A mechanistic approach to phenol methylation on Cu1-xCoxFe2O4: FTIR study

Mathew, Thomas ; Vijayaraj, Munusamy ; Pai, Shivanand ; Tope, Balkrishna B. ; Hegde, Sooryakant G. ; Rao, B. S. ; Gopinath, Chinnakonda S. (2004) A mechanistic approach to phenol methylation on Cu1-xCoxFe2O4: FTIR study Journal of Catalysis, 227 (1). pp. 175-185. ISSN 0021-9517

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Official URL: http://www.sciencedirect.com/science/article/pii/S...

Related URL: http://dx.doi.org/10.1016/j.jcat.2004.07.005


The interaction of phenol, methanol, and possible reaction products of phenol methylation with the Cu1-xCoxFe2O4 system has been studied by FTIR spectroscopy in the temperature range between 373 and 623 K. The spectra obtained from the chemisorption of methanol onto Cu1-xCoxFe2O4 above 373 K indicate progressive oxidation to formate and/or dioxymethylene and then to CO, CO2, and H2. Phenol is predominantly adsorbed as phenolate species by the dissociative adsorption on an acid-base site and the phenyl ring of phenol is perpendicular to the catalyst surface, facilitating selective ortho methylation by methyl cations. Characteristic νC—O bands observed for ortho-methylated phenols on the catalyst surface allow the identification of the same from the reaction mixture adsorbed on catalysts at 473 K, well below the optimum reaction temperature of 623 K, on Cu-containing catalysts. However, CoFe2O4 shows little interaction of phenol with MeOH, when they are coadsorbed, and might be a limiting factor to the overall reaction. Coadsorption of acidity probes with phenol and methanol indicates that the same acid-base sites are responsible for the reaction. Methylated phenols show a weak interaction with the surface compared to phenol and are susceptible to desorption at reaction temperatures and thus facilitate efficient methylation.

Item Type:Article
Source:Copyright of this article belongs to Elsevier Science.
Keywords:Cu1-xCoxFe2O4; Phenol; Methylation; O-cresol; 2,6-xylenol; Drift; Adsorbate Interaction; Reaction Mechanism; Acid-base Pair; IR
ID Code:61853
Deposited On:15 Sep 2011 12:13
Last Modified:15 Sep 2011 12:13

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