/' MICROPOROUS

MATERIALS
ELSEVIER Microporous Materials 6 (1996) 235-257

Review

X-Ray photoelectron spectroscopy on zeolites and related

materials I
Michael St6cker
SINTEF Chemistry in Oslo, Department of Hydrocarbon Process Chemistry, P.O. Box 124 Blindern, N-0314 Oslo,
Norway
Received 3 January 1996; accepted 5 March 1996

Abstract
XPS has become an important tool for the characterization of surface properties of zeolites and related materials.
Since catalysis is mainly a surface phenomenon detailed knowledge of the behavior of zeolites and related materials
is valuable with respect to the application of those materials in connection with catalyzed chemical reactions and
processes. After a short introduction of the basic principles of XPS some general aspects are addressed before the
more specific items related to XPS investigations of zeolites and related materials are discussed. These chapters are
followed by the characteristics of zeolites and related materials studied by XPS in relation to the surface properties,
the nature and electronic state of metals, their redox behavior as well as investigations of metal clusters/complexes in
zeolites and related materials. Furthermore, the dispersion of metals and metal oxides, the application in catalysis,
the coke formation and finally the acidity and basicity of zeolites will be addressed.

Keywords." X-Ray photoelectron spectroscopy; Zeolites; Molecular sieves; Review

Contents 5. T h e characteristics o f zeolites a n d related

1. I n t r o d u c t i o n ............................................. 236
2. Physical principle o f X P S ........................ 236
3. X P S - general aspects .............................. 238
3.1. X P S intensities a n d s a m p l e
c o m p o s i t i o n / q u a n t i f i c a t i o n ............... 238
3.2. X P S b i n d i n g energies a n d o x i d a t i o n
states/chemical shifts ......................... 238
3.3. S h a k e - u p a n d s h a k e - o f f excitations .. 239
3.4. C o m p o s i t i o n - d e p t h profiling ............ 239
3.5. S t a t e - o f - t h e - a r t X P S ......................... 239
3.6. C h a r g i n g / c a l i b r a t i o n ......................... 240
3.7. A u g e r p a r a m e t e r ( A P ) ...................... 240
4. X P S a p p l i e d to zeolites a n d related
m a t e r i a l s - o v e r r i d i n g i m p o r t a n c e ........... 240
m a t e r i a l s including i n c o r p o r a t e d species .. 243
5.1. Surface p r o p e r t i e s ............................. 243
5.2. N a t u r e a n d electronic state o f
m e t a l s / r e d o x b e h a v i o r ....................... 246
5.3. M e t a l clusters/complexes in zeolites
a n d related m a t e r i a l s ........................ 249
5.4. D i s p e r s i o n o f m e t a l s a n d m e t a l
oxides in zeolites ............................... 251
5.5. Catalysis a n d c o k e f o r m a t i o n ........... 251
5.6. C h a r a c t e r i z a t i o n o f acidity a n d
basicity in zeolites ............................. 253
6. C o n c l u d i n g r e m a r k s ................................. 255
A c k n o w l e d g e m e n t s ....................................... 255
References ..................................................... 255

1 Dedicated to Dr. Hellmut G. Karge on the occasion of his

65th birthday.

0927-6513/96/$32.00 © 1996 Elsevier Science B.V. All rights reserved

PII S0927-6513 (96) 00034-X
236 M. St6cker/Microporous Materials 6 (1996) 235-257
1. Introduction
Among the methods of surface analysis based
on ultra high vacuum techniques, which have been
developed dramatically during the past years, only
X-ray photoelectron spectroscopy (XPS or ESCA,
which stands for 'electron spectroscopy for chemi-
cal analysis'), besides Auger electron spectroscopy
(AES) and secondary ion mass spectrometry
(SIMS) became well established in the field of
materials surface analysis [1]. XPS provides spa-
tially resolved compositional information in the
form of spectra from defined areas (microanalysis),
and the use of the technique to derive functional
group information from chemical shifts in photo-
electron energies is well known [2]. There is now
a huge knowledge of experience and data in almost
all areas of material science [2], and the objective
of this review is to survey XPS results on zeolites
and related materials, including other microporous
materials such as A1PO4 molecular sieves.
2. Physical principle of XPS
From the early pioneering work of Kai Siegbahn
(Nobel prize awardee 1981) and his group at
Uppsala, Sweden, XPS became one of the most
powerful and valuable methods of surface analysis
currently available, mainly through intensive years
of instrumental, interpretational and applicational
development over the last decade [2]. The physical
principles of XPS are well known, and only the
essential points will be presented in the following.
Those readers who are interested in more details
should consult Refs. [1-4].
XPS has its origin in the investigations of the
photoelectric effect in which X-rays were used as
the exciting photon source. In addition to the
valence electrons, which provide the bonding for
the systems, each atom present in the surface
(except H2 and He) possesses core electrons not
directly involved in the bonding. The so-called
'binding energy' (Eb) of each core electron (concep-
tually, but not strictly, equivalent to the ionization
energy of that electron) is characteristic of the
individual atom to which it is bound [2]. In the
basic XPS experiment, the sample surface is irradi-
ated by a source of low-energy X-rays under ultra-
high vacuum conditions. Photoionization then
takes place in the sample surface (depth of analysis
between 1.5 and 6nm). The resultant photo-
electrons (emitted particles) have a kinetic energy
(Ek) in the range of 20 to 2000 eV, which is related
[2] to the X-ray energy (hv) and Eb by Eq. 1 (cf.
Fig. 1):
Ek=hv- Eb--~p (1)
where h is Planck's constant, v is the frequency of
the exciting radiation and (p is the work function
of the spectrometer (i.e., the energy required to
bring an electron from the Fermi level of the
spectrometer to its zero level).
If the photoelectrons have sufficient kinetic
energy they are able to escape from the surface by
overcoming the work function, and photoemission
happens (Fig. 1). Since the energy levels are quan-
tized, the photoelectrons have a kinetic energy
distribution consisting of a series of discrete bands
which essentially reflect the 'shell' form of
electronic structure of the atoms in the sample [2]
(Fig. 2). In a way, XPS is the experimental deter-
Photoelectron(e~,)
KL~ Augerelectron
Levels [ EK (eL)
vacuum i~
Fermi
2p~(L3~ -=
2p~a(!_z) -
2s (L,) ; ~.
hw
Is (K) Photoemis;on Auger process
XPS)
Fig. 1. Photoemission (XPS) and the Auger process. Left: An
incident X-ray photon is absorbed and a photoelectron emitted.
Measurement of its kinetic energy allows one to calculate the
binding energy of the photoelectron. The atom stays behind as
an unstable ion with a hole in one of the core levels. Right: The
excited ion relaxes by filling the core hole with an electron from
a higher shell. The energy released by this transition is taken
up by another electron, the Auger electron, which leaves the
samples with an element-specific kinetic energy [4].
 M. St~cker/Microporous Materials 6 (1996) 235-257 237

