Ligand and ensemble effects in bimetallic NiFe phosphide catalysts for the hydrodeoxygenation of 2-methyltetrahydrofuran

Ara Cho, Jieun Shin, Atsushi Takagaki, Ryuji Kikuchi, S. Ted Oyama

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

A series of supported nickel-iron phosphide catalysts were used to study the hydrodeoxygenation (HDO) of 2-methyltetrahydrofuran (2-MTHF), a model compound for biomass-derived pyrolysis oil. The catalysts were prepared by incipient wetness impregnation of the active components onto potassium ion-exchanged USY zeolites followed by temperature-programmed reduction. The samples were denoted as Ni2P/KUSY, NiFeP(3:1)/KUSY, NiFeP(1:1)/KUSY, NiFeP(1:3)/KUSY, and FeP/KUSY, where the numbers in parenthesis are the Ni:Fe molar ratios. The results of the studies can be understood from ensemble and ligand effects. X-ray diffraction analysis indicated the presence of alloys in the mixed composition samples, and this was supported by CO chemisorption and infrared measurements. Uptakes of CO decreased as the iron content increased, suggesting that iron present on the surface of the catalysts blocked chemisorption sites. Fourier transform infrared (FTIR) measurements showed a single peak for linearly adsorbed CO whose intensity decreased with Fe content, in agreement with the uptake results. Moreover, the FTIR peak shifted monotonically consistent with a ligand effect in an alloy formed in the Ni 2P and FeP particles. The reactivity in 2-MTHF HDO was studied at 250-325 °C and 0.5 MPa and it was found that the conversion was highest for the Ni 2P/KUSY sample and decreased steadily with Fe content. However, the turnover frequency did not change significantly, indicating that the rate-determing step was activation of 2-MTHF on single Ni sites. The selectivity at low conversion (3 %) changed from mostly n-pentane and n-butane for Ni 2P/KUSY to mostly 1-pentanol for the ironcontaining samples, suggesting that in subsequent steps an ensemble effect was operational with the iron influencing the reaction chemistry. At high conversion (70 %) all the samples produced mostly n-pentane and n-butane.

Original languageEnglish
Pages (from-to)969-980
Number of pages12
JournalTopics in Catalysis
Volume55
Issue number14-15
DOIs
Publication statusPublished - Oct 1 2012
Externally publishedYes

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Carbon Monoxide
Iron
Ligands
Catalysts
Butane
Chemisorption
Infrared radiation
Fourier transforms
Zeolites
Nickel
Impregnation
X ray diffraction analysis
Potassium
Oils
Biomass
Pyrolysis
Chemical activation
Ions
2-methyltetrahydrofuran
Chemical analysis

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Cite this

Ligand and ensemble effects in bimetallic NiFe phosphide catalysts for the hydrodeoxygenation of 2-methyltetrahydrofuran. / Cho, Ara; Shin, Jieun; Takagaki, Atsushi; Kikuchi, Ryuji; Oyama, S. Ted.

In: Topics in Catalysis, Vol. 55, No. 14-15, 01.10.2012, p. 969-980.

Research output: Contribution to journalArticle

Cho, Ara ; Shin, Jieun ; Takagaki, Atsushi ; Kikuchi, Ryuji ; Oyama, S. Ted. / Ligand and ensemble effects in bimetallic NiFe phosphide catalysts for the hydrodeoxygenation of 2-methyltetrahydrofuran. In: Topics in Catalysis. 2012 ; Vol. 55, No. 14-15. pp. 969-980.
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