SURFACE AND INTERFACE ANALYSIS

Surf. Interface Anal. 2001; 31: 1031–1041

Catalytic cooperation at the interface of physical

mixtures of CaO and MgO catalysts during steam
gasification of naphthalene
Nelson Alarcón,1† Ximena Garcı́a,1 Miguel Centeno,2 Patricio Ruiz3 and Alfredo Gordon1∗
1
Chemical Engineering Department, University of Concepción, Chile
2
Departamento Quı́mica Inorgánica e Instituto de Ciencia de Materiales, Universidad de Sevilla-CSIC, Sevilla, España
3
Unité de Catalyse et Chimie des Matériaux Divisés, Université Catholique de Louvain, Belgium

Received 28 September 2000; Revised 13 July 2001; Accepted 17 July 2001

Oxides CaO, MgO and a physical mixture of 10% CaO + 90% MgO were used as catalysts for the steam
gasification of naphthalene. A synergistic effect in the conversion was observed with the mixture. Catalysts
were characterized by diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and XPS
techniques. Basicity was significant for CaO as compared to MgO and the mixture, but did not correlate
with catalytic activity. Bidentate carbonate-type formation, which remained even in the presence of steam
at high temperature (1033 K), was observed on CaO. Carbonates on MgO and on the mixture are unidentate
and disappeared when steam was present. Formates, carboxylic and aldehydic groups also were formed, at
723 K on MgO and at 423 K on the mixture and on CaO. These species disappeared at 873 and 1033 K for the
mixture and CaO, respectively, thus indicating their greater stability on CaO than on the mixture and on
the MgO. Deposition of carbonaceous matter on solids was observed. The order of the deposited content
is mixture < MgO < CaO. No indication of mutual contamination by the metal composing the oxides was
observed. A higher carbonate removal and less carbonaceous matter deposition were observed in CaO
when in the mixture, as compared with CaO alone, suggesting a beneficial effect of MgO in the mixture.
The synergistic effect observed using the 10% CaO + 90% MgO mixture was related to the inhibition
of carbonaceous matter and carbonate formation on the catalysts. This inhibition is due to a catalytic
cooperation between both oxides, as two separate phases. The presence of MgO is assumed to avoid the
formation of stable bidentate carbonates on CaO, promoting instead unidentate species formation; this
facilitates the gasification of naphthalene by steam. Copyright  2001 John Wiley & Sons, Ltd.

KEYWORDS: magnesium–calcium catalyst; naphthalene gasification; XPS; DRIFTS

INTRODUCTION Although both oxides exhibited good activity and selectivity

Alkaline-earth metal oxides CaO, MgO and physical mix-
tures of the two have been used widely as catalysts for steam
gasification of different materials such as coal, biomass and
tars.1 – 5 The latter are generated in some coal and biomass
gasification processes and could be gasified with steam
to enhance the yield of fuel gases, to avoid clogging the
lines and to reduce pollution. Owing to the high complex-
ity and heterogeneity of tars, gasification studies by using
representative model compounds, such as naphthalene and
benzene, have been performed6 – 9 and the catalytic activity
of calcium and magnesium oxides has been demonstrated.
Ł Correspondence to: A. Gordon, Chemical Engineering
Department, University of Concepción, Chile.
E-mail: agordon@diq.udec.cl
† Present address: Escuela de Ciencias Ambientales, Universidad
Católica de Temuco, Chile.
Contract/grant sponsor: FONDECYT, Chile; Contract/grant
number: 1980474.
Contract/grant sponsor: National Foundation for Scientific
Research (FNRS, Belgium).
to generate gaseous products (carbon conversions over 50%),
differences have been observed with regard to catalytic
inhibition by carbonate formation and carbonaceous matter
deposition, which occurred to a larger extent when CaO was
used as a gasification catalyst.6,8,10
Previously, we have shown that a synergistic effect in
the steam gasification of naphthalene, used as a model
compound, was observed when a simple physical mixture
of 10% CaO C 90% MgO has been used as catalyst.11 In fact,
a 79% conversion was reached with the mixture vs. 54% and
62% for MgO and CaO, respectively, which represents a 44%
synergistic enhancement. This effect has not been reported
previously in the literature.
The BET surface area of fresh calcined samples (before
exposure to steam gasification) corresponds to the aver-
age weighted value of the components (¾50 m2 g1 ). After
reaction, the BET surface area of each of the solids work-
ing separately and of the mixture diminishes but, again,
the measured value in the mixture is close to the expected

DOI: 10.1002/sia.1137 Copyright  2001 John Wiley & Sons, Ltd.