xl0 s Table 1
1.00 | Core-level electron binding energies (in eV) of elements relevant
0"901- 01s to zeolites and related materials (2)
0.801 -
Element lsl/2 2sl/2 2pl/2 2p3/2 3sl/2 3Pl/2 3p3/2
0.70 F
OKL2,aL2,3(Auger)
,~~'°~°I~
"~ 0.601- Nals
~, K4M2,3'~,,31 I
3 Li
4 Be
55
111
0.40 5B 188
8 0.30
0.20 -- "- " ' - ' - ' ~
~ aK/~.3L=,3(Auger)
. - K2~ AI2s
6C
7N
284
399
[ ~,s t v Si2s~,~i2p 80 532 24
0.10 9F 686 31
i i i l i i i - - - llNa 1072 63 31
0.00 1200 1000 800 600 400 200 0
12Mg 1305 89 52
Binding Energy (eV)
13A1 118 74 73
Fig. 2. A1 Kct-excited photoelectron spectrum of 14 Si 149 100 99
offretite/erionite (30% erionite). 15 P 189 136 135
19K 377 297 294 34
20 Ca 438 350 347 44 26
22 Ti 564 461 455 59 34
mination of the kinetic energy distribution by 23 V 628 520 513 66 38
analysis of the photoelectrons produced by expo- 26 Fe 846 723 710 95 56
sure to X-rays. 27 Co 926 794 779 101 60
Routinely used X-ray sources are Mg K~ 31Ga 1298 1t43 1116 158 107 103
(1253.6eV) and A1 K~ (1486.3eV) as incident
particles, which normally cover an area of many
mm 2. A1 K~ radiation can be monochromated, why X-ray sources often contain a dual anode of
and this leads to some focusing, maybe to a spot Mg and AI [2,4].
diameter of about 100/~m (lateral resolution). The Photoelectron peaks are labeled according to
XPS spectrum is usually a plot of the intensity of the quantum number of the level from which the
photoelectrons versus the binding energy Eb. Fig. 2 electron originates. Table 2 summarizes the spec-
shows the XPS spectrum of offretite/erionite. Peaks troscopic nomenclature.
due to Si, A1, K, Na, O and C, due to the
ubiquitous contamination by hydrocarbons, are Table 2
Spectroscopic nomenclature in XPS (4)
easily assigned by consulting binding energy tables
(Table 1). n" lb jc X-ray level Electron level
In addition to the expected photoelectron sig-
nals, the spectrum in Fig. 2 contains peaks due to 1 0 1/2 K ls
Auger electrons as well. The latter arise from the 2 0 1/2 L1 2s
2 1 1/2 L2 2pl/2
deexcitation of the photoion by an Auger trans- 2 1 3/2 L3 2p3/2
ition (Fig. 1), or, in other words, the photoioniza- 3 0 1/2 M1 3s
tion produces not only photoelectrons, but also, 3 1 1/2 M2 3Pl/2
via Auger decay of the electron hole formed, Auger 3 1 3/2 Ma 3p3/2
electrons [2,4]. Obviously, the Auger electron 3 2 3/2 M4 3da/2
3 2 5/2 M5 3d~/2
energy is independent of the X-ray energy used to 4 3 5/2 N6 4f5/2
create the hole, whereas the photoelectron energy 4 3 7/2 N7 4f7/2
is related to the X-ray energy via Eq. 1. Hence,
the apparent binding energy of Auger peaks "Quantum number of the level from which the electron
originates.
appears to change on going from A1 K~ to Mg b Orbital momentum (0, 1, 2, 3.... indicated as s, p, d, f, ...).
Kot radiation, whereas photoelectron peaks do not ¢ Total momentum j = 1 + s (with spin momentum s = + 1/2 or
shift in binding energy. This is the main reason - 1/2).
238 M. St6cker/Microporous Materials 6 (1996) 235-257
3. XPS - general aspects
XPS yields information on the elemental com-
position (elemental analysis), the oxidation state
of the elements and in favorable cases on the
dispersion of one phase over another [4]. XPS can
be used to give reasonable quantitative accuracy
(better than ___10%) provided that good calibration
standards are used [2]. The detection limit is about
10 -3"
A major advantage of the technique is that the
photoelectron energy is dependent on the precise
chemical configuration of the surface atoms, and
pronounced chemical shifts are produced in the
position of the peaks in the XPS spectrum. XPS
is amenable to virtually all vacuum-compatible
samples since the incident X-rays do not normally
cause surface damage due to the beam. Therefore,
the technique can be used even with very delicate
materials [2]. Usually, the sample charging is
minimal. The collection of spectra is normally fast
(typically less than 5 min), and the reproducibility
of results is high [2]. XPS shows a narrow range
of sensitivities, and the variation in sensitivity
across the element range is about a factor of 10.
However, the capability for small area analysis is
limited, and the depth resolution in composition--
depth profiling is poor. Finally, large user data
bases and good support data are available, which
make the application of XPS a routine technique.
XPS is compatible with AES and SIMS within the
same instrument, and multi-technique instruments
will continue to have an important part to play in
surface analysis [2].
A few (and most important) aspects related to
XPS are discussed in the following.
3.1. XPS intensities and sample
composition~quantification
A set of binding energies is characteristic for an
element, and XPS can, therefore, be used to ana-
lyze the composition of samples. According to the
inelastic mean free path of the elements, the prob-
ing depth of XPS varies between 1.5 and 6 nm,
depending on the kinetic energy of the photo-
electron. For example, the A1 2p peak in the
spectrum of offretite/erionite (Fig. 2) probes
deeper into the sample than the O 1s peak. When
determining concentrations, this effect must be
taken into account [4]. The quantification of XPS
spectra can be described as follows: The obtained
value for the peak intensity (peak area followed
by background removal) of the principle spectral
feature of each element detected in the XPS
spectrum is used to calculate the fractional atomic
concentration, CA of element A by:
IA/SA (2)
cA- (,./s.)
n
where I, is the measured peak intensity for element
n and S, is the relative atomic sensitivity factor
(ASF) for that peak.
3.2. XPS binding energies and oxidation
states/chemical shifts
Binding energies are not only element specific
but contain chemical information as well, because
the energy levels of core electrons depend slightly
on the chemical state/environment of the atom.
Siegbahn found that this chemical shift is detectable
within a range of 0.1 and 10 eV in magnitude. It
was this ability of the technique that led Siegbahn
to coin the term 'electron spectroscopy for chemi-
cal analysis' (ESCA), a term that has often been
used since, in preference to the more correct name
'X-ray photoelectron spectroscopy' (XPS). In
simple terms, chemical shifts arise from the varia-
tion of electrostatic screening experienced by core
electrons, as valence electrons are drawn towards
or away from the atom of interest [2]. Usually,
the binding energy increases with increasing oxida-
tion state, and for a fixed oxidation state with the
electronegativity of the ligands. There are excep-
tions, however, as with the alkali metals [4].
As already mentioned earlier, the binding energy
is not equal to the energy of the orbital from
which the photoelectron is emitted; the difference
is caused by the reorganization of the remaining
electrons when an electron is removed from an
inner shell. As a consequence, the binding energy
of a photoelectron contains both information on
the state of the atom before photoionization (the
initial state) and on the core-ionized atom left
 M. Strcker/Microporous Materials 6 (1996) 235-257
behind after the emission of an electron (the final
state). Fortunately, it is often correct to interpret
binding energy shifts in terms of the initial state
effects. The charge potential model elegantly
explains the physics behind such binding energy
shifts [4], by means of Eq. 3:
Eb i = kqi + q~ +Eb r°f (3)
rij
in which Ub is the binding energy of an electron
from the atom i, qi is the charge on the atom, k is
a constant, qj is the charge on a neighboring atom
j, rij is the distance between atom i and atom j,
and Ubef is the suitable energy reference [4].
The first term in Eq. 3 indicates that the binding
energy goes up with increasing positive charge on
the atom from which the photoelectron originates.
In ionic solids, the second term counteracts the
first, because the charge on a neighboring atom
will have the opposite sign. Because of its similarity
to the lattice potential in ionic solids, the second
term is often referred to as the Madelung poten-
tial [4].
A few words about energy referencing are appro-
priate: Fermi levels of conducting samples which
are in contact are the same. Hence, the Fermi level
provides a convenient energy zero. Of course,
electrons at the Fermi level are still bound to the
metal and have an ionization potential equal to
the work function ~0. However, electrons coming
from the Fermi level of the sample are detected
with a kinetic energy equal to hv-~o, where ~0 is
the work function of the spectrometer [4].
3.3. Shake-up and shake-off excitations
XPS spectra of transition metal containing com-
pounds often show additional peaks in the
spectrum. These so-called shake-up and shake-off
peaks are final state effects which arise when the
photoelectron imparts energy to another electron
of the atom. This electron ends up in a higher
unoccupied state (shake-up) or in an unbound
state (shake-off). As a consequence, the photo-
electron loses kinetic energy and appears at a
higher binding energy in the spectrum. Those
peaks have diagnostic value, as the precise loss
239
structure depends on the environment of the atom.
One result is that the XPS peaks of metals are
asymmetrically broadened towards higher binding
energies, and the effect is most pronounced in
d-metals [4].
3.4. Composition-depth profiling
It is (in principle) possible to use XPS to investi-
gate the variation of composition with depth into
the sample in several ways, thereby producing a
composition-depth profile of the surface of inter-
est. Generally, different approaches are available
to arrive at the desired profile, such as analysis by
using different core-levels of the same element, use
of different X-ray energies, use of different emis-
sion angles and the so-called sputter-depth profil-
ing method (for further details see Ref. [4]).
However, as mentioned previously, the depth reso-
lution in composition-depth profiling is rather
poor.
3.5. State-of-the-art X P S
Until recently, spatial (lateral) resolution in
XPS has been of the order of several millimeters,
and this has proven a major limitation and handi-
cap in many areas of application. Within the last
few years, however, attempts have been made to
improve spatial resolution both by focussing the
incident X-rays and by imaging the emitted photo-
electrons. Commercially available small-spot X-ray
source photoelectron spectrometers make use of
X-ray back-diffraction from a suitable quartz crys-
tal microfocus monochromator. However, the con-
ventional (standard) X-ray monochromators are
based on the so-called Johann approximate focus-
sing geometry, which gives excellent monochro-
matization of the source, but produces a fairly
large irradiated area on the specimen. The best
spatial resolution that can be expected using this
method is in the range of 100/~m [2]. In addition,
angle-depending XPS measurements on single crys-
tals contain structural information, such as layer
thickness and adsorption geometries [4]. In conclu-
sion, XPS is among the most frequently used
techniques in catalysis. The advantages of XPS are
that it readily provides the composition of the
240 M. Stdcker/Microporous Materials 6 (1996) 235-257
surface region and that is distinguishes between
chemical states of one element. Finally, imaging
XPS is likely to be one of the most fruitful and
exciting areas of development over the next few
years [2,4].
3.6. Charging~calibration
By convention, binding energies refer to core-
level energy relative to the spectrometer Fermi-
level. For conducting specimens in good electrical
contact with the spectrometer, the Fermi levels of
both the sample and the spectrometer will be
equivalent, and absolute measurements of core-
level binding energies can be made [2]. However,
an experimental problem in XPS is that electrically
insulating samples (like zeolites) may charge
