. Ted Oyama, Atsushi Takagaki, Antonia Infantes-Molina, Haiyan Zhao, Dan Li, Enrique Rodríguez-Castellón, Antonio Jiménez López

Research output: Contribution to journalArticle

132 Citations (Scopus)

Abstract

A series of silica-supported metal phosphides was prepared by two methods involving the reduction of phosphite (I) or phosphate (A) precursors and was studied for the hydrodeoxygenation (HDO) of 2-methyltetrahydrofuran (2-MTHF). The I method required lower temperature than the A method and resulted in catalysts with higher surface area. The activity was evaluated in a packed-bed reactor on the basis of equal CO chemisorption sites (30 μmol) loaded in the reactor with comparison made to a commercial Pd/Al 2O 3 catalyst. At 300 °C and 1 atm, the order of activity was Ni 2P > WP > MoP > CoP > FeP > Pd/Al 2O 3. The principal HDO products for the iron group phosphides (Ni 2P and CoP) were pentane and butane, whereas for the group 6 metal phosphides (MoP and WP), the products were mostly pentenes and pentadienes. For the Pd/Al 2O 3 and the low-activity FeP/SiO 2 catalyst the products were mostly pentenes and C4 mixtures. There were no significant differences in the turnover frequency between materials prepared by the two methods, except possibly for the case of WP. There were likewise no great changes in selectivity toward HDO products at 5% total conversion, except for WP. The differences in the case of WP were attributed to the surface P/W ratio that X-ray photoelectron spectroscopy (XPS) showed to be twice as large for the I method than the A method. Contact-time studies were used to develop reaction networks for the most active catalysts, Ni 2P/SiO 2 and WP/SiO 2. For Ni 2P/SiO 2 by both methods, the selectivity profiles were similar and could be explained by a rake mechanism with pentenes as primary products, 2-pentanone as a secondary product, and pentane as a final product. In contrast, for WP/SiO 2, the selectivity depended greatly on the preparation method, but produced a preponderance of unsaturated compounds. The results could be explained from the surface composition.

Original languageEnglish
Pages (from-to)184-198
Number of pages15
JournalJournal of Catalysis
Volume294
DOIs
Publication statusPublished - Oct 1 2012
Externally publishedYes

Fingerprint

phosphides
Biofuels
Transition metals
Alkenes
transition metals
Catalysts
synthesis
products
Alkadienes
Metals
catalysts
Unsaturated compounds
Phosphites
selectivity
pentanes
Time and motion study
Butane
Packed beds
Carbon Monoxide
Chemisorption

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Physical and Theoretical Chemistry

Cite this

Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound. / Bui, Phuong; Cecilia, Juan Antonio; Oyama, S. Ted; Takagaki, Atsushi; Infantes-Molina, Antonia; Zhao, Haiyan; Li, Dan; Rodríguez-Castellón, Enrique; Jiménez López, Antonio.

In: Journal of Catalysis, Vol. 294, 01.10.2012, p. 184-198.

Research output: Contribution to journalArticle

Bui, P, Cecilia, JA, Oyama, ST, Takagaki, A, Infantes-Molina, A, Zhao, H, Li, D, Rodríguez-Castellón, E & Jiménez López, A 2012, 'Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound', Journal of Catalysis, vol. 294, pp. 184-198. https://doi.org/10.1016/j.jcat.2012.07.021
Bui, Phuong ; Cecilia, Juan Antonio ; Oyama, S. Ted ; Takagaki, Atsushi ; Infantes-Molina, Antonia ; Zhao, Haiyan ; Li, Dan ; Rodríguez-Castellón, Enrique ; Jiménez López, Antonio. / Studies of the synthesis of transition metal phosphides and their activity in the hydrodeoxygenation of a biofuel model compound. In: Journal of Catalysis. 2012 ; Vol. 294. pp. 184-198.
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AU - Infantes-Molina, Antonia

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