1032 N. Alarcón et al.
average of the values for each component. This suggests
that the principal phenomenon occurring during naph-
thalene gasification with the mixture is sintering of the
oxides, because it occurs when the oxides work separately.
Differential thermogravimetry/differential thermal analysis
(DTG/DTA) measurements have shown the presence of
carbonate in the solids; the higher Ca content of the lat-
ter requires a higher temperature for carbonate elimination.
Briefly stated, these results show a greater tendency to deac-
tivation of calcium-containing catalysts. X-ray diffraction
(XRD) analysis of the fresh and used oxides shows that: crys-
talline phases present in the fresh solids (calcite and metal
hydroxides (from Ca and Mg)) were not modified during
the reaction; and no new mixed oxide phase that would
associate Mg and Ca was detected. These results show that
oxides in the physical mixture remain unaltered and no
new compound formed among them was found to explain
the observed catalytic synergistic effect. This experimental
information suggests that the synergism could be explained
based on a catalytic cooperation among the Ca and Mg
oxides, taking place during the gasification reaction.
Thus, BET surface, DTG/DTA, non-conclusive transmis-
sion/absorption FTIR measurements of absorbed deuterated
chloroform and XRD analysis provide mainly bulk informa-
tion that is insufficient to give a decisive explanation to the
observed effect shown by the 10% CaO C 90% MgO mixture.
Because the catalytic properties of the oxides and the reaction
mechanism involved are related to surface phenomena that
take place during gasification, the superficial characteriza-
tion of CaO, MgO and the mixture of 10% CaO C 90% MgO
has to be performed to get a clearer interpretation of the
synergism.
The purpose of this work is the application of more appro-
priate and sensitive surface characterization techniques to
evaluate surface phenomena and particularly to study: any
alteration on the surface during the reaction; possible chem-
ical contamination of oxides by element transfer from one
oxide to the surface of the other; modification in basicity
of the pure oxides and the mixture; the nature of inter-
mediate species formed and the differences between them
when oxides work separately and in mixtures; and the car-
bonate formation or carbon deposition and the extent to
which it occurs in the different solids. In order to reach these
objectives, the following techniques were considered.
Diffuse reflectance infrared Fourier transform spec-
troscopy (DRIFTS) was used to determine basicity so as to
correlate it with the catalytic activity in gasification. Deuter-
ated chloroform, instead of CO2 , was selected as the adsorbed
probe molecule in order to minimize alterations of basic-
ity determinations by interactions and/or the formation of
bulk polydentate species, as has been reported.12 With CO2
adsorption, the formation of unidentate carbonate over a
basic site is possible only at high pressures, whereas at low
pressures (this work) the formation of a bidentate carbon-
ate occurs over basic and acid sites of the solid.10 Thus,
deuterated chloroform adsorption, a reliable technique, was
preferred due to the generation of IR peaks at characteris-
tic wavelengths, which depend on the basic strength of the
adsorption sites. This technique also was used to characterize
Copyright  2001 John Wiley & Sons, Ltd.
catalyst samples that were pretreated with steam or CO2 . The
latter experiments were performed to determine the affin-
ity and type of carbonate formation on the catalysts and
the stability of those carbonates when samples are sub-
jected to similar atmosphere and thermal conditions to those
encountered during the reaction.
X-ray photoelectron spectroscopy was selected for the
identification of surface atoms with regard to carbonaceous
matter deposition and carbonate and/or intermediate for-
mation or inhibition. Apart from surface composition, XPS
allows the identification of compounds that are considered
relevant to the synergistic effect or deactivation described for
the catalysts and it was used to investigate fresh and used
catalysts.
EXPERIMENTAL
Catalyst characterization
Catalysts
Both MgO (light, BDH Chemicals Ltd, 95% pure) and CaO
(Riedel de Häen, 96% pure) were used as catalyst precursors.
Oxides CaO, MgO and a 10% CaO C 90% MgO mixture were
prepared as a mud with distilled water, dried at room
conditions for 100 h and afterwards at 378 K in an oven.
Activation of the solids was carried out in situ, i.e. within
the reactor, by heating up to reaction temperature in argon
(99.999% pure) ambient and soaking at those conditions for
30 min. These catalysts were utilized for steam gasification
of naphthalene, as reported elsewhere.8
Diffuse reflectance infrared Fourier transform
spectroscopy
In situ DRIFTS spectra were collected using a Brucker
IFS88 infrared spectrometer equipped with KBr optics
and a DTGS detector. The samples were placed without
any treatment, such as pressure or dilution, inside an
environment-controlled chamber (Spectra-Tech 0030-103)
attached to a diffuse reflectance accessory (Spectra-Tech
collector). The frequency domain was 4000–400 cm1 and
the spectral resolution was 4 cm1 . The signal-to-noise ratio
was maximized for the accumulation of 200 scans and the
reference spectrum was obtained from an aluminium mirror,
thus allowing automatic spectra correction by subtraction.
Basicity determination. As reported,12,13 deuterated chloro-
form (a weak acid) may form hydrogen bonds with the basic
sites of a solid. The IR spectrum of deuterated chloroform
adsorbed on the surface of the solid shows two character-
istic bands (stretching vibration band, CD ) corresponding
to two different adsorption modes, namely at ¾2250 cm1
and 2210–2225 cm1 wavenumbers. Band location allows
estimation of the basic site strength, because the first band
represents weak basic sites and the second range represents
strong basic sites. Likewise, displacement of a band to lower
wavenumbers indicates an increase of the basic strength of a
site.13
Samples (particle size <0.2 mm) were placed in the
atmosphere- and temperature-controlled chamber and
treated for 2 h with N2 at 1033 K, prior to deuterated chlo-
roform adsorption. The outgassed sample was subjected to
Surf. Interface Anal. 2001; 31: 1031–1041

