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From Bulk CeO, to Supported Cerium-Oxygen Clusters: A Diffuse
Reflectance Approach
A. Bensalem, J. C. Muller and F. Bozon-Verduraz*
Published on 01 January 1992. Downloaded by Benemerita Universidad Autonoma de Puebla on 14/05/2018 19:24:17.
Laboratoire de Chimie des Materiaux Divises et Catalyse, Universite Paris 7-2, place Jussieu, 75251,
Paris cedex 05, France
The diffuse reflectance spectra (UV-VlS) of bu!k and silica-supported CeO, ( <1.10% Ce) are presented. Very
small supported cerium oxide particles (10-15 A) are obtained, which exhibit distinct spectral features assigned
to surface cerium oxygen species.
In contrast with insulating oxides,' the band gap of semicon- sion and the particle size estimated by transmission electron
ducting oxides lies in the 2.5-4 eV interval (20000-35000 microscopy.
cm-')and the intense absorption due to the interband tran- The DR spectra of supported samples, which must be con-
sition occurs in the UV part of the spectrum. It entails a sig- sidered as true DR spectra because silica is by far the major
nificant contribution of specular components in the diffuse component, are compared in Fig. 1 with the (true) DR spec-
reflectance (DR) spectra of these oxides. The aim of this paper trum of pure CeO,. It appears that all supported samples
was first to present the true UV-VIS DR spectrum of CeO,. exhibit a peak centred near 280 nm (B) instead of 350 nm (A)
The second purpose was to explore the DR spectra of very for bulk CeOz. This peak was rather wide for COS,, (B), but
small cerium-oxygen 'clusters' where the collective properties
are expected to vanish. The DR spectra were recorded on a
Beckman 5270 spectrometer equipped with a microcomputer.
The cell used was designed to work under controlled atmo-
sphere.
A
Bulk CeO,
The spectrum of bulk CeO, exhibits a strong group of peaks B a
composed of two maxima near 275 nm (36000 cm-') and
350 nm (28 500 cm- '). To overcome the specular reflectance,
the CeO, powder was mechanically mixed with a high area
silica (380 m2 g- ').
When decreasing the CeO, concentration, the absorbance
of the peak near 275 nm diminished and, for a sample with
2% CeO,, only the peak near 350 nm (A) was left. Hence A
was considered as the true UV-VIS feature of CeO, and the
wavenumber of the absorption edge was taken as an estimate
of the band gap. (A x 400 nm -+ v x 25000 cm-' -,E , x 3.1
eV), in agreement with the values obtained (3.1-3.3 eV) by
transmission on single crystals or films., Ce02
.--------\
DR Spectra of Supported CeO,
Silica-supported CeO, was prepared as follows: (i) silica was
heated under reflux in a benzene solution of CeIV acetyl-
acetonate for 2 h, (ii) the solid obtained was dried at 353 K
and calcined in flowing oxygen at 773 K for 2 h. Some char-
acteristics of the samples are collected in Table 1. The cerium
content was determined by inductively coupled plasma emis-
cerium content
sample (wt.Yo) particle size"
was narrowed for COS, and COS, (the latter showing a Table 2 Assignment of UV-VIS bands
doublet) with a shoulder near 325 nm (unresolved on COS,,).
Hence it appears that A is typical of an infinite three- bands Ifnm Gfcm-' assignment ref.
dimensional array of cerium and oxygen atoms, while B is C 265 38 000 LC Ce"'-oxygen 3
related to the presence of small crystallites which show a high charge transfer
surface/volume ratio. This shift of the absorbance towards B 280 35 700 LC Ce'"-oxygen
shorter wavelengths (blue shift) could then be explained by charge transfer
1
Published on 01 January 1992. Downloaded by Benemerita Universidad Autonoma de Puebla on 14/05/2018 19:24:17.
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spectra with BaSO, as a standard Communication 1/05227F; Received 16th October, 1991