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J. CHEM. SOC. FARADAY TRANS., 1992, 88(1), 153-154 153

FARADAY COMMUNICATIONS
From Bulk CeO, to Supported Cerium-Oxygen Clusters: A Diffuse
Reflectance Approach
A. Bensalem, J. C. Muller and F. Bozon-Verduraz*
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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-

Table 1 Description of samples

cerium content
sample (wt.Yo) particle size"

pure CeO, 81.4 lo00

cos10 1.10 10-15 I
300
I
500
I
701
cos7 0.022 -
A/n m
cos j 0.007 -
Fig. 1 DR spectra of bulk and silica-supported CeO, (standard:
" According to observations by electron microscopy silica) Bulk CeO, = 2% CeO, mixed with silica

154
was narrowed for COS, and COS, (the latter showing a
doublet) with a shoulder near 325 nm (unresolved on COS,,).
Hence it appears that A is typical of an infinite three-
dimensional array of cerium and oxygen atoms, while B is
related to the presence of small crystallites which show a high
surface/volume ratio. This shift of the absorbance towards
shorter wavelengths (blue shift) could then be explained by
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the predominance of CeIv-oxygen charge transfers occurring
on low coordination Ce" ions. Experiments were conducted
in a controlled atmosphere to give information on this point.
Fig. 2 presents the influence of various thermal treatments on
the DR spectrum of the COS,, sample. After outgassing at
1073 K overnight, B was replaced by a shoulder C at 265 nm
and a band D near 325 nm. Oxygen adsorption at 293 K,
partly restored B and gave rise to a broad band E near 425
nm. Consecutive heating in oxygen at 873 K for 30 min
brought back the initial B band. Finally another outgassing
at 1073 K led to the reappearance of C and D. The assign-
ment of the different bands, presented in Table 2 will now be
discussed.
The C band can be ascribed to a Ce"'-oxygen charge
transfer, by analogy with the model compound Ce"'(H,O),,
which shows a band at 253 nm.3 Although no Ce"(H,O),
species is known, the CeIv-oxygen charge transfer should
occur at a lower energy (greater wavelength) as the Ce" ion
is more reducible4 and the assignment of B (A = 280 nm)
agrees well with this observation. In addition, the restoration
of B after heating in oxygen supports this view. The E band
can be ascribed to the adsorbed 0, ion, previously observed
*-. --.
0'280 '.
I I I I
300 400 500 600
A/n m
Fig. 2 Influence of consecutive thermal treatments on the DR spec-
trum of COS,, (1.10% CeO,). ( a ) Initial sample, (b) after outgassing
at 1073 K overnight, (c) 0, adsorption at 293 K, 100 Torr, (d) after
heating in 0, at 873 K, (e) after outgassing at 1073 K overnight, all
spectra with BaSO, as a standard
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J. CHEM. SOC. FARADAY TRANS., 1992, VOL. 88
Table 2 Assignment of UV-VIS bands
bands Ifnm Gfcm-' assignment ref.
C 265 38 000 LC Ce"'-oxygen 3
charge transfer
B 280 35 700 LC Ce'"-oxygen
charge transfer
1
D 325 31000 in terband
A 350 28 600 transition
E 425 23 500 0; or 0; adsorbed 5
LC = low coordination.
on MgO (A = 420 nm) although the presence of the peroxide
ion 0; cannot be d i s ~ o u n t e d . ~
The disappearance of the A band on supported CeO, (Fig.
1) must now be examined further. According to the interpre-
tation presented above, the bands corresponding to
'localized ' charge transfers are believed to predominate over
the interband transition which arises from collective effects.
On the other hand, several studies in semiconductor physics
have shown that decreasing the size of semiconducting micro-
crystallites entails a blue shift of the absorption edge of the
interband transition. This is the 'quantum confinement
reported, for example, in CdS and CuCl which
present a forbidden gapwidth of the same order of magnitude
as in CeO, (2.5-3.2 eV). These studies, which were carried
out on three-dimensional microcrystals of semiconductors
grown in a transparent silicate glass, did not consider the
influence of surface species on the optical spectrum. At the
present time, both interpretations may account for the blue
shift of the absorption edge.
Conclusion
Among successful investigations concerning non-metallic
solids,8 DR spectroscopy appears to be a valuable tool to
characterize very small cerium oxide particles (cerium-
oxygen clusters). Cerium amounts as low as 20 ppm may be
detected. Investigations dealing with other oxides of d and f
elements are now in progress.' The blue shift of the interband
absorption edge and the occurrence of additional bands
beyond this edge appear to be a valuable criteria for the char-
acterization of well dispersed semiconducting oxides which
are of growing interest as catalytic materials, ceramics and
coatings.
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J. C. Muller and F. Bozon-Verduraz, in preparation.
Communication 1/05227F; Received 16th October, 1991