chloroform adsorption for 30 min. Deuterated chloroform
was transported to the sample by a CDCl3 -saturated N2 flow
(30 ml min1 ), which bubbled previously into a saturator
at room temperature. The DRIFTS spectra were registered
before cleaning and before and after adsorption. Finally,
the sample was heated under N2 until disappearance of
the deuterated chloroform band. The areas of the adsorbed
chloroform bands were calculated with the aid of software
(Brucker OPUS IR/2.2).
Reactive atmosphere simulation. To simulate steam gasification,
fresh catalysts were analysed after treatment under a CO2
and steam atmosphere at 1033 K (the reaction temperature).
Adsorption of CO2 on alkaline-earth oxides occurs in differ-
ent ways, depending on the experimental conditions. These
were detected by characteristic IR bands12,14 – 18 correspond-
ing to the formation of unidentate-type carbonates (bands
at 1430 and 1530 cm1 ), bidentate carbonates (at 1300 and
1620 cm1 ), bridged-type carbonates (1780 cm1 ) and bicar-
bonates (1220, 1420 and 1650 cm1 ). The latter only appear
if surface hydroxyl groups, acting as bases, are present. In
particular, the adsorption of CO2 on MgO occurs as bidentate
form for low surface coverage and as unidentate form for
higher coverage. The CO2 adsorption on CaO always occurs
as bidentate carbonate, independent of surface coverage.10
Furthermore, the presence of unidentate or bidentate car-
bonates can be differentiated by the lower thermal stability
of the former.12
As described above, researchers12,14 – 18 differ in the
assignment of characteristic bands and the differences are
attributed to the diversity of precursors and pretreatment of
the solids. In spite of that, it is possible to differentiate
the carbonate species by splitting of the carbonate ion
asymmetric stretching band (¾1415 cm1 ), i.e. band splitting
would be 100, 300, 400 cm1 or more for unidentate, bidentate
and ‘bridged’ carbonate types, respectively.
Other bands could be present, corresponding to: different
formate species,12,17 – 19 as reaction products from CO read-
sorbed (2130 cm1 ) and OH groups; carboxylic groups with
hydrogen bridges (C O at 1790 and O–H at 2500 cm1 )20 ;
or aldehydic groups (C O at 1790 and C–H at 2900 cm1 )20 .
All these species would be formed by interaction between
CO2 , CO and OH or water adsorbed on the solids.
Water adsorption on alkaline-earth metals was detected
by IR bands of OH groups and water itself. Type I OH groups
are formed by oxygen bonded to the metal (M–OH, band at
3740 cm1 )12 and type II OH groups by oxygen bonded to two
metallic atoms (M–OH–M, 3670 cm1 ).12 Adsorbed water
presents a wide band15,21 – 23 at 3600–2800 cm1 wavenumber
and a shoulder21 – 23 at 1635 cm1 .
Type I OH groups are basic and show nucleophilic
character, which explains their reactivity to CO, leading
to species such as formates (HCOO ).12 According to the
literature,12,17 – 19 the formation of different formates should
be detected by the following characteristic bands: uniden-
tate formate ((CH) at 2811 cm1 , as (OCO) at 1649 cm1
and s (OCO) at 1304 cm1 ); bidentate formate ((CH) at
2750 cm1 , as (OCO) at 1610 cm1 and s (OCO) at 1388 cm1 );
and bridged-type formate ((CH) at 2839 cm1 , as (OCO) at
1622 cm1 and s (OCO) at 1342 cm1 ).
Copyright  2001 John Wiley & Sons, Ltd.
Catalytic cooperation at the interface of CaO/MgO catalysts 1033
The samples (particle size <0.2 mm) were placed in
the analysis chamber and a spectrum was recorded under
flowing N2 (30 ml min1 ) for 20 min. After cleaning the
samples by heating up to 1033 K and keeping them at
this temperature for 60 min, a spectrum was taken. Then,
CO2 desorption was monitored as follows: samples were
cooled to room temperature and subjected to a CO2 flow
