Phenol methylation over nanoparticulate Co2FeO4 inverse spinel catalysts

the effect of morphology on catalytic performance

Nicola Ballarini, Fabrizio Cavani, Sauro Passeri, Lucilla Pesaresi, Adam F. Lee, Karen Wilson

Research output: Contribution to journalArticle

Abstract

A series of CoFe2O4 nanoparticles have been prepared via co-precipitation and controlled thermal sintering, with tunable diameters spanning 7–50 nm. XRD confirms that the inverse spinel structure is adopted by all samples, while XPS shows their surface compositions depend on calcination temperature and associated particle size. Small (<20 nm) particles expose Fe3+ enriched surfaces, whereas larger (∼50 nm) particles formed at higher temperatures possess Co:Fe surface compositions close to the expected 1:2 bulk ratio. A model is proposed in which smaller crystallites expose predominately (1 1 1) facets, preferentially terminated in tetrahedral Fe3+ surface sites, while sintering favours (1 1 0) and (1 0 0) facets and Co:Fe surface compositions closer to the bulk inverse spinel phase. All materials were active towards the gas-phase methylation of phenol to o-cresol at temperatures as low as 300 °C. Under these conditions, materials calcined at 450 and 750 °C exhibit o-cresol selectivities of ∼90% and 80%, respectively. Increasing either particle size or reaction temperature promotes methanol decomposition and the evolution of gaseous reductants (principally CO and H2), which may play a role in CoFe2O4 reduction and the concomitant respective dehydroxylation of phenol to benzene. The degree of methanol decomposition, and consequent H2 or CO evolution, appears to correlate with surface Co2+ content: larger CoFe2O4 nanoparticles have more Co rich surfaces and are more active towards methanol decomposition than their smaller counterparts. Reduction of the inverse spinel surface thus switches catalysis from the regio- and chemo-selective methylation of phenol to o-cresol, towards methanol decomposition and phenol dehydroxylation to benzene. At 300 °C sub-20 nm CoFe2O4 nanoparticles are less active for methanol decomposition and become less susceptible to reduction than their 50 nm counterparts, favouring a high selectivity towards methylation.
Original languageEnglish
Pages (from-to)184-192
Number of pages9
JournalApplied Catalysis A: General
Volume366
Issue number1
Early online date10 Jul 2009
DOIs
Publication statusPublished - 15 Sep 2009

Fingerprint

Methylation
Phenol
Phenols
Methanol
Decomposition
Catalysts
Surface structure
Carbon Monoxide
Nanoparticles
Benzene
Sintering
Particle size
Temperature
Reducing Agents
Coprecipitation
Crystallites
Calcination
Catalysis
X ray photoelectron spectroscopy
Gases

Keywords

  • heterogeneous catalysis
  • inverse spinel
  • phenol methylation
  • clean technology
  • XPS
  • nanoparticles

Cite this

Ballarini, Nicola ; Cavani, Fabrizio ; Passeri, Sauro ; Pesaresi, Lucilla ; Lee, Adam F. ; Wilson, Karen. / Phenol methylation over nanoparticulate Co2FeO4 inverse spinel catalysts : the effect of morphology on catalytic performance. In: Applied Catalysis A: General. 2009 ; Vol. 366, No. 1. pp. 184-192.
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Phenol methylation over nanoparticulate Co2FeO4 inverse spinel catalysts : the effect of morphology on catalytic performance. / Ballarini, Nicola; Cavani, Fabrizio; Passeri, Sauro; Pesaresi, Lucilla; Lee, Adam F.; Wilson, Karen.

In: Applied Catalysis A: General, Vol. 366, No. 1, 15.09.2009, p. 184-192.

Research output: Contribution to journalArticle

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T1 - Phenol methylation over nanoparticulate Co2FeO4 inverse spinel catalysts

T2 - the effect of morphology on catalytic performance

AU - Ballarini, Nicola

AU - Cavani, Fabrizio

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AB - A series of CoFe2O4 nanoparticles have been prepared via co-precipitation and controlled thermal sintering, with tunable diameters spanning 7–50 nm. XRD confirms that the inverse spinel structure is adopted by all samples, while XPS shows their surface compositions depend on calcination temperature and associated particle size. Small (<20 nm) particles expose Fe3+ enriched surfaces, whereas larger (∼50 nm) particles formed at higher temperatures possess Co:Fe surface compositions close to the expected 1:2 bulk ratio. A model is proposed in which smaller crystallites expose predominately (1 1 1) facets, preferentially terminated in tetrahedral Fe3+ surface sites, while sintering favours (1 1 0) and (1 0 0) facets and Co:Fe surface compositions closer to the bulk inverse spinel phase. All materials were active towards the gas-phase methylation of phenol to o-cresol at temperatures as low as 300 °C. Under these conditions, materials calcined at 450 and 750 °C exhibit o-cresol selectivities of ∼90% and 80%, respectively. Increasing either particle size or reaction temperature promotes methanol decomposition and the evolution of gaseous reductants (principally CO and H2), which may play a role in CoFe2O4 reduction and the concomitant respective dehydroxylation of phenol to benzene. The degree of methanol decomposition, and consequent H2 or CO evolution, appears to correlate with surface Co2+ content: larger CoFe2O4 nanoparticles have more Co rich surfaces and are more active towards methanol decomposition than their smaller counterparts. Reduction of the inverse spinel surface thus switches catalysis from the regio- and chemo-selective methylation of phenol to o-cresol, towards methanol decomposition and phenol dehydroxylation to benzene. At 300 °C sub-20 nm CoFe2O4 nanoparticles are less active for methanol decomposition and become less susceptible to reduction than their 50 nm counterparts, favouring a high selectivity towards methylation.

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