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Catalysis Communications 8 (2007) )50-156
CATALYSIS
COMMUNICATIONS
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Vanadia supported on ceria: Characterization and activity
in liquid-phase oxidation of ethylbenzene
T. Radhika, S. Sugunan *
Dcpurtmcnt of Applied Chemistry. Cochin University of Science and Technology, Cochin-Tl, Kerala 682022, India
Received 8 March 2006; received in revised form 8 May 2006; accepted 23 May 2006
Available online 3 June 2006
ties of ceria (Ce
4
+ /Ce
H
) and the high lability of its lattice
oxygen are among the most important factors that contrib-
ute to the catalytic reactivity in oxidation reactions [IOJ.
Side-chain oxidation of alkyl aromatics using cleaner
peroxide oxidants catalyzed by heterogeneous catalysts
has been much interesting [11 J, Effective utilization of eth-
ylbcnzene, available in the xylene stream of the petrochem-
ical industry to more value added products is a promising
one in chemical industry. The oxidation products of ethyl-
benzene are widely employed as intermediates in organic,
steroid and resin synthesis [12-14]. Zeolite encapsulated
Cot llj, Ni(ll) and Cu(Il) complexes gave acetophenone
as the only partial oxidation product during ethyl benzene
oxidation with H
20 2
[15]. Titanosilicates mainly catalyze
ring hydroxylation of arenes with H
20 2
, whereas vanadium
and chromium substituted zeolites and aluminophosphate
molecular sieves have been known to favour side-chain oxi-
dation selectively [16].
In the present work. we report the structural character-
ization of ceria supported vanadia catalysts for various
loading of V205 observed using different physico-chemical
1-
, author. Tel.: +91 4842575804: fax: +9\ 484 2577595.
E-mail adiln.s.\"_ssg@cusat.ac.in (S. Sugunanj.
I 1. Introduction
! Supported vanadium oxide catalysts have been exten-
I
".:jy used for catalyzing several oxidation reactions [1-
5J..The redox chemistry of ceria is a critical parameter in
I
u:::""\ffieiency of multifunctional components of three-way
automotive catalysts and applications of these materials
I
other catalytic processes such as oxygen perme-
ation membrane systems. deNO, catalysis, oxidation of
I
... and catalytic wet oxidation are being extensively
studied (6,7J. In recent years vanadia/ceria combination
,",-='ysts have been the subjects of numerous investigations
I because of its wide range applications in catalysis and
•• science [8,9]. Generally, oxidation rate is limited
I by the oxygen transfer from the liquid phase to the metal
,..":'e sites. while ceria is able to enhance this oxygen trans-
I fer to efficiently catalyze the reactions. The redox proper-
.:)
...,..,
Abstract
I
,'"""'I
""anildia/ceriil catalysts (2 iO wt':;', of V20
5)
were prepared by wet impregnation of ammonium mctavanadate in oxalic acid solution.
'StJilIl,ctural characterization was done with energy dispersive X-ray analysis (EDX). powder X-ray diffraction (XRD), BET surface area
I FT-IR spectroscopy and nuclear magnetic spectral analysis (
51V
MASNMR). XRD and 5lV MASNMR results show
I dispersed vanadia species at lower loadings and the formation of CeV0
4
phase at higher V
20S
loading. The catalytic activity
I
o..:1talysts was conducted in liquid phase oxidation of ethylbenzenc with H
20 2
as oxidant. The oxidation activity is increased with load-
ing up to 8 wt% V205 and then decreased with further increase in V205 content to 10 wt%. Different vanadia species evidenced by various
, were found to be selective towards ethylbenzene oxidation. The CeV0
4
formation associated with increased concentration of
I vanadia on ceria results the production of acetophenone along with 2-hydroxyacetophenone.
Elsevier B.V. All rights reserved.
Vanadia: Ceria: CeVO.; Ethylbenzenc oxidation: SIV MASNMR
1-
1566-7367/5 - see front matter © 2006 Elsevier B.V. All rights reserved.