during measurements, since photoelectrons leave
the sample. Due to the positive charge on the
sample, all XPS peaks in the spectrum shift by the
same amount to higher binding energies.
Therefore, it is not possible to make absolute
binding energy measurements, and it is necessary
to rely on some internal standard for energy refer-
encing. This calibration is done by using the bind-
ing energy of a known compound, usually the
always present carbon contamination with a C ls
binding energy of 284.4 eV [2,4].
3.7. Auger parameter (AP)
The Auger parameter (AP) concept was intro-
duced by Wagner [5,6] to exploit the greater
information available from the study of both
Auger and photoelectron lines together rather than
either alone. The Auger parameter was defined
originally as
=Ek(jkl)--Ek(i) (4)
where Ek(jkl) is the kinetic energy of the Auger
transitionjkl and Ek (i) is the kinetic energy of the
photoelectron emitted from atomic level i. Eq. 4 is
equivalent to
e = Ek(jkl) + E b q ) - h v (5)
where Eb(i) is the binding energy of an electron in
level i and hv is the energy of the exciting radiation.
Eqs. (4) and (5) can produce negative values of c~
and therefore a modified Auger parameter, ~' was
introduced [3]:
~' = ~ + hv = Ek(jkl) + Eb(/) (6)
The Auger parameter is an empirical measure with
a unique value for each chemical state and can
therefore be used as a fingerprint for characterizing
such states [3].
4. XPS applied to zeolites and related materials -
overriding importance
During the last 20 years, the application of XPS
to zeolites and related materials has addressed a
number of questions, like surface sensitivity, the
capability of giving direct information on the
valence states, the effective charges, the bond ionic-
ities and the band energy structures of zeolites and
related materials. Pioneering studies on zeolites by
XPS performed by Shpiro et al. [7] and Barr and
coworkers [8-11] were mainly dealing with the
variations of the chemical compositions between
the surface and the bulk of the zeolite crystal, the
establishment of the nature of the cation-zeolite
framework bond, the demonstration of regularities
as a function of the valence state of transition
elements and their migration to the external sur-
face, the validity of a correlation between the XPS
data and those obtained from zeolite catalytic
studies, the states of metals and ligands in com-
plexes synthesized in a zeolite matrix, the inter-
action of highly dispersed metal particles with the
zeolite framework and studies of adsorption on
zeolites [7]. A number of important reviews by
those groups, covering the XPS research on zeolites
performed during the 1970's and 1980's, are well
known, and the interested reader should consult
those publications for further details from that
time [7-11]. At this stage, only a few highlights
from that period will illustrate the practical impor-
tance of XPS related to zeolites and microporous
materials.
The ratios of the surface Si and A1 concen-
trations vs. those in the bulk have been found to
be linear. However, the surface and bulk composi-
tions of zeolites of types A, X, Y and mordenite
are close together, whereas in dealuminated faujas-
 M. Strcker/Microporous Materials 6 (1996) 235-257
ite the surface Si/A1 ratio increases by a factor of
two [7]. This result may lead to a non-uniform
aluminum distribution between the surface and the
bulk crystal. As the binding energy shifts observed
in XPS are a direct consequence of variations in
the total charge fields, the following pattern was
observed for zeolites: a shift to higher binding
energy for all constituents, as the size of the cage,
the cation charge and the Si/A1 ratio increase [8].
In addition, a collective pattern was realized by
different binding energies, suggesting the registra-
tion of selective 'groups' rather than 'elemental'
chemical shifts. The two primary chemical groups
identified in many of the zeolites seem to be the
SiO2 unit and another one that mimics the
cation-AIO2 unit [10]. Furthermore, it was con-
cluded that the surfaces of certain zeolites are
compromised such that substantial proportions of
their total surface aluminum are actually present
in alumina or sodium aluminate residues [10].
A first detailed XPS study of the valence band
spectra of zeolites was presented by Barr and
coworkers [11 ]. Based on the general features of
these spectra, the authors subdivided the zeolites
into two, somewhat artificial, classes: group I,
systems of Si/A1 ratios from 1 to 3, typified by
structures dominated by interlaced tetrahedral
silica aluminate cages, e.g. A, X, Y and L zeolites,
and group II, systems of large Si/A1 ratios from 5
to >100, typified by structures dominated by
interlaced chains, e.g. mordenite, ZSM-5 and sili-
calite [ 11 ].
The valence band spectra exhibited by these
zeolites are not just additive renditions of that for
silica and for alumina, but rather the zeolite spectra
reveal complex shiftings and alterations. In addi-
tion, the valence band results for the group II
systems appear to be quite similar in appearance
to silica, suggesting a silica-dominated system with
increasing aluminate perturbation as the Si/A1
ratio decreases, i.e., silicalite < ZSM-5 <
mordenite [ 11 ].
Whereas earlier work related to XPS on zeolites
was mainly devoted to possible variations of the
chemical composition between the surface and the
bulk of the zeolite crystal, the investigation of
components introduced into the zeolite lattice or
deposited on the external surface has been the
241
domain of XPS since then [12]. Again, a few
recent papers of more general character are
reviewed to begin with, before the main chapters
dealing with the more specific items related to XPS
and zeolites/micro- and mesoporous materials will
be discussed.
XPS binding energies have been measured for a
number of zeolites (A, X, Y, mordenite and
ZSM-5) in a wide range of Si/A1 ratios from 1 to
15 in the Na and H forms. Typical trends of the
binding energies with the chemical compositions
were reproduced as known. Measurements of the
Auger parameter for zeolites of different Si/A1
ratios showed final-state effects to be irrelevant for
the explanation of the binding energy trends.
Furthermore, the Madelung energies at the atomic
sites in the zeolite lattice were estimated by lattice-
energy calculations for energy-minimized zeolite
models ranging from Na-X to Na-ZSM-5 and for
models of H-Y of different Si/A1 ratios. These
calculations show that the binding energy trends
upon variation of the A1 content are mainly due
to changes in the Madelung potential. Binding
energy shifts associated with the exchange of Na
by H reflect increased covalent interactions, which
reduce the charges on the atoms contributing to
the Madelung potential. It was suggested that
covalent effects may be involved also in binding
energy shifts in the framework under the influence
of Li and other cations of high electronegativity
[12].
The nature of the bonding chemistry in zeolites
has been investigated by Barr [ 13], both by analyz-
ing the XPS core level and valence band results.
The emphasis in this study was put on the
covalent/ionic character of the chemical bondings.
The zeolite binding energies were seen to shift in
a regular progressive fashion with changes in the
Si/A1 ratio: higher Eb values with increasing Si/A1
ratios. The most unusual feature of these changes
is that the binding energies of all the elements shift
in the same direction at the same time. The
following relations were established, based on XPS
results, and they are, therefore, particular relevant
to the surface regions of the zeolites (however,
they should at least correlate with similar proper-
ties for the bulk): The Si-O bond in the silica
system is much more covalent than is the A1-O
 242 M. St6cker/Microporous Materials 6 (1996) 235-257
bond in an alumina system. Increasing the Si/AI
ratio provides a system in which the natural cova-
lency of the Si-O units in the silica begins to
dominate, driving up the relative ionicity of the
AI-O bond and the Na-O bond. The relative
Brensted acidity of these zeolite systems was shown
to follow a similar progression. Thus, when the
Si/A1 ratio is relatively small, the O - H bond is
reported to be relatively covalent and the acidity
weak. As the relative amount of silica is increased
with its covalent Si-O bond, the ionicity (Bronsted
acidity) of the O - H bond increases. The correla-
tion between progressive XPS shifts and the change
in zeolite bonding properties is also shown to
relate to the calculated oxygen charge in a manner
related to the Sanderson electronegativity (see
Fig. 3). The author demonstrated that the oxide
in a zeolite is a highly polarizable unit. Further,
he concluded that XPS valence band spectra of
zeolites are often more informative than the core
level results of the same systems [13].
A number of practical aspects related to the
surface behavior of zeolites have been studied by
Barr using comparative XPS and N M R results
[14]. During the conversion of parent Y zeolites
to their ultrastable form, certain cation
by-products have been found by XPS to be selec-
tively transported to the outer surface.
Furthermore, in connection with applications
SiO2
A of the binding energy especially of oxygen, whereas
532.0
0
C ~ , ~axNaY
Q
CaXo ~
_c
_~¢ 531.0
an
\\.,x
oc. \\
530.¢
-0.2 -0.3 -0.4
No
Fig. 3. Shift in zeolite O ls binding energies with change in
oxygen charge, No, based on Sanderson electronegativity
(reproduced by permission of Elsevier Science B.V.,
Amsterdam).
many zeolites are often bound to selected aluminas
or clays to enhance their stability. XPS analysis
has demonstrated that these binders often coat
most of the zeolite particles with a thin layer that
is not detected by NMR. In some cases, these
coatings are found to alter various aspects of the
adsorptive and catalytic properties of these sys-
tems. In other cases, however, N M R and XPS
results suggest detection of the same species [14].
Several zeolites (Na-Y, ZSM-5, L- and T zeolite)
and SAPO-5 were investigated by Stoch et al. [15],
resuming that for all network elements only sym-
metrical peaks of the binding energies were
observed, indicating a very homogeneous distribu-
tion of the electron densities around the atoms
throughout the lattice. The authors found that the
binding energies of Si 2p, O ls and A1 2p in
zeolites increased with increasing concentration of
aluminum, which is in contradiction to previously
published results. For aluminum, however, the
dependence between the A1 2p binding energies
and the aluminum content is not as obvious as for
Si 2p and O ls bands. The values either do not
depend on or increase slightly with the aluminum
content. The changes might be interpreted either
to be due to variations in the polarity of AI-O
bonds and/or to the increasing concentrations of
counter cations that localize charges and, hence,
cause a slight depletion of electrons at the A1a ÷
lattice site. The XPS results indicate that phos-
phorus (in SAPO-5) increases the electron densities
at all other network elements, leading to a lowering
the effect upon aluminum and silicon is less pro-
nounced [ 15 ].
The electronic structure of zeolites was demon-
strated to depend strongly on both the composition
and the cation involved. It was suggested by
Okamoto et al. that the basic strength of frame-
work oxygen increases with increasing A1 content,
regardless of the crystal structure, and with
decreasing electronegativity of the counter cation
o Na~120* [16].
For zeolites that exhibit ion conductivity, the
surface charge in the application of surface spectro-
scopy, like XPS, may be significantly reduced by
using elevated measurement temperatures. This
technique permits the straightforward detection of
 M. St6cker/Microporous Materials 6 (1996) 235-257 243

