Topics in Catalysis 8 (1999) 189–198 189

Generation of superoxide ions at oxide surfaces

Masakazu Anpo a , Michel Che b , Bice Fubini c , Edoardo Garrone c , Elio Giamello c and Maria Cristina Paganini c
a Department of Applied Chemistry, College of Engineering, Osaka Prefecture University, Gakuen-cho 1-1, Sakai, Osaka 599-8531, Japan
b Laboratoire de Réactivité de Surfaces, Université P. et M. Curie (Paris VI), 4 Place Jussieu, 75252 Paris, France
c Dipartimento di Chimica IFM, Università di Torino, Via P. Giuria 9, 10125, Torino, Italy

The superoxide radical anion O− 2 is both an important intermediate in heterogeneous catalytic oxidation and a useful probe for
positive charges in ionic solids, such as metal oxides and zeolites. The paper illustrates the main circumstances under which stable
superoxide anions are formed at surfaces: (i) direct surface–oxygen electron transfer; (ii) photoinduced electron transfer; (iii) surface
intermolecular electron transfer; (iv) decomposition of hydrogen peroxide.
Keywords: superoxide ions, radical ion, oxide surfaces, EPR study, hydrogen peroxide

1. Introduction cationic fields, the principal routes to generate superoxide

Reactive oxygen species adsorbed at surfaces are impor-
tant intermediates in both total and selective catalytic oxida-
tion [1–3], as well as in various phenomena taking place at
gas–solid and liquid–solid interfaces, such as those involv-
ing the contamination of highly pure materials [4] or in the
pathogenic activity of some solid materials [5]. Among the
various species reported in the literature [2,3], the superox-
ide radical anion O− 2 has been widely investigated because,
being paramagnetic, the EPR (electron paramagnetic reso-
nance) technique provides a great deal of information on
its structure, location, stability, surface mobility and on-site
dynamics.
The adsorbed superoxide ion, besides having an intrinsic
interest in the above mentioned fields, costitutes a particu-
larly useful probe of the electric field at the surface of ionic
solids, particularly of oxides [6]. This is because its EPR
features depend on the local positive field felt by the neg-
ative anion, usually stabilized on positive ions at the solid
surface. In this way, in some instances, the features of the
superoxide species formed during a catalytic process yield
information on the nature of the active sites. In other cases
the superoxide is generated at the surface of ionic solids or
in the framework of zeolites in order to obtain information
on the cationic fields present in the system.
The present article presents a brief survey of the condi-
tions in which O− 2 species can be formed at the surface of
metal oxides (by far the ionic solids most relevant to cataly-
sis) and to illustrate the possible methods for the generation
of the species and for its use as a surface probe. Compari-
son with similar, but more general, review work [2,3] will
show that in the present case the approach is more lim-
ited: for instance, it does not take into consideration the
structural features of the various oxygen species nor does
it make a systematic analysis of all the possible types of
oxide. Nevertheless the merit of the present article is that,
after a second section devoted to pointing out the prop-
erties of the superoxide radical ion as a probe of surface
on metal oxides or in zeolites, not previously compared,
will be illustrated and collectively reviewed.
2. The adsorbed superoxide radical anion as a probe
of the surface crystal field
The superoxide radical anion O− 2 is characterized by the
presence of three electrons in the two 2π ∗ antibonding or-
bitals, thus rendering it a paramagnetic species. However,
an EPR spectrum is only observed when the degeneration
of the two orbitals is removed by an external perturbation,
such as the electric field of surrounding ions. Particular
cases are when the superoxide radical is trapped in the bulk
of an ionic solid, or when it is adsorbed at the surface of
an oxide. The latter case is the one which is treated in this
paper.
As the unpaired electron of the superoxide ion is con-
fined in a π type orbital, its EPR spectrum is intrinsically
orthorhombic, in that the three axes of the molecule are
magnetically unequivalent. The expected principal values
of the g tensor were first derived by Känzig and Cohen [7]
for the case of superoxide impurities in the bulk of alkali
halides. Assuming that the z direction corresponds to the
internuclear axis and the y direction to the orbital hosting
the unpaired electron, these are as follows:
gxx = ge ;
gyy = ge + 2λ/E;
gzz = ge + 2λ/∆,
where ge is the free spin value (2.0023), λ is the spin–orbit
coupling constant for the oxygen atom, and E and ∆ are
the two energy intervals reported in the scheme of figure 1.
The original expressions given by Känzig and Cohen are
more complex: the first-order approximation adopted here
is, however, compatible with the scope of the present arti-
cle. E and ∆ (figure 1) contribute to determine the gyy and

