Insight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study

TitleInsight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study
Publication TypeJournal Article
Year of Publication2005
AuthorsVijayaraj, M, Murugan, B, Umbarkar, SB, Hegde, SG, Gopinath, CS
JournalJournal of Molecular Catalysis A - Chemical
Date PublishedAPR
Type of ArticleArticle
KeywordsAniline, Cu1-xZnxFe2O4, desorption limited, DRIFT, IR, Methanol, N-methylaniline, N-methylation, reaction mechanism

Mechanism of selective mono-N-methylation of aniline with methanol on Cu1-xZn2FeO4 catalysts was investigated in detail. The interaction of reactants (aniline. methanol and methanol: aniline) and possible products (N-methylaniline (NMA), N,N-dimethylaniline (DMA) and o-toluidine (OT)) on catalysts surface was studied by temperature-dependent in situ FTIR spectroscopy. Methanol adsorbs dissociatively over catalysts surface at 373 K as methoxy species and is oxidized to formate species at high temperature through dioxymethylene and/or formaldehyde as a surface intermediate species. On the other hand, adsorption of aniline:methanol mixtures shows that methanol oxidation was completely hindered in the presence of aniline. Aniline adsorbs on the Lewis acid sites at <= 373 K with phenyl ring oriented in a perpendicular manner to the catalyst surfaced however, N-H bond scission occurs above 373 K. A comparison of adsorbed NMA and methanol: am line (3:1) mixture on Cu0.5Zn0.5Fe2O4 shows NMA forms from the reaction mixture at 473 K. However, maximum activity at 573 K in catalytic reaction studies suggests that desorption limits the methylation kinetics. FTIR study displays stable aniline and methyl species on ZnFe2O4 even at 573 K; however. no methyl species is detected on Cr0.95Zn0.05Fe2O4 at 473 K due to methanol reforming reaction and that limits the overall reaction and hence low catalytic activity. It is proposed that methanol is protonated on catalysts surface by the labile H+ due to N-H bond scission. Co-adsorption of acidity probes with aniline and methanol indicates that aniline methylation takes place at single acid-base site. (c) 2005 Elsevier B.V. All rights reserved.

Type of Journal (Indian or Foreign)


Impact Factor (IF)3.958
Divison category: 
Catalysis and Inorganic Chemistry