differential-charging effects in XPS with zeolites. 0.6

This method is applicable to those zeolites that 0.5 Y(U.S.)

exhibit an increased conductivity at elevated tem-
peratures, however, a limitation lies in the elevated + 0.4
/ Na-A
temperatures required for the measurements,
which may give rise to modifications of the 0.3
samples [ 17]. FerrieriteJ u ZK'5
0.2 -I.-Edonite~ __Clinoptilolite
,,,°,,,e

5. The characteristics of zeolites and related 0.1 ,~o Merdenite

~ZSM-5
materials including incorporated species 0 I I I I I
0.1 0.2 0.3 0.4 0.5 0.6
5.1. Surface properties Framework AI/(Si + AI)

Fig. 5. Plot of framework A1/(Si +A1) vs. surface AI/(Si +A1)

The surface composition and electronic structure (reproduced by permission of Elsevier Science B.V.,
of a number of synthetic and mineral zeolites with Amsterdam).
well characterized bulk and framework composi-
tions over a wide range of Si/A1 ratios have been decreases with an increase in the Si/AI ratio. The
characterized by XPS for the determination of binding-energy separation [Si 2 p - A 1 2s] also
Si/A1 composition of external layers [18]. The shows a similar trend.
results of the XPS and bulk analyses of the zeolites The dealumination of zeolites by different meth-
studied showed that, with the exception of ther- ods and the subsequent migration of the removed
mally treated samples exhibiting significant frame- aluminum species has been monitored by XPS,
work dealumination, the surface Si/A1 ratios are since catalysis is mainly regarded as a surface
generally equal to or slightly greater than the bulk phenomenon, and dealuminated zeolites are still
stoichiometric ratios for most of these zeolites (see of great interest from an industrial point of view
Fig. 4). In addition, the surface composition of due to their modified acidity. Therefore, a number
the same series of zeolites is generally silica- of authors have studied this important topic mainly
enriched relative to the framework composition on Y zeolite but also on other microporous materi-
(except for USH-Y) as determined by 29Si MAS als. However, the results do not always point in
N M R spectroscopy (see Fig. 5) [18]. Furthermore, the same direction. Depending on the dealumina-
the binding energy of the A1 2p photoelectron line tion method used and which binding energies for
Si (Si 2s or Si 2p) are applied for calculating the
0.6 Si/A1 ratio, different conclusions were drawn by
the different groups.
0.5 H'Y(U.S.)~ / The enrichment of aluminum at the surface of
<
0.4 Y zeolite has been observed by several authors
÷
and is interpreted as an accumulation of non-
v
< 0.3 framework aluminum species which migrate out
8 of the micropore system towards the zeolite surface
0.2 Clin°pt~--sFerderite [19-22]. Such a Si/A1 profile indicates that the
e dealumination mechanism is diffusion controlled
0.1
"Chabazite within the zeolite pores [21 ]. The aluminum species
~"ZSM-5
I I I I I expelled from the zeolite lattice and enriching the
0.1 0.2 0.3 0.4 0.5 0.6 zeolite surface most likely form a thin amorphous
Bulk AI/(Sl + AI)
aluminum oxide/hydroxide layer. Secondary ion
Fig. 4. Plot of bulk A1/(Si+A1) vs. surface A1/(Si+A1) (repro- mass spectrometry (SIMS) detects the dealumi-
duced by permission of Elsevier Science B.V., Amsterdam). nated zeolite already at depths of about 50 .A [20].
244
The Si/AI ratios of the external layers show for
the thermochemically dealuminated Y zeolite a
strong dependence on the temperature of treat-
ment, and at high temperatures, can become nearly
three times higher than that of the bulk [19]. A
quantitative analysis of XPS intensities for dealum-
inated Y zeolites was done by Grohmann and
Gross who concluded that the respective A1/Si
XPS intensity ratios of highly dealuminated Y
zeolites are explained by dispersion of the non-
framework A1 on the mesopores surface [23].
However, partial removal of aluminum from the
surface of zeolites (Y, X and A) during a dealumi-
nation procedure was observed by several groups
[24-26]. In addition, Si enrichment was investi-
gated in detail by Japanese researchers using XPS
with argon-ion etching, who concluded that sili-
con-rich configurations are localized at the surface
rather than in the interior or bulk of Y zeolite or
mordenite (see Fig. 6) [27]. Finally, the external
shell formed on a Y zeolite during steaming was
shown by XPS to contain both aluminum and
silicon extracted from the framework [28]. The
presence of tricoordinated aluminum at the surface
of dealuminated mordenites with bulk Si/A1 atomic
ratios higher than 40 were registered by Remy
et al. [29].
The surface atomic ratio of framework and non-
framework aluminum in a deep-bed steamed H-Y
zeolite and in an H-Y zeolite dealuminated by
SIC14 has been determined by XPS. The results
showed that the deep-bed dealuminated zeolite
contained two aluminum species (75.0 and 73.8 eV,
A1 2p transitions), which can be assigned to frame-
work and non-framework atoms, respectively.
Moreover, migration of the non-framework alumi-
Surface Interior
: :
:i:i:i:i:i:i:i:i:i:i:i:i:i:i:i:i?i:i:!:!:!:!:i:i:i:!:i:i:i:i:i:i:i
Fig. 6. Conceptional illustration of surface, interior and bulk
of a zeolite (reproduced by permission of the American
Chemical Society, Washington, DC).
M. Stdcker/Microporous Materials 6 (1996) 235-257
num to the surface takes place during the deep-
bed calcination of NH4-Y zeolite, the extent of
dealumination being higher inside the crystal than
at the outer surface [30].
The transport resistance experienced by ethane
molecules on traversing the surface layer of
CaNa-A type zeolite crystallites was examined by
K~irger et al. [31]. It was found that a hydrother-
mal pretreatment leads to an enhancement of the
surface resistance which is most pronounced for
the specimen with the lower calcium content.
Studying the surface composition of the zeolite
crystallites by XPS, the enhancement of the surface
barrier was shown to be accompanied by a decrease
of the cation content in the surface layer, indicating
a structural collapse of the surface layer of the
zeolite crystallite [31 ].
The composition of the surface layer of different
Fe-, Co- and Cu-doped A zeolites have been
investigated by Knecht et al. applying XPS. They
concluded that the concentrations of the transition
metals in the surface layer and the bulk material
are significantly different, with higher transition
metal concentrations in the surface [32-34].
Framework silicates with the sodalite structure
have been studied by Herreros et al. [35], who
demonstrated that purely siliceous sodalite gave a
unique set of binding energies and valence band
patterns similar to those for silica, while the XPS
pattern of an aluminosilicate sodalite is similar to
that of zeolite Na-A. The small differences in
binding energies for aluminosilicate sodalite are
due to the presence of some K ÷ and Mg 2- and
the fact that the framework Si/A1 ratio is slightly
higher than unity. XPS was thus shown to be
sensitive to the structure as well as to the composi-
tion [35]. In continuation of this work, solid-state
N M R showed that blue and pink ultramarines
etching) with bulk compositions Si/AI=I.04 and 1.11,
respectively, violate Lrwenstein's rule. XPS
revealed that the surface Si/A1 ratio of blue ultra-
) Bulk
marine is 1.20, which corresponds to positive shifts
in core level binding energies. Pink ultramarine
has an even higher surface Si/A1 ratio and a
corresponding growth in its core lines. Core level
peak positions for zeolite losod, a compact and
highly aluminous framework silicate (Si/A1 about
 M. Strcker/Microporous Materials 6 (1996) 235-257 245

1.0), are very close to those for aluminosilicate
sodalite and zeolite Na-A [36].
XPS measurements were used to identify surface
properties of silica-rich zeolites such as offretites,
ZSM-5, ZSM-11 and mordenites. The peak posi-
tions of the AI and Si Auger lines were measured
in Mg K~ XPS experiments. The A1 and Si
KL 2L 3 Auger transitions are referenced to the C
ls line at 284.6eV. Data from the A1 and Si
KL2L3 Auger lines and the A1 2p and Si 2p
transitions for the silica-rich zeolites have been
used to construct A1 and Si chemical state plots
shown in Fig. 7 and Fig. 8, respectively [37].
The A1 chemical state plot has a wide range of
modified Auger parameters from 1456.2 to
1460.3 eV and binding energies ranging from 73.4
to 75.2 eV. The A1 KL 2L 3 transition has a very
large range from 1383.2 to 1387.1 eV. The same
materials have a much smaller spread on a Si
chemical state plot. The modified Auger parameter
varies from 1711.3 to 1708.8eV. The Si KL2L 3
Auger line ranges from 1608.0 to 1610.6 eV. The
Si 2p binding energy ranges from 101.3 to
103.5 eV [37].
The chemical state of A1 at the surface of
dealuminated mordenites has been investigated by
XPS. The A1 2p signals can reasonably be decom-
posed into two components. The A1 KLL Auger
transition is more sensitive to the A1 coordination
than the AI 2p transition, and three components
can be separated in the corresponding peaks. It
appeared that three types of A1 were present at
the surface of dealuminated mordenite, namely
hexa-, tetra- and tricoordinated A1 [38].
Two series of offretite and omega zeolites were
modified by ammonium exchange and sequential
steaming/acid leaching by Ponthieu and Grange
[39]. XPS was used to quantitatively and qualita-
tively analyze the surface of these solids. The
superficial A1 concentration significantly differs

/ // / o./~/
1387/
/o/ 1460
/ / / / -/
/ / [] 1459
[] / / 0 // /
1386

-: / -

,~'/ /
1388 / []
®

o ,/ / /
.u_
i ~.