 J.C. Baltzer AG, Science Publishers

190 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
the gzz values, respectively: in the absence of the splitting
∆ the relaxation time of the radical is too small to give an
observable linewidth to the EPR spectrum. Since E  ∆,
gzz is the g-tensor element most sensitive to the cationic
Figure 1. Energy levels scheme for the superoxide O−
2 radical ion ad-
sorbed on a surface.
Figure 2. A typical EPR spectrum of the O−
2 radical ion adsorbed on MgO and exhibiting heterogeneity of the gzz component.
field felt by the adsorbed anion and is therefore a suitable
parameter for measuring the extent of the surface electro-
static interaction.
The value of gzz depends on the ionic charge of the
cation on which the O− 2 ion radical is adsorbed (or, more
precisely, on its charge to radius ratio) and values rang-
ing from 2.12–2.13 (monovalent cations) to 2.02–2.04 for
hexavalent cations [3] have been reported in the literature.
The merit of this method, however, goes beyond the mere
identification of the cation charge. This has been shown, for
instance, in the case the superoxide adsorbed on MgO [8].
In figure 2, a spectrum of O− 2 on MgO is shown. The gzz
region reveals a clear and well resolved heterogeneity in the
adsorbed species, despite the fact that only one positively
charged chemical entity (the divalent Mg2+ ) is present at
the surface. The various components of the gzz region have
to be ascribed [8] to superoxide ions adsorbed on surface
Mg2+ ions differing in their local coordination. The surface
field of a cation increases when the number of anions sur-
rounding the cation decreases. The highest gzz value is thus
ascribed to superoxide species adsorbed on five-coordinate
Mg2+ ions, whereas the lowest value is due to particularly
well exposed three-coordinate cations exerting a stronger
electric field as a result of their low coordination. Such an
interpretation, first advanced on the basis of an empirical
 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
correlation [8] between the gzz values and the Madelung
constant of different families of surface cations [9], has re-
cently been confirmed by quantum chemical calculations
on the O− 2 /MgO system [10]. The population of the vari-
ous gzz components observed in figure 2 is not the same
in all cases of O−
2 on MgO, as it depends on the procedure
adopted for the superoxide generation (see section 3.3 and
figure 8).
3. The formation of adsorbed superoxide species via
direct oxide–dioxygen electron transfer
When molecular oxygen is contacted with the surface of
a metal oxide, the formation of O− 2 will in principle occur
if the energy of the adsorbed negative moiety lies below the
Fermi level of the solid. Since the electron affinity of oxy-
gen is positive but rather small (0.44 eV), the electrostatic
contribution to the stabilisation of the anionic species on the
positive ions at the surface plays a fundamental role. The
energies relating to the various steps of the electron transfer
from an oxide to molecular oxygen have recently been ana-
lyzed by quantum chemistry calculations [10], for the case
of O− 2 formation on magnesium oxide containing surface
trapped electrons (Fs centers). Although the stability of the
electrons in the surface traps is substantial, the large electro-
static energy related to the O− 2 Mg
2+
interaction becomes
the driving force that allows the electron transfer. With this
in mind, it is easy to divide pure or mixed oxides into two
classes. The former class (section 3.1 below) groups the
relatively few systems capable of electron transfer towards
oxygen without any preliminary reductive treatment, while
the latter (sections 3.2 and 3.3 below) encompasses oxides
which must be prereduced prior to oxygen adsorption.
Figure 3. EPR spectra of oxygen radical species on MgO–CoO: (a) in the presence of a low pressure of oxygen; (b) after evacuation. The process is
reversible.
191
3.1. Electron transfer from isolated transition metal ions
embedded in an insulating matrix
An insulator like MgO is not capable of direct electron
transfer towards dioxygen, since all the electrons in the full
valence band (the top of which is separated by a large gap of
about 8 eV from the bottom of the empty conduction band)
lies at lower energy than that of an hypothetical adsorbed
superoxide ion. The properties of the insulating oxide can
be modified by introducing a transition metal ion into the
framework of the oxide. This, in electronic terms, corre-
sponds to modifying the band structure of the solid by the
formation of new localized states which usually lie within
the band gap of the insulator. Interesting results have been
obtained by doping MgO with Co2+ ions, due to the mutual
solubility of MgO and CoO over the whole range of mo-
lar concentrations. Fully dehydrated (but not prereduced)
MgO–CoO solid solutions directly adsorb oxygen giving
rise, depending on the adsorption temperature, to different
EPR spectra [11]. Two stable species have been identi-
fied at 77 K, transforming at 120–140 K into two other
species, stable up to room temperature (figure 3(a)). Both
the low temperature species and one of the room temper-
ature species (species A in figure 3(a)) are stabilized on
cobalt ions, as shown by the complex superhyperfine struc-
ture due to the interaction between the unpaired electron
and the 59 Co nucleus (nuclear spin I = 7/2, multiplicity
(2I + 1) = 8 lines). As indicated by a detailed analysis of
their spin-Hamiltonian parameters [12], their nature can be
roughly indicated as Co3+ O− 2 . The ionic model, however,
is not totally adequate, and models derived from coordi-
nation chemistry have to be adopted to explain the metal
ion–oxygen chemical bond satisfactorily [12]. The fourth
192 M. Anpo et al. / Generation of superoxide ions at oxide surfaces

