%0 Journal Article %J Journal of Molecular Catalysis A - Chemical %D 2005 %T Insight into the mechanism of selective mono-N-methylation of aniline on Cu1-xZnxFe2O4: a DRIFTS study %A Vijayaraj, M. %A Murugan, B. %A Shubhangi B. Umbarkar %A Hegde, S. G. %A Gopinath, Chinnakonda S. %K Aniline %K Cu1-xZnxFe2O4 %K desorption limited %K DRIFT %K IR %K Methanol %K N-methylaniline %K N-methylation %K reaction mechanism %X

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.

%B Journal of Molecular Catalysis A - Chemical %I ELSEVIER SCIENCE BV %C PO BOX 211, 1000 AE AMSTERDAM, NETHERLANDS %V 231 %P 169-180 %8 APR %G eng %N 1-2 %9 Article %3

Foreign

%4 3.958 %R 10.1016/j.molcata.2005.01.014