x
J
[] / /- 1458
,- Z / /I-,
/ :
I
1384 ~ [] 16o8 ~ 17o9 ~
1487

// /,
/°/ /
74 73
/ / /
76 78 104 103 102 101
2P Bindingenergy (eV) 2P Bindingenergy (eV)

Fig. 7. Aluminum chemical state plot, 1-4: different offretites,
5: H-ZSM-5, 6: H-ZSM-11, 7: H-MOR, 8: Norton-MOR, 9
and A: different Na-A, X: Na-X, Y: Na-Y, Z: H-zeolon (repro-
duced by permission of the American Chemical Society,
Washington, DC).
Fig. 8. Silicon chemical state plot, 1-4: different offretites, 5:
H-ZSM-5, 6: H-ZSM-11, 7: H-MOR, 8: Norton-MOR, 9 and
A: different Na-A, X: Na-X, Y: Na-Y, Z: H-zeolon (reproduced
by permission of the American Chemical Society,
Washington, DC ).
246 M. St6cker/Microporous Materials 6 (1996) 235-257
from the bulk one in synthetic solids. The greatest
modifications arise from acid-leaching treatments.
The surface of hydrothermally dealuminated
offretites often contains relatively more A1 than
does the bulk, whereas dealuminated omega zeo-
lites generally display Al-depleted surfaces [39].
Furthermore, offretites, erionites and their
intergrowths (T zeolites) were studied by XPS by
a few more groups. Surface dealumination was
observed for all investigated zeolites [40,41].
ZSM-5 and ZSM-11 samples have been investi-
gated by several groups with respect to the chemi-
cal compositions at the surface and bulk. XPS
data showed that the outermost layers are on an
average, richer in A1 than the inner layers [42],
which was confirmed for ZSM-5 samples treated
by strong dealumination procedures, too [43].
However, an inhomogeneous distribution of alumi-
num in ZSM-5 polycrystalline aggregates, con-
sisting of a siliceous outer surface and an
aluminum-rich interior was found by Hughes et al.
[44]. The surface depletion of aluminum marks a
sharp contrast with some recent surface studies of
ZSM-5. For example, Suib et al. and Dwyer et al.
found no differences between the Si/A1 ratios of
the surface and bulk [45,46]. However, von
Ballmoos and Meier [47] measured an enrichment
of aluminum at the surface of ZSM-5, while
Derouane et al. [48] found similar surface and
bulk Si/AI ratios for large crystals (5-8 #m) but
an enrichment of surface aluminum for smaller
crystals (< 1 #m). As Derouane et al. suggested,
this variance of results is due to the fact that
ZSM-5 is not a uniform material [48]. Hence
conclusions drawn about the aluminum distribu-
tion of ZSM-5 prepared by one particular method
may not necessarily be applicable to all ZSM-5
preparations [44].
The XPS spectra of the natural zeolite natrolite
were measured, and a comparison of the binding
energies of the Si 2p, A1 2p, Fe 2p3/2, Na 2s, Ca
2p3/2 and O ls transitions with published data on
similar substances confirmed that the coordination
numbers of Si and A1 in the natrolite structure
were equal to 4. In addition, the following coordi-
nation numbers were found: Fe=4, Na=6, C a =
6 and O = 2 [49].
5.2. Nature and electronic state of metals/redox
behavior
Transition metal containing zeolites are impor-
tant catalysts for a number of chemical reactions.
The nature and electronic state of those metals
are, therefore, important items to investigate, and
a number of papers dealing with this topic are
reviewed in the following.
XPS studies of hydrated, dehydrated and
reduced CuNa-Y and CuNa-X zeolites were car-
ried out by Kevan et al. [50,51]. With sufficient
analytical resolution, both the Cu 2pl/2 and 2p3/2
transitions were resolved into two components in
hydrated CuNa-Y. The higher binding energy
component (about 935-936 eV) and the shake-up
satellites decreased in intensity upon dehydration.
The higher binding energy component was
assigned to octahedrally coordinated Cu 2+ in the
large a-cages of the zeolite, and the lower binding
energy component (about 933-934 eV) to tetrahe-
drally coordinated Cu 2+ in the small r-cages of
the zeolite [50]. Cu + and Cu °, obtained by
hydrogen reduction at high temperature, showed
single XPS peaks at about 932eV without
shake-up satellites [51].
Four states of Cu have been characterized in A,
X and Y zeolites with XPS by Sexton et al. [52].
By applying the 2p3/2 and L 3 M4,5 M4,5 Auger
lines the authors identified Cu 2+, Cu +, 1 nm metal
clusters and bulk metal crystallites. The Cu-species
present in the zeolite depend on the degree of
reduction. Cu + can be exclusively generated by
mild reduction of X or Y zeolite with CO. One nm
clusters are generated in the supercages of zeolite
A by mild hydrogen or CO reduction [52].
Migration of Cu species into the zeolite channels
at elevated temperatures was observed for a mix-
ture of Cu20 and NH4-Y zeolite by Jirka et al.
[53]. The same group demonstrated that the Cu
2pa/2 line-shape changes for cupric ions exchanged
in Y-zeolite are caused mainly by their reduction
to Cu ÷ during the XPS experiment. Similar (but
much faster) effects, understandable in the same
way, have been observed for Cu-ZSM-5 zeolite
[541.
The determination of the oxidation state of Cu
in Cu-exchanged ZSM-5 is important for under-
 M. St6cker/Microporous Materials 6 (1996)235-257
standing its role in the mechanism of decomposi-
tion and selective reduction of NO [55]. Cu-ZSM-5
catalysts prepared by ion exchange and by impreg-
nation have been investigated by XPS. In both
preparations, the external surface region of the
catalyst is highly enriched in Cu. In the ion-
exchanged zeolite, the observation of high XPS
binding energies and unexpectedly low Auger
kinetic energies showed that Cu is present as
isolated ions or small clusters. In the impregnated
material large aggregates of metallic Cu at the
external zeolite surface were produced by reduction
in hydrogen, which were not dispersed by treat-
ment in oxygen or NO. In the exchanged materials,
the Cu became more evenly distributed across the
zeolite crystal as a result of calcination or reductive
treatment [56].
The surface characteristics of Ni containing
ZSM-5 prepared by ion exchange, impregnation
and mechanical mixing have been monitored by
XPS. Ni can exist in many forms on the surface
of the zeolite, e.g. as NiO, Ni(OH)2 and
NiA1204. The degree of reduction of Ni 2÷ species
depends mainly on its form, and decreases in the
order NiO>Ni(OH)2>NiA1204. The surface
analysis indicates that ZSM-5 does not have a
uniform composition. Surface enrichment of alu-
minum and nickel was observed and can be
explained be several factors, including the sample
preparation method, the stage of the redox cycle
and the treatment conditions [57]. A Ni-exchanged
ZSM-5 sample was used for the xylene isomeriza-
tion and checked with respect to the state of the
nickel under those operating conditions. The
authors found that the presence of nickel sup-
pressed catalyst aging significantly and, in addi-
tion, the nickel ions did not undergo any major
chemical modification during the pilot plant trial
[58].
XPS analyses of hydrated and hydrogen-reduced
NiNa-X and NiCa-X zeolites have been per-
formed, indicating that reduction at 327°C is
sufficient to reduce some of the Ni 2÷ in NiNa-X
to the metallic form. Deconvolution of the broad
XPS peak shape indicates three components
assignable to Ni 2÷, Ni ÷ and Ni °. XPS data indi-
cate that hydrogen reduction of Ni 2÷ to Ni ÷ and
Ni ° occurs at lower temperatures in NiNa-X than
in NiCa-X zeolite. Concerning the Y zeolite, the
247
opposite observation has been reported [59].
Nickel in NH4NiNa-Y zeolite has been observed
in a highly dispersed state [60]. An intrinsic
method for measuring the true kinetic and binding
energies of photoelectrons has been described by
Steinbach et al. [61] applying their technique to
Ni containing A, X, Y and ZSM-5 zeolites. The
binding energies of O ls and Si 2p transitions
increased with increasing Si/A1 ratio of the zeolites,
for the A1 2s transition, however, the increase was
less marked. The influence of the cation on the
binding energy values of the O 1s, Si 2p and AI 2s
was examined only for Y zeolite: no influence of
the cation on Eb was observed [61].
The behavior of Fe 3÷ cations in H-Y zeolite
which had been subjected to various treatments
has been studied by XPS. The self-reduction of
Fe 3+ to Fe 2÷ after vacuum heat treatment and
the partial reduction to Fe ° after hydrogen treat-
ment was found in the zeolite surface layers in
accordance with results of studies of the bulk
zeolite. The binding energies of Fe cations were
found to be close to those of the corresponding
oxides [62]. Furthermore, the external surface
composition of Fe-exchanged Y zeolite with
respect to percent exchange and thermal treatment
was investigated by Kulkarni et al. [63] who
concluded that the Si/A1 ratios of the external
surface were higher than the corresponding bulk
ratios and showed a small increase with the percen-
tage ferric exchange. This indicates that the exter-
nal zeolite surface is aluminum deficient [63].
The extent of the electron deficiency of Pd