species (B in figure 3(a)) is overlapped by species A and

has been identified as a “classic” superoxide ion on Mg2+
this being formed by spillover of O− 2 from the less stable
of the cobalt adducts upon increasing the temperature from
77 to 298 K.
The most noticeable feature of the signal of the Co3+ O−2
species in figure 3(a) is that it disappears upon evacuation
at room temperature and consequent oxygen release, leav-
ing only species B at the surface (figure 3(b)). Readmission
of oxygen at room temperature restores the cobalt–oxygen
adduct. This reversible adsorption of oxygen indicates that
a fraction, at least, of the surface cobalt centres behaves
as oxygen carriers exactly like those of iron or cobalt ions
in natural and synthetic oxygen carriers. The basic rea-
son for this unique property of the MgO–CoO surface is
that the symmetry of the Co2+ coordination environment
(C4v ) reproduces that of the molecular analogues mentioned
above [13].

3.2. Electron transfer from reducible (semiconducting)

oxides

Oxides capable of electron transfer towards dioxygen af-

ter a preliminary reductive treatment (thermal treatment un-
der vacuum or chemical reduction in mild conditions) are in
many cases semiconductors, showing deviations from stoi-
chiometry and/or possessing cations stable in more than one
oxidation state. In an n-type semiconductor, for instance,
the donor centres are occupied electron levels lying in the
band gap, quite close to the lower limit of the conduction
band, and the Fermi level of the solid lies between the
donor levels and the conduction band itself. At relatively
low temperature (for example, at ambient temperature) the
electrons occupying the donor levels are easily excited into
the conduction band. The electron transfer towards oxygen
occurs because the energy level of the LUMO orbital of O2
lies below the energy of the Fermi level of the solid. Elec-
tron transfer causes a decrease in the electron population in
the conduction band and a concomitant decrease of the solid
conductivity. In the interfacial region of the solid a posi-
tive charge develops, forming, with the negative charge of Figure 4. EPR spectra of superoxide radical ions adsorbed on: (a) TiO2
(anatase); (b) TiO2 supported WO3 .
the adsorbed species, an electrical double layer [14]. This
causes an increase of the electrical work function or, in
other words, generates an energy barrier (Schottky barrier) tion. When such a partially reduced solid is contacted with
which increases with progressive electron transfer, thereby oxygen at room temperature the grey colour immediately
limiting the electron transfer itself. In terms of energy band vanishes, the solid no longer perturbs the quality factor of
schemes, this can be seen as a bending of the bands of the the EPR cavity, and also its IR transparency improves. In
solid with consequent vanishing of the energy difference such conditions, the sample exhibits an EPR spectrum (fig-
between the energy level of the surface adsorbed oxygen ure 4(a)), readily assigned to O−2 ions stabilized on Ti
4+

and the Fermi level of the solid [14].
An example of this behaviour is given by titanium diox-
ide, when outgassed at 883 K. Non-stoichiometry is en-
hanced because of oxygen loss and the solid turns to pale
grey. The conduction band becames populated by a cer-
tain quantity of electrons, causing a loss of transparency in
the IR, perturbations of the Q factor of the cavity in the
EPR and by modifications of the profile of the UV absorp-
cations at the solid surface. More than one gzz compo-
nent characterises the spectrum: the most abundant species
corresponds to a gzz value of 2.023, and less abundant
species correspond to shoulders at 2.027 and 2.020 indicat-
ing a weakly heterogeneous distribution of the superoxide
adsorption sites.
An example of the role of adsorbed superoxide as probe
of cationic sites is found when comparing the results de-
 M. Anpo et al. / Generation of superoxide ions at oxide surfaces 193

