A mechanistic approach to phenol methylation on Cu 1− x Co x Fe 2O 4: FTIR study

• Published in: Journal of catalysis Vol. 227; no. 1; pp. 175 - 185
• Main Authors: Mathew, Thomas, Vijayaraj, Munusamy, Pai, Shivanand, Tope, Balkrishna B., Hegde, Sooryakant G., Rao, B.S., Gopinath, Chinnakonda S.
• Format: Journal Article
• Language: English
• Published: Elsevier Inc 2004
• Subjects: 2,6-Xylenol; Acid–base pair; Adsorbate interaction; Cu 1− xCo xFe 2O 4; DRIFT; Methylation; o-Cresol; Phenol; Reaction mechanism; Cu 1− x Co x Fe 2O 4; Phenol; Acid–base pair; Reaction mechanism; IR; Methylation; o-Cresol; DRIFT; Adsorbate interaction; 2,6-Xylenol
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2004.07.005

The interaction of phenol, methanol, and possible reaction products of phenol methylation with the Cu 1− x Co x Fe 2O 4 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 Cu 1− x Co x Fe 2O 4 above 373 K indicate progressive oxidation to formate and/or dioxymethylene and then to CO, CO 2, and H 2. 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 ν C 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, CoFe 2O 4 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.