clusters in Y zeolite with varying proton concen-
trations and locations has been identified by XPS.
The electron sharing between Pd clusters and
protons in Pd/Na-Y zeolite results in an upward
shift of the binding energy of Pd 3d5/2 of about
0.4 eV. No surface enrichment of Pd was observed,
and the metal was homogeneously distributed.
Reduction of the ion-exchanged Pd/Na-Y zeolite
in hydrogen at elevated temperatures led to a Pd
3d line shift to lower binding energies (see Fig. 9)
[64].
XPS studies of Pd-exchanged NaX zeolite indi-
cate that, under suitable ion exchange and sample
treatment condition, unstable oxidation states of
Pd 3+ and Pd ÷ can be stabilized and characterized.
The peak at a binding energy of 339.0 eV (Pd
248 M. Sti~cker/Microporous Materials 6 (1996) 235-257
450
350'
300
250
200'
150'
100 '
20
337.0 347.0
Ee'eV
Fig. 9. Positions of the Pd 3d line at increasing temperatures
for Pd/Na-Y zeolite (reproduced by permission of the Royal
Society of Chemistry, Cambridge.).
3d5/2 transition) in oxidized samples of Pd/Na-X
zeolite can be unambiguously assigned to Pd 3+.
In samples reduced in static hydrogen the XPS
peak at 336.4 eV corresponds to Pd + , but if flow-
ing hydrogen is used this peak seems to correspond
to small charged Pd clusters [65]. XPS has been
used to characterize different oxidation states of
Pt in Y zeolite. Monoatomically dispersed Pt °
atoms exhibit an usually small relaxation energy
(+ 1.3 eV shift), and 10 or 20 ,~ metallic Pt clusters
present a significant positive XPS shift (+ 0.7 eV).
A comparison with Pt clusters on silica (+ 0.3 eV)
and a study of the ability of charge transfer
complex formation have shown that electron
transfer occurs between the metallic clusters and
the zeolitic support, resulting in strong electron
donor properties of the support [66]. Under the
conditions applied for the ion exchange of Na +
by transition-metal cations (Pt 2+ and Co2+), alu-
minum containing ensembles of Na-Y zeolite
migrate toward the external surface resulting in
surface enrichment of aluminum. Comparison of
the ion-exchanged and impregnated samples
revealed that transition metal ions are really
exchanged into the zeolite but their distribution is
not homogeneous in the subsurface layer. The
simultaneous presence of Co 2÷ and Pt 2+ ions
results in an increased sensitivity of Pt to oxidation
or in the formation of a mixed Pt oxide/ CoOn
phase. Co 2÷ ions also affect the electronic state
of Pt o particles as displayed in the positive binding
energy shift of the Pt 4d5/2 transition. The binding
energy shift of the Co 2p3/2 line evidences the
formation of bimetallic particles within the zeolite
support. Pt 2÷ ions exchanged before the Co 2÷
ions hinder the migration of the latter into deeper
zeolite layers, suggesting the formation of 'cherry'-
type particles. Pt ° particles were unambiguously
proven to assist the reduction of Co 2÷ ions in the
cavities of Na-Y zeolite [67].
Rhodium exchanged Y zeolites have been shown
to exhibit a wide variety of catalytic properties,
and XPS studies indicate that Rh a ÷ may be ther-
mally reduced to Rh metal in the zeolite Y lattice.
It was strongly suggested that metallic Rh pro-
duced by the activation of Rha+-exchanged Y
zeolite rather than the Rh 3÷ cations, are the
probable catalytic species in so-called Rh 3÷ zeolite
catalysts [68]. A stable zeolite-supported Rh cata-
lyst was studied by Liu et al., and the active Rh
component was found to be trivalent, and Rh in
the catalyst was in form of ions which partly
occupied the Na ÷ sites in the lattice of ZSM-5 [69].
Ru-exchanged Na-Y zeolites were studied with
XPS in order to determine changes in the location
and state of the Ru after subjecting the samples
to both oxidizing and reducing environments.
When oxygen was excluded from the system, Ru
remained inside the zeolite cavities following the
reduction in hydrogen and after the zeolite had
catalyzed the methanation reaction. At elevated
temperatures, before or after reduction, the pres-
ence of oxygen resulted in the formation of
RuO2 on the external surface of the zeolite. The
peak intensity of the Ru 3d5/2 line increased by
more than a factor of five when Ru migrated to
the surface. Positive binding energy shifts of
approximately 1 eV were detected for small clusters
(< 10 .A) of reduced Ru when compared with larger
metal particles within the zeolite or on its external
 M. St6cker/Microporous Materials 6 (1996) 235-257
surface [70]. A Ru/K-L zeolite has been studied
by Liu et al. [71], who demonstrated that Ru 3+
and Ru ° atoms are present in the zeolite catalyst.
The activity for carbonyl hydrogenation remained
the same after several reaction runs, independent
of the conversion [71].
Faujasite-type zeolites containing La introduced
by various techniques and in different amounts
were studied by XPS in order to elucidate the
influence of the zeolite matrix on the binding
energy and the shape of the La 3d line. Significant
differences in the La 3d line shapes and binding
energies between La203 and La zeolites were
ascribed to final-state effects arising from the
hybridization of La final states with valence bands
of different extension. The La 3d line shape of the
La zeolites investigated at elevated temperatures
was found to respond to structural changes in the
surface region of the samples (dehydration, ion
migration, formation of highly dispersed La-O
structures on extra-framework sites) [72]. Rare-
earth ion-exchanged Y-type zeolites were investi-
gated by Arakawa et al., who showed that the 4f
levels of Eu-Y zeolite were drastically changed by
degassing at low temperature: the relative inten-
sities of the 4f levels for Eu 3+ decreased, and the
4f line of Eu 2+ increased as the sample was
degassed at 400°C [73].
Catalysts consisting of Ga203 mechanically
mixed with H-ZSM-5 zeolite have been examined
via XPS both before and after reduction with
hydrogen. The XPS measurements have shown
that there is a Ga transfer upon hydrogen reduc-
tion of Ga203/H-ZSM-5 catalysts prepared by
mechanical mixing the pure components.
Experiments with Ar+-etched samples show that
Ga ions are transferred into the bulk of the zeolite.
The Ar ÷ bombardment leads to an increase in the
Ga 3d binding energy [74].
The chemical bonding of Ti in Ti-silicalite has
been investigated using XPS. A distinctively higher
binding energy of the Ti 2p photoelectrons in
Ti-silicalite was found compared to those mea-
sured for titania- or anatase-containing silicalite.
Ti had the same oxidation state in all solids
investigated. The difference in binding energy was
attributed to different oxygen coordinations of Ti
in the framework of Ti-silicalite (tetrahedral) and
249
anatase (octahedral). Non-framework TiO2
species containing octahedrally coordinated Ti
could also be distinguished by XPS [75].
Ti-silicalite samples with MEL structure (TS-2)
and different Ti loadings have been examined by
Trong On et al. [76] using XPS (among others).
It was shown that as the Ti content increased, the
Ti 2p3/2 binding energy decreased from 459.8 eV
to 458.3 eV, which corresponds to a change from
tetrahedrally coordinated Ti to octahedrally coor-
dinated Ti-species [76].
A series of alkali-cation-exchanged and some
proton-exchanged zeolites have been investigated
with respect to cation-framework interactions. The
XPS study revealed that the higher the electronega-
tivity of the counterion is, the lower the framework
element binding energies of Si 2p, A1 2p and O ls
are. However, the extent of these changes depends
strongly on the Si/A1 ratio of the zeolites [77]. A
study of Na-, Li- and Ce-exchanged Y-type zeolites
using conventional Mg K~ and high-energy mono-
chromatic Ag L~ radiation has been described by
Edgell et al. [78]. The chemical changes induced,
predominantly in Na-Y zeolites, involve the reduc-
tion of the Na + cations to the metallic state,
apparently following their diffusion from the bulk
to the surface. The Auger parameters of silicon
and aluminum and the derived oxygen polarizabil-
ity decrease with the electronegativity of the
charge-balancing cation for this series of simple
cations [78].
The interaction between the mono- and poly-
cationic forms of Y-zeolites containing Ni, Co,
Cu, Cr and CO, oxygen or CO +oxygen under
conditions similar to those of catalytic CO oxida-
tion has been monitored by XPS. Upon interaction
of Ni-containing Y zeolites with CO or with
CO+oxygen, Ni 2+ is reduced to Ni + and Ni °.
The ability of metal reduction decreases in the
following series of polycationic forms:
Cr > Co > Ni > Cu. The treatment of CuNiNa-Y
and CoNiNa-Y zeolites with CO leads to the
formation of Cu +, Cu ° and Co °, respectively [79].
5.3. Metal clusters~complexes in zeolites and
related materials
The position, structure and distribution of metal
clusters/complexes in zeolites and related materials
250 M. St6cker/Microporous Materials 6 (1996) 235-257