scribed above for titanium dioxide with those arising from

the same treatment of WO3 supported on TiO2 (TW), in
which a surface layer of hexavalent tungsten partially cov-
ers the surface of titania [15]. When the supported oxide is
reduced under vacuum the binary TW sample reacts with
oxygen at room temperature leading to the EPR spectrum
in figure 4(b), whose features are different from those of the
spectrum in figure 4(a). In particular, in the gzz region only
one sharp component is present, at g = 2.019: it should
be noticed that, with respect to the other components (gyy
and gxx ) this gzz component is lower than in the previous
case. Although the gzz values observed in the two cases
are quite close, it seems reasonable to infer that O− 2 in the
TW case (figure 4(b)) is not stabilized on the same Ti sites
as are available on bare TiO2 but, most probably, is stabi-
lized on Wx+ ions of the WO3 overlayer. The g value is in
fact in agreement with those reported for superoxide ions
on WO3 /SiO2 [16].
The reduction of molecular oxygen at the surface of
slightly reduced transition metal oxides described above
is an important step in the complex series of redox re-
actions occurring during oxidation processes taking place
on mixed or supported oxide systems with at least one re-
ducible oxide phase. The mechanism was first described
by Mars and van Krevelen in the 1950s for the selective
oxidation of aromatic hydrocarbons [17]. A good candidate
for catalysing selective oxidation reactions is an oxide with
a certain propensity to lose oxygen and a good electronic
conductivity to ensure efficiency for the described redox Figure 5. EPR spectra of: (a) activated ZrO2 containing surface Zr3+
process. The capability of superoxide formation after mild ions; (b) the same sample after contact with O2 and surface adsorbed
reducing treatments is thus a property linked with the effi- superoxide formation.
cency of a given solid for catalysing oxidation reactions.
A behaviour similar to that of TiO2 is shown by zirco- of charge carriers delocalized in the solid and available for
nium dioxide (an oxide which is the object of increasing electron transfer in given conditions.
attention as a catalyst or catalyst support). Figure 5(a) re-
ports the EPR spectrum of a sample of zirconia after activa-
tion in vacuo at 873 K: the weak signals at g values lower 3.3. Electron transfer from localized electron defect
than the free-spin value (gk = 1.953 and g⊥ = 1.978) centres
are due to surface Zr3+ ions [18]. Contact with oxygen
at 423 K gives rise to the intense orthorhombic signal re- It is known since the early sixties that irradiation of
ported in figure 5(b), readily assigned again to superoxide some oxides with highly energetic radiation generates de-
ions. The gzz value is clearly compatible with a tetrava- fects consisting of electrons trapped in anionic vacancies,
lent adsorption site, so that the assignment to the O− 2 /Zr
4+ the so-called F centres or colour centres [19]. Such cen-
system is straightforward. The electron transfer does not tres can also be generated by addition of a low ionisation
occur at room temperature. This indicates that the process energy metal to the solid: if the addition is performed at a
is slightly activated. The intensity of the superoxide species reasonably moderate temperature (from RT to 600 K), the
(figure 5(b)) overwhelms that of the Zr3+ signal in the centres are localized at the solid surface [20,21]. In fig-
starting sample (figure 5(a)). This latter, moreover, does ure 6(a) the EPR spectrum of MgO containing F centres
not completely disappear after superoxide formation (fig- is reported. The visible ones are one-electron centres, but
ure 5(b)). This indicates that the majority of the oxygen two-electron diamagnetic centers are also present. The sur-
molecules are not reduced by Zr3+ ions and that the reduc- face colour centres are unstable towards oxygen and O− 2
ing centres, if localized, are not paramagnetic. It seems, radical ions are formed by oxygen adsorption at low tem-
however, more probable, due to the semiconducting prop- perature as indicated by the spectrum in figure 6(b). The
erties of the oxide, that the electrons transferred to the sur- electronic state corresponding to F centres lies in the band
face adsorbed dioxygen are, in the partially reduced solid, gap of the oxide. As mentioned before, the electron transfer
delocalized over the conduction band. The formation of to oxygen occurs due to the contribution of both the elec-
superoxide species can thus be used to monitor the amount tron affinity of oxygen and the Madelung stabilisation of
194 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
the adsorbed anion on positive centres at the surface. This
latter contribution is by far larger than the former [10].
Electron transfer to oxygen from localized defects has
also been observed in the past in the case of variously acti-
vated zeolitic systems (mainly activated by irradiation with
high energy photons) [22]. More recently, similar inves-
tigations have been performed to understand the nature of
the reduced centers in new synthetic molecular sieves and
to confirm the isomorphous substitution of a given element
in the framework of such systems [23–25]. For instance,
superoxide radical ions adsorbed on Ti4+ ions incorporated
Figure 6. (a) EPR spectrum of surface F+ s centres on MgO; (b) EPR
spectrum of adsorbed superoxide formed upon contact of oxygen with
the surface containing F centers. The higher intensity of the superoxide
spectrum indicates that a fraction of the surface trapped electrons are kept
in diamagnetic centres.
into a silicalite framework (in the case of the TS-1 titanium
silicate) exhibit different gzz features from superoxide ad-
sorbed on titanium ions introduced in the zeolitic channels
by ion exchange [23], thus allowing unambiguous discrim-
ination for isomorphous substitution.
4. Photoinduced electron transfer
An alternative method to generate adsorbed superoxide
ions, when the solid-to-dioxygen electron transfer does not
occur spontaneously, consists of irradiating the solid in the
presence of molecular oxygen. This method was employed
in early work on zeolites [26,27] using both γ and UV ir-
radiation to check the magnitude of the electric field in the
framework as a function of the metal ions exchanged in the
structure. More recently superoxide photoformation was
used to characterise the efficiency of photocatalytic sys-
tems based on highly dispersed titanium oxide [28]. The
spectrum in figure 7 has been obtained by UV irradiation
at 77 K, in the presence of molecular oxygen, of a sam-
ple of titanium dioxide highly dispersed on porous Vycor
glass. The intensity of the spectrum increases linearly with
irradiation time. The g values of the spectrum are reported
in the figure. The gzz value is, as expected, very close to
the value recorded for superoxide on polycrystalline TiO2
(figure 4). It is worth mentioning that highly dispersed
titanium dioxide is normally photoluminescent due to the
Figure 7. EPR spectrum of superoxide ions formed upon irradiation of
TiO2 highly dispersed on porous Vycor glass.
 M. Anpo et al. / Generation of superoxide ions at oxide surfaces 195

following charge transfer process

hν
Ti4+ O2−  [Ti3+ O− ]∗
hν 0
0
The luminescence hν is quenched by adsorption of oxygen.
Oxygen addition thus affords an alternative route for the
transfer of the excitation energy. A photoformed electron is
transferred and stabilized on the adsorbed molecule, which
is reduced to superoxide radical ion. Analogous results
have been found in the case of the photocatalytic oxida-
tion of propene occurring on divanadium pentoxide highly
dispersed on a porous Vycor glass (PVG) support [29].

5. Surface intermolecular electron transfer

Although the formation of O− 2 at the surface of an insu-

lating oxide by direct electron transfer is limited by the low
energy of the electrons in the solid, it has been shown that
several hydrocarbons (propene and toluene, for instance)
are oxidized by molecular oxygen in mild conditions at the
surface of MgO with formation of oxidized products and
cleavage of carbon–carbon bonds. In the case of propene,
for example, the contact with oxygen at the surface of MgO
causes the formation of adsorbed acetates, formates and car-
bonates at ambient temperature and total oxidation at higher
temperature. This fact is the fingerprint for an electrophilic
oxidation taking place through a superoxide ion or an O−
species [1]. Superoxide O− 2 ions were actually observed at
the surface of thoroughly outgassed MgO in the presence
of hydrocarbon–oxygen mixtures. This fact has been in-
terpreted introducing the concept of surface intermolecular
electron transfer (SIET) [30–33]. The fundamental factor
promoting the observed reactivity is the basic nature of
the MgO surface. Particularly low-coordinate surface ox-
ide O2− ions are able to split the hydrocarbon molecule Figure 8. EPR spectra of superoxide radical ions on MgO formed upon:
heterolytically forming a proton (stabilized as OH− ) and a (a) propene–O2 surface interaction; (b) adsorption of oxygen on the
carbanion: hydrogen-precovered surface.