is of importance with respect to catalytic applica-
tions of modified zeolites. Therefore, several
attempts have been made to characterize these
metal-complex catalysts in the light of their poten-
tial use.
An XPS study of Mo clusters in zeolite Y formed
by adsorption and decomposition of Mo(CO)6 has
been reported by Yong et al. [80]. The XPS data
showed that this method produced a uniform
dispersion of Mo. The Mo clusters have a Mo 3d
binding energy ca. 1.2 eV higher than that of bulk
Mo, which is attributed to their small size (equal
or less than 12 A) [80]. The adsorption and decom-
position of the volatile carbonyl complexes
Mo(CO)6, Fe(CO)5, Co2(CO)8 and Co(CO)3NO
in various zeolites have been studied by XPS.
Mo(CO)6 produces highly dispersed zero-valent
clusters in the zeolites Na-Y, Na-X and K-L, and
a mixture of oxidized species in La-Y zeolite.
Fe(CO)5 produces initially zero-valent clusters in
Na-Y, but these migrate to the external surface on
heating to higher temperatures. Migration of iron
out of the zeolite is inhibited by exchanging the
divalent cations Co 2÷ and Ni 2÷ into the zeolite.
Coz(CO)a decomposes extensively on the external
surface of Na-Y and Na-X zeolite, but the mono-
nuclear complex Co(CO)3NO is readily adsorbed
into Na-Y; decomposition produces a mixture of
zero-valent and oxidized cobalt species [81 ].
Transition metal complexes fixed in Y zeolites
by 'surface assembling' (Ni-, Co-, Cu- and
Ru-phthalocyanines) have been investigated by
XPS. Metal phthalocyanines were found to be
located in supercages as isolated complexes which
interact with zeolitic OH groups via meso N atoms
of the porphyrin ring [82]. Furthermore, XPS was
used to investigate the formation and location of
Ni 2÷- and C02÷-bis(dimethylglyoximato) com-
plexes following the reaction of Ni 2÷- and
Co 2÷-exchanged Na-X zeolites with dimethylgly-
oxime. The formation of the complexes and the
location within or on the outer surface of the
zeolite matrix was sensitive to the reaction condi-
tions and the sequence of reaction steps [83].
Cobalt phthalocyanine (CoPc) was synthesized
within the cavities of Y zeolites and characterized
in all steps of the synthesis and purification by
(among others) XPS. While the binding energies
for Si 2s, AI 2p, O ls and Na ls remained
unchanged, a small shift toward lower energies for
the Co 2p and N 1s transitions was observed when
CoPc was in contact with the zeolite (see Fig. 10).
The surface atomic ratio for Co/Si was higher than
for the bulk Co/Si ratio. On the other hand, the
corresponding N/C atomic ratios are about the
same [84].
XPS investigations of methylene blue incorpo-
rated into faujasites and AIPO4 molecular sieves
were reported by Hoppe et al. [85]. The exchange
of the methylene blue cation into the zeolites
resulted in high dispersions of the dye, but could
cause a local destruction of the zeolite framework
at the crystal surface. The structure-directing role
of the dye was recognized for methylene blue
loaded SAPO-5 and SAPO-34, exhibiting an
improved phase purity [85].
PY
laY
n$
~aY
~e
n$
810 800 790 780 770
eV
Fig. 10. XPS binding energies of the Co 2p transitions for cobalt
phthalocyanine (CoPc), CoPc with Na-Y, CoPcNa-Y, CoNa-Y
and CoNa-Y with pyridine (py). The vertical scale is not the
same for all the samples (reproduced by permission of the
American Chemical Society, Washington, DC).
 M. Strcker/Microporous Materials 6 (1996) 235-257
5.4. Dispersion of metals and metal oxides in
zeolites
Metal loaded zeolites are widely used in petro-
chemical processes and are broadly investigated
with respect to applications within catalysis. The
zeolite matrix has proved to be especially suited
for the production of monomodal metal disper-
sions, which have been identified mainly by TEM.
The conclusion has been drawn from the electron
micrographs that monodispersed metal phases can
be located exclusively inside the zeolite matrix. It
is, therefore, desirable to check such an assumption
by a surface sensitive method like XPS. This was
done by Schulz-Ekloff et al. with a series of
faujasite supported catalysts with monomodal dis-
persed phases of nickel, palladium and platinum,
exhibiting narrow particle size distributions as
characterized by XPS [86].
No XPS evidence was found for the migration
of Pt to the external surface of Pt/Ca-Y zeolite
crystallites, whereas this phenomenon was indeed
observed for a sample of Pt/Na-Y which was
reduced directly in hydrogen at 350°C. In addition,
differences in metal-support interactions were not
evident from the binding energy data for the
several types of reduced platinum examined in this
study [87]. Pt and Pd ions in Y-type zeolites were
investigated by Vedrine et al. [88], and both ions
were found to be ionically bonded to lattice
oxygen. Atomically dispersed Pt ° and Pd ° were
shown to give significant XPS positive chemical
shifts: + 1.3 eV and + 1.4 eV for Pt 4f and Pd 3d
lines, respectively. These shifts were assigned to
smaller relaxation energies. The positive XPS
chemical shifts detected for metal Pt aggregates on
zeolites compared with those for Pt on silica
strongly suggest that electron donation occurs
from the metal aggregates to the zeolite lattice [88].
XPS has been used to elucidate the state of Cr
in the surface layers of Cr/H-Y zeolite. The binding
energy value of the Cr 2p level for chromium in
the zeolite differs from that of bulk chromium
oxide compounds or that of Cr supported on silica.
The counter-Cr 3÷ ions in the surface layers of Y
zeolite are reduced by heat treatment both in CO
and in vacuo to Cr 2+, unlike the Cr 3 + ions in the
zeolite bulk, which are not self-reduced. The stable
251
isolated Cr 5+ and Cr 6+ ions present in the oxidized
zeolite bulk were not detected by XPS in the
surface layers because of their reduction in vacuo
and/or by X-ray irradiation in the XPS system
[89].
A series of MOO3, NiO and MoO3 +NiO on
ultrastable H-Y zeolite (USHY) catalysts with
different oxide loadings and different procedures
of preparation have been studied by (among
others) XPS. It has been found that Mo and Ni
species are highly dispersed, and both oxides can
be found in the supercages of the Y zeolite. In the
case of N i O + M o O a / U S H Y catalysts, an inter-
action between Ni and Mo was established through
oxygen bonds. The degree of interaction depends
on the order of incorporation of the metals and
on the Ni/Mo ratio. The strongest interaction was
observed in the sample in which the Mo was
impregnated first [90]. The identification and study
of the electronic properties and location of CdS
and CdO particles in faujasites have been per-
formed using XPS. Depending on the preparation
procedure, CdS aggregates have different disper-
sions and can be located either inside the zeolite
structure or on the external surface. Small CdS
particles (1.5-2 nm) exhibit XPS band shifts indi-
cating a semiconductor size quantization effect.
Larger CdS particles (6-8 nm) exhibit electronic
and relaxation properties rather close to those of
bulk CdS. Strong surface enrichment with these
particles was also observed. The CdO aggregates
are formed during Cd-Y treatment with NaOH
and calcination in air. The identification of CdO
is based on an abnormally low binding energy of
Cd, which is characteristic for CdO only [91].
Finally, a paper dealing with the quantification
of XPS data of supported catalysts using the
so-called sheet stacking model with surface segre-
gation was published by Sayari et al., and the
interested reader should consult this paper for
further details [92].
5.5. Catalysis and coke formation
XPS is more and more successfully applied to
problems related to catalysis and coke formation.
The quantitative use of XPS intensity ratios,
although not yet fully developed, has interesting
252 M. Strcker/Microporous Materials 6 (1996) 235-257
potential applications in the characterization of
zeolite catalysts having quite complex structural
features. It is especially noteworthy that, by using
XPS, these features can be examined whatever the
chemical environment of the metallic elements
under consideration, as demonstrated with
FePd/ZSM-5 catalysts prepared by two different
techniques and used for deoxygenation of organic
compounds in the presence of CO [93]. The varia-
tions of the (Me/Si)xPs atomic ratios are calculated
from the peak areas of the corresponding photo-
electron transitions by Eq. 7:
IM~ OSi Dsi 2Si
(Me/Si)xPs =
/Si 0"MeDMe '~Me
where I is the XPS intensity, a is the photoelectron
cross-section, 2 the escape depth and D the effi-
ciency of collection [93].
A splitting of the O Is peak in the XPS of a
dehydrogenating coked FeHNa-Y zeolite catalyst
has been observed by Kulkarni (see Fig. 11) [94].
527.8
(b)
J ratio. This may also indicate that Cu is preferen-
¢
(a)
528.4 ,~
| I
520 540
Binding energy (eV) ~,
Fig. 11. XPS spectra (O ls transitions) of the Fe/Na-Y (a) and
Fe/Na-Y (b) (coked) catalysts (reproduced by permission of
Scientific Publishers, Jodhpur, India).
The splitting is due to the charge donation from
the coke to the framework oxygens of the
FeHNa-Y zeolite. The strongly basic oxygens and
the hydrogen-deficient coke are the active center
in the dehydrogenating coked FeHNa-Y zeolite
catalyst. The O ls XPS peak at 527.8 eV for the
coked FeHNa-Y zeolite is the fingerprint peak for
the catalysts active in the dehydrogenation reac-
tions [94].
These investigations have been extended by the
same author to include mordenite and H-ZSM-5
catalysts. The multiple structure of the Si 2s peak
in the XPS of coked zeolites indicates that the
coke deposit interacts strongly with SiO4 tetrahe-
(7)
dra [95].
The liquid-phase hydration of acrylonitrile to
acrylamide has been studied using Cu-exchanged
Y zeolite. Identification of oxidation states reveals
that during dehydration Cu hydroxyl species are
formed. During the calcination, autoreduction of
Cu 2+ to a lower oxidation state was seen. The
catalyst is reduced almost completely under
hydrogen atmosphere to the Cu ° state. However,
in the used catalyst, only Cu 2+ in a CuO phase
was observed. During the reaction, it is possible
for the Na in the catalyst sample to migrate from
the surface to pores that are inaccessible to X-ray
radiation during XPS analysis. A comparison of
surface atomic ratios of elements in fresh and used
catalysts indicates that in the used catalyst the
silicon concentration has been reduced consider-