− −
(surf) → R(ads) + OH(surf)
R–H + O2− The same mechanism has been shown to apply when
superoxide species are formed on alkaline earth oxides
The carbanion, which has indeed been observed by UV
(MgO and CaO) by adsorption of oxygen on a hydrogen-
spectroscopy [34], is unstable towards molecular oxygen
precovered surface (figure 8(b)). In this case the superoxide
and readily transfers an electron to dioxygen itself:
ion is formed by electron transfer from a surface adsorbed
R− − − −
(ads) –OH(surf) + O2(g) → O2 + OH(surf) + R
hydride. This comes from the heterolytic dissociation of
molecular hydrogen on a pair of Mg2+ O2− ions having par-
A minor fraction of the superoxide ions formed is captured ticularly low coordination and hence high polarizing power.
and stabilised by low coordination Mg2+ ions (near to a The whole process is summarized as follows:
surface hydroxyl) and becomes EPR visible (figure 8(a)).
The remaining species react, probably in their protonated
form HO2 , with the radical R leading to the cleavage of
the molecule and the formation of oxidized products. The
above described SIET mechanism shows how an oxida-
tion reaction involving superoxide species can take place
without direct activation of molecular oxygen by electron The above reaction scheme has been recently confirmed
transfer from the solid. In this case the driving force of the by IR investigations which show the formation of a hy-
process is merely the basic strength of the oxide ions at the dride band on contact with H2 and its disappearance when
surface. oxygen is subsequently admitted [35]. The superoxide ion
196 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
resulting from the above process exhibits the EPR spectrum
in figure 8(b). As in the case of figure 8(a), the magnetic
interaction with a nearby hydroxyl group is witnessed by
the hydrogen superhyperfine doublets visible on the gyy and
gzz components, as discussed in a previous paper [36]. The
difference in the gzz regions in figures 8(a) and (b) (indi-
cating that different species are formed) is related to the
different chemistry of the two processes described above,
and will be discussed elsewhere [37].
6. Interaction with hydrogen peroxide
A new method to generate superoxide at the surface of
oxides has recently been proposed by some of us [38]. It
consists of the treatment of an oxide with a solution of
hydrogen peroxide, followed by drying the solid and heat-
ing under vacuum at a suitable temperature. This method
derives from the observation that many oxides catalyse
the decomposition of hydrogen peroxide, a reaction which
occurs via radical intermediates, some of which are, in
particular conditions, stabilized at the surface. The main
goal of the research was to monitor the reaction interme-
diates during heterogeneous catalytic oxidation by H2 O2 .
Indeed, an increasing importance has recently been as-
sumed by the processes of heterogeneous oxidation of var-
ious substrates (alcohols, olefins, aromatic rings) on ze-
olitic catalysts such as TS-1 titanium silicate [39]. All
these processes, however, occur in competition with the
spontaneous decomposition reaction of H2 O2 to water and
molecular oxygen, the only process taking place by con-
tact of H2 O2 with the solid in the absence of the organic
substrate. Adsorbed superoxide is not the only intermedi-
ate species formed in the H2 O2 –oxide interaction but it is
by far the one most easily observed. In the case of the
H2 O2 –MgO system stable hydroxyl OH radicals were also
observed [40].
A typical example of superoxide generation via catalytic
decomposition of hydrogen peroxide is that observed in the
case of zirconium dioxide. When this solid is contacted
with an H2 O2 /H2 O solution the decomposition of hydrogen
peroxide is readily catalysed as is shown by the abundant
development of oxygen. The solid (dried at 343 K) exhibits
an intense EPR spectrum (figure 9), readily assigned to a
superoxide O− 2 radical ion adsorbed on a Zr
4+
ion at the
surface. The spectrum is closely similar to that reported in
figure 5(b). There is no doubt, therefore, about the forma-