ably, resulting in a lowering of the Si/AI atomic
tially replacing Si on the surface. As the surface
of the used catalyst is rich in Cu, the Cu from the
pores of the zeolite must have migrated to the
surface during the hydration reactions [96].
Rh/Y zeolite catalysts were investigated with
XPS, and it was found that a considerable amount
of Rh ÷ was produced as a stable intermediate
during the reduction of Rh 3÷ to rhodium metal
by the heat treatment of the Rh/Y catalysts in
vacuum. It was demonstrated that Rh ÷ in the
zeolite is active for the hydrogenation and the
dimerization of ethylene and that Rh metal is
active for the hydrogenation of both ethylene and
acetylene. Strong correlations between liquid sys-
tems containing dissolved Rh complexes and solid
 M. StScker/Microporous Materials 6 (1996) 235-257
Rh/Y zeolite catalysts were found regarding the
active state of Rh and probably the reaction mech-
anism. Rh in the zeolites showed considerable
migration, clustering and sintering during the acti-
vation process. It was suggested that the structure
of Rh in the zeolite correlates strongly with the
chemical nature of Rh [97].
The hydrogenation of CO has been studied on
a series of Pd catalysts supported on H-ZSM-5,
Na-ZSM-5, H-Y, Na-Y zeolites and SIO2. XPS
results showed no shifts in binding energies indicat-
ing that metallic Pd was the predominant active
species [98].
The isomerization of n-butane over Y type and
offretite zeolites was carried out by St6cker et al.
[99] applying XPS (among others) for the charac-
terization of the zeolites. For Na-offretite, two
types of Na-sites were disclosed through chemical
shifts in the Na ls binding energy and the Na
KLL Auger kinetic energy. After ion-exchange to
H-offretite, only the lower photoelectron binding
energy and the higher Auger kinetic energy sites
remained occupied, in reduced amounts, though
(see Fig. 12). This observation indicates the exis-
tence of both non-exchangeable and exchangeable
Na-ions in Na-offretite, the former being located
in a more electron-rich environment in the zeolite
framework [99].
Two ZSM-5 zeolites with different Si/A1 ratios
(39 and 74, respectively) were used as catalysts for
the conversion of methanol. The coke formation
on the external and internal surfaces of the ZSM-5
crystals was readily distinguished by using XPS to
follow the C/Si ratio. This ratio increased linearly
at a low rate with internal coke formation, and
exponentially when external coke was formed.
Internal coke formation predominated during
methanol conversion over ZSM-5 until the catalyst
was essentially deactivated. External coke was then
formed, probably by the thermal cracking of meth-
anol [100]. The reaction of toluene with ethanol
over H-ZSM-5 (Si/AI ratio of about 27) was
followed by XPS analysis of the partially coked
catalyst. As a result of the coke deposition, the Si
2s and C ls binding energies were decreased by
1.0 eV due to the electron charge transfer from the
coke to the framework Si- and O-atoms. After the
reactivation of the coked sample, the framework
253
H-offretite ~ 990.2
/xl0
.,~ I,t~ 987.9
g90,3~/xl
I I I
996.6 986.6 976.6
Auger kineticenergy(eV)
Fig. 12. Na KL2,3L2, 3 Auger electron spectra of H- and
Na-offretite (AI Kc~ X-rays).
oxygen atoms become more basic in nature. The
results suggest that the coke was deposited on
SiO4 tetrahedra [ 101 ].
XPS results concerning the adsorption of
organic bases on H-Y zeolites outgassed at
different temperatures have been reported by
Defosse and Canesson [102]. The position of the
N ls level of aniline adsorbed on H-Y zeolite
undergoes a shift of approximately - 2 eV when
the calcination temperature exceeds 400°C, which
is the dehydroxylation temperature for the zeolite.
The XPS line position seems to depend on whether
the adsorption takes place on Bransted or Lewis
sites [102].
5.6. Characterization of acidity and basicity in
zeolites
The XPS method has been proposed for the
identification and quantitative determination of
Brensted and Lewis acid sites in zeolites, and
inspiring work has been done by Borade et al.
254 M. St6cker/Microporous Materials 6 (1996) 235-257
[103]. The method consists of deconvoluting the
N ls XPS level of chemisorbed pyridine and
measuring the relative intensities of the peak com-
ponents. It was found that pyridine is chemisorbed
in three different states on, for example ZSM-5,
corresponding to N ls binding energies of 398.7,
400.0 and 401.8 eV, respectively. The first peak at
398.7 eV was assigned to the N ls level of pyridine
adsorbed on Lewis sites, while the second and
third were assigned to the N ls levels of pyridine
adsorbed on relatively weak and strong Bronsted
acid sites, respectively (an example with Y zeolite
is shown in Fig. 13 [104,105]). Comparisons of
the concentrations of the various acid sites as
determined from the relative intensities of the N
1s components with IR data showed that XPS has
potential applications in the identification and the
quantitative determination of Bronsted and Lewis
acid sites in zeolites [106]. Moreover, the XPS
technique has the ability of providing the relative
concentrations of strong and weak Bransted sites.
LL__
jk.
392 397 402 407 412
Binding Energy(eV)
Fig. 13. Deconv01uted N ls XPS spectra of pyridine chemi-
sorbed on H-Y zeolites with different surface Si/A1 ratios of 3.6
(A), 4.1 (B) and 12.9 (C) (reproduced by permission of Elsevier
Science B~V., Amsterdam).
Usually such measurements cannot be made by
IR spectroscopy [103]. Isomorphous substitution
of Fe for Si or A1 in the ZSM-5 framework leads
to a slight decrease in the binding energy of the N
1s Lewis component. In the case of boron substitu-
tion in ZSM-5 a decrease in the binding energy of
all three N ls components was observed [107].
The same research group silylated H-ZSM-5
using different agents and investigated the acidity
of the samples by XPS of chemisorbed pyridine.
The results suggest that the removal of a Bransted
acid site produces a framework trigonal A1 atom,
which is the Lewis acid site in H-ZSM-5 zeolites.
Compared with the IR spectra, the XPS spectra
of chemisorbed pyridine are more sensitive in
distinguishing Brensted acid sites of different
strengths. The removal of external silanol groups
does influence the distribution of surface acid sites
by increasing the proportion of strong surface
Bronsted acid sites [108]. The comparison of the
ratio of the Bronsted and Lewis acid sites deter-
mined from the relative intensities of the N ls
peaks with IR spectroscopic data showed that
there is an inhomogeneous distribution of Brensted
and Lewis acid sites in H-ZSM-5 [109].
The large pore zeolites containing 12-membered
ring pore openings designated as omega, beta,
ZSM-20 and mordenite have been investigated for
their acidic properties using N l s XPS of chemi-
sorbed pyridine [110]. Deconvolution of N ls XPS
spectra revealed that all zeolite samples contained
relatively strong Bransted, weak Bronsted and
Lewis acid sites. The binding energy of the N ls
component peak associated with strong Bronsted
acid sites in omega zeolite was found to be signifi-
cantly higher than those Bronsted acid sites present
in the other zeolites. The results were compared
with normal H-Y zeolite which contained one type
of Brensted acid site and Lewis acid sites. Based
on the N l s binding energy value zeolites are
arranged for their Brensted acid strength as fol-
lows: omega > beta > ZSM-20 > mordenite > H Y
zeolite [110].
The acid strength of Mg-exchanged X- and
Y-type zeolites was examined by Viner et al. using
XPS. The high activity of these zeolites was
reflected in their Mg 2p binding energies which
were higher than those in the oxide and salts. The
 M. Strcker/Microporous Materials 6 (1996) 235-257
AI 2p and Si 2p binding energies were smaller than
those of the oxides [ 111 ].
Finally, an XPS method was proposed for the
characterization of Lewis basic sites in alkali-
cation faujasite zeolites by Huang et al. [112]. The
technique consists of deconvoluting the N ls XPS
line of chemisorbed pyrrole and measuring the
relative intensities of the peak components. It was
found that, whenever the zeolite sample contains
two kinds of alkali cations, two different deconvo-
luted N ls peaks corresponding to pyrrole chemi-
sorbed on these two sites are obtained. Combined
with IR observations, the results offer further
evidence for the basic sites being the framework
oxygen adjacent to the alkali cations in faujasite
zeolites. The stronger the basic site, the lower the
N ls binding energy level of the corresponding
peak component is. An N ls peak corresponding
to polymerized pyrrole species was also detected
in the cases of Li-Y and Na-Y zeolites [112]. An
example is demonstrated in Fig. 14 which shows
the N ls XPS lines of pyrrole chemisorbed on
391 396 401 406 411
Binding energy, eV
Fig. 14. N ls XPS lines of pyrrole chemisorbed on alkali
exchanged X zeolites (reproduced by permission of Elsevier
Science B.V., Amsterdam).
255
alkali exchanged X zeolites [ 113]. One component
(400.6 eV) is formed in all spectra (see Fig. 14),
and as it is the dominant peak in the spectrum of
Na X zeolite, it is ascribed to pyrrole chemisorbed
on a surface oxygen adjacent to a sodium cation.
The other major peak (399-401 eV) is assigned to
pyrrole chemisorbed on the basic sites associated
with the other cation. The binding energy for these
sites is in the order of increasing electropositivity:
Li > Na > K > Rb > Cs. Thus the lower binding
energy is associated with higher basic strength.
Similar results were obtained for a series of alkali
exchanged Y zeolites [113].
6. Concluding remarks
It has been shown that XPS is a powerful tool
for the characterization of zeolites and related
materials. The author is aware that not all contri-
butions published so far could be taken into
account in connection with the preparation of this
review. However, he hopes that this paper can
provide an overview within this part of surface
characterization of zeolites and related materials
research.
Acknowledgements
The author is indebted to Tordis Whist for
technical assistance in connection with the prepara-
tion of the figures, and the relevant publishers are
gratefully acknowledged for their permission to
reproduce the figures as cited in the text. Financial
support by The Research Council of Norway
(NFR) and SINTEF Chemistry is gratefully
acknowledged.
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