tion of superoxide on zirconia also after contact with H2 O2 .
This indicates, quite surprisingly, that the surface exposed
Zr4+ ions capable of O− 2 coordination are similar in the
two cases, one of which relates to ZrO2 which has been
strongly dehydrated at 870 K (figure 5(a)) and the other to
ZrO2 mildly dehydrated at 343 K (figure 9). The absence
of any appreciable heterogeneity in the gzz component of
the superoxide spectrum on ZrO2 indicates furthermore that
only one family of surface ions acts as sites for superoxide
coordination. The reaction mechanism leading to the stabil-
Figure 9. EPR spectrum of O−2 superoxide ions formed at the surface of
zirconium dioxide by interaction with hydrogen peroxide.
isation of an adsorbed superoxide has been already widely
discussed [38,40] and it is based on the following series of
elementary steps:
H2 O2 → 2OH·
OH· + H2 O2 → H2 O + HO2 ·
The HO2 · hydroperoxyl radical is a weak acid and is also
the protonated form of the superoxide radical ion which
easily forms at the surface of the oxide according to the
following reaction:
HO2 · −→ H+ + O−
MeO
2
The unavoidable contact of the oxide with an aqueous
phase may be a limit of this method with some solids. In
certain cases, however, this method has clear advantages
over other procedures. This is the case, for instance, with
zeolites. Superoxide ions in zeolites have been widely in-
vestigated in the past employing as the method of forma-
tion γ irradiation or UV irradiation of the thoroughly de-
hydrated solid in the presence of oxygen, a method which
involves the creation of defects in the aluminosilicate struc-
ture [26,27]. Some of us have recently shown [41] that
superoxide species can be formed under much milder con-
ditions by the mere interaction of a hydrogen peroxide so-
lution with the zeolite. Outgassing the system at relatively
low outgassing temperatures (370–470 K) after this treat-
ment, causes the appearance of a superoxide spectrum. The
spectrum is then observed up to temperatures between 670
and 770 K. This indicates that the stability of the intraze-
olitic superoxide ions is higher than that of the “classic”
superoxide species adsorbed on the surface of a bulk ox-
ide, which is usually destroyed by treatments under vacuum
at 470–500 K.
Figure 10 reports a series of spectra recorded in a NaY
zeolite after treatment with hydrogen peroxide and succes-
sive dehydration at increasing temperature. The progressive
change in the EPR spectrum monitors the different electro-
static situation present in the zeolite cavity containing the
superoxide as the temperature is raised and provides in-
 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
Figure 10. EPR spectra of superoxide radical ions formed upon interaction
between hydrogen peroxide and NaY zeolite and successive outgassing at
increasing temperature. The outgassing temperature of each experiment is
indicated on the left hand side of the corresponding spectrum.
formation on the variation of the electrostatic field in the
zeolite which parallels the progressive dehydration. A full
interpretation of these preliminary results [42] has not yet
been accomplished but there is ample evidence already to
show that the use of hydrogen peroxide and its decomposi-
tion to produce intrazeolitic superoxide ions is a promising
method to improve knowledge of the properties of zeolitic
materials.
7. Conclusions
Only in a few cases is O− 2 formed on a substantially
unperturbed surface. In most cases the surface needs to
be activated, prior to O−
2 formation, by a suitable chemical
and/or thermal treatment causing a significant (though often
very small) perturbation of the bare surface. The EPR spec-
trum of surface-adsorbed superoxide ions provides a useful
tool for monitoring the surface electric field of an oxide
catalyst. Similar investigations can be also performed, by
EPR, using the NO radical molecule as a probe. The advan-
tage of employing NO is that the molecule can be directly
adsorbed on the unperturbed surface. The NO molecule,
197
however, is rather reactive and its reactivity often limits the
applicability of the method as a diagnostic tool. The use
of EPR-active probes complements the use of diamagnetic
probes of the surface crystal field such as the CO mole-
cule whose interaction with the surface can be followed by
changes of the C–O stretching frequency monitored by IR
spectroscopy [43].
References
[1] A. Bielanski and J. Haber, Oxygen in Catalysis (Dekker, New York,
1991).
[2] M. Che and A.J. Tench, Adv. Catal. 31 (1982) 77.
[3] M. Che and A.J. Tench, Adv. Catal. 32 (1983) 1.
[4] D.J. Miller, D. Haneman, Phys. Rev. B 3 (1971) 2918.
[5] B. Fubini, L. Mollo and E. Giamello, Free Rad. Res. 23 (1995) 593.
[6] M. Che and E. Giamello, Stud. Surf. Sci. Catal. 57 B (1990) 265.
[7] W. Känzig and M.H. Cohen, Phys. Rev. Lett. 3 (1959) 509.
[8] E. Giamello, E. Garrone and P. Ugliengo, J. Chem. Soc., Faraday
Trans. I 85 (1989) 1373.
[9] E. Garrone, A. Zecchina and F.S. Stone, Phil. Mag. B 42 (1980) 683.
[10] G. Pacchioni, A. Ferrari and E. Giamello, Chem. Phys. Lett. 255
(1996) 58.
[11] E. Giamello, Z. Sojka, M. Che and A. Zecchina, J. Phys. Chem. 80
(1986) 6084.
[12] Z. Sojka, E. Giamello, M. Che, K. Dyrek and A. Zecchina, J. Phys.
Chem. 92 (1988) 1541.
[13] M. Che, K. Dyrek, E. Giamello and Z. Sojka, Zeit. Phys. Chem.
Neue Folge 152 (1987) 397.
[14] J.R. Morrison, The Chemical Physics of Surfaces (Plenum, New
York, 1977).
[15] M.C. Paganini, L. Dall’Acqua, E. Giamello, L. Lietti, P. Forzatti and
G. Busca, J. Catal. 166 (1997) 195.
[16] R.F. Howe, J. Chem. Soc., Faraday Trans. I 71 (1975) 1689.
[17] P. Mars and D.W. van Krevelen, Chem. Eng. Sci. 3 (1954) 41.
[18] C. Morterra, E. Giamello, L. Orio and M. Volante, J. Phys. Chem.
94 (1990) 3111.
[19] A.J. Tench and R.L. Nelson, J. Colloid and Interface Sci. 26 (1968)
364.
[20] E. Giamello, A. Ferrero, S. Coluccia and A. Zecchina, J. Phys. Chem.
95 (1991) 9385.
[21] E. Giamello, D. Murphy, L. Ravera, S. Coluccia and A. Zecchina,
J. Chem. Soc., Faraday Trans. 90 (1994) 3167.
[22] J.C. Védrine, A. Abou-Kais, J. Massardier and G. Dalmai-Imelik,
J. Catal. 29 (1973) 120.
[23] A. Tuel, J. Diab, P. Gelin, M. Dufaux, J.F. Dutel and Y. Ben Taarit,
J. Mol. Catal. 63 (1990) 95.
[24] S.B. Hong, S.J. Kim and Y. Sun Hu, J. Phys. Chem. 100 (1996)
15923.
[25] A.M. Prakash, V. Kurshev and L. Kevan, J. Phys. Chem. B 101
(1997) 9794.
[26] P.H. Kasai, J. Chem. Phys. 43 (1965) 3322.
[27] K.M. Wang and J.H. Lunsford, J. Phys. Chem. 74 (1970) 1512.
[28] M. Anpo, N. Aikawa, Y. Kubokawa, M. Che, C. Louis and E.
Giamello, J. Phys. Chem. 89 (1985) 5017.
[29] M. Anpo, T. Suzuki, Y. Yamada, E. Giamello and M. Che, in: New
Developments in Selective Oxidation, eds. G. Centi and F. Trifirò,
Stud. Surf. Sci. Catal. 11 (1990) 683.
[30] E. Garrone and F.S. Stone, in: Proc. 8th Int. Conf. Catal., Vol. 4,
Berlin, 1984 (Verlag Chemie, Weinheim, 1984) p. 441.
[31] E. Garrone, E. Giamello, S. Coluccia, G. Spoto and A. Zecchina, in:
Proc. 9th Int. Conf. Catal., Vol. 4, Calgary, 1988, eds. M.J. Phillips
and M. Ternan (Chem. Inst. Canada, Ottawa, 1988) p. 1577.
[32] E. Giamello, E. Garrone, S. Coluccia, G. Spoto and A. Zecchina,
in: New Developements in Selective Oxidation, eds. G. Centi and F.
Trifiró, Stud. Surf. Sci. Catal. 11 (1990) 817.
198 M. Anpo et al. / Generation of superoxide ions at oxide surfaces
[33] E. Garrone, E. Giamello, M. Ferraris and G. Spoto, J. Chem. Soc.,
Faraday Trans. 88 (1991) 333.
[34] E. Garrone, A. Zecchina and F.S. Stone, J. Catal. 62 (1980) 396.
[35] E. Knözinger, K.H. Jacob and P. Hofman, J. Chem Soc., Faraday
Trans. 89 (1993) 1101.
[36] E. Giamello, P. Ugliengo, E. Garrone, M. Che and A.J. Tench,
J. Chem. Soc., Faraday Trans. I 85 (1989) 3987.
[37] E. Giamello, manuscript in preparation.
[38] E. Giamello, P. Rumori, F. Geobaldo, B. Fubini and M.C. Paganini,
Appl. Mag. Res. 10 (1996) 173.
[39] M.G. Clerici, G. Bellussi and U. Romano, J. Catal. 129 (1991) 159.
[40] E. Giamello, L. Calosso, B. Fubini and F. Geobaldo, J. Phys. Chem.
97 (1993) 5735.
[41] B. D’Anna and E. Giamello, Appl. Mag. Res. 10 (1996) 591.
[42] E. Giamello et al., to be published.
[43] V. Bolis, C. Morterra, B. Fubini, P. Ugliengo and E. Garrone, Lang-
muir 9 (1993) 349.