(30 ml min1 ) for 15 min after which each sample was heated
sequentially (under CO2 flow) up to 423, 573, 723, 873 and
1033 K. Samples were kept for 30 min at each temperature
level and a spectrum was taken. At 1033 K, the exposure to
CO2 flow was followed by 5 or 15 min treatment under wet
nitrogen (obtained by bubbling N2 in liquid water at room
temperature) and the corresponding DRIFTS spectrum was
recorded.
X-ray photoelectron spectroscopy
Surface composition, deposited carbon and variations of
binding energies of the C 1s, O 1s, Mg 2s and Ca 2s peaks of
selected fresh and used samples (before and after reaction,
respectively) were obtained by XPS analysis. These samples
were not subjected to any treatment prior to analysis. Solids
were pressed into stainless-steel sample holders of 4 mm
diameter size, which then were placed in a ceramic carousel.
A Ni grid covered the latter, located 3 mm from the top of
the samples. Both the ceramic carousel and the grid were
utilized to avoid charge effects, because the samples are
semiconductors. They are also protected from charge effects
by a charge neutralizer (an 8 eV flood gun). The solids
were outgassed overnight at 7 ð 105 Pa vacuum and room
temperature. The XPS data were obtained with a Surface
Science Instruments SSX-100 model 206 spectrometer with
a monochromatized Al K˛ source AlK˛1,2 D 1486.6 eV).
The residual pressure inside the analysis chamber was
<6.65 ð 107 Pa. The angle between the surface normal and
the axis of the analyser lens was 55° . The spot size was
1000 µm (10 kV and 20 mA) and the pass energy was set at
50 eV. In these conditions, the resolution determined by the
full width at half-maximum (FWHM) of the Au 4f7/2 peak of a
standard gold sample was 1.1 eV. The atomic concentrations
were calculated using peak areas that were normalized based
on acquisition parameters and sensitivity factors provided
by the manufacturer (mean free path varying according
to the 0.7th power of the photoelectron kinetic energy;
Scofield cross-sections; transmission function assumed to be
constant). Because the mean free path of the photoelectrons
is ¾0.4–4 nm24 under the experimental conditions used, the
results obtained correspond to the uppermost atomic layers
of the surface (depth of ¾1–8 nm).25
For analysis, the C 1s peak (of deposited carbon) was
used as reference by adjusting its binding energy C–(C–H)
to 284.8 eV; peak decomposition was performed with a
Gaussian/Lorenzian ratio of 85/15. Curve fitting of the
C 1s peak was utilized to determine, after the reaction,
carbonaceous matter deposition and carbonate formation
on the catalyst samples. For this purpose, the atomic
percentage of carbon was split into two contributions: one
from carbonate by C 1s at ¾290 eV; and one contribution of
carbonaceous matter, determined as the summation of C 1s
peaks at 284.8 and 286.3 eV.
Surf. Interface Anal. 2001; 31: 1031–1041
1034 N. Alarcón et al.

RESULTS AND DISCUSSION

3701
1510
1419

3645
Analysis by DRIFTS 1631
Basicity determination 1120
For in situ DRIFTS analyses, sample cleaning was possible 3 1795
at the reaction temperature (1033 K) prior to deuterated

Absorbance Units
3714
chloroform adsorption. This allowed good removal of 1
1071
surface carbonates. Two adsorption peaks for deuterated 2
2 3560
chloroform, corresponding to weak and strong basicity, were
detected (not shown). Integration of characteristic basicity 3720
2500
peaks at 2162 and 2250 cm1 allows the determination of
the amount of strong and weak basic sites, respectively. 1 3
4
The strong basicity values were 42.53, 11.7 and 11.42 3490 5
absorbance units (a.u.) for CaO, MgO and the physical 6
mixture, respectively, which are significantly higher values 0 7
than the weak basicities of 0.60, 0.42 and 0 for the same 1000 1500 2000 2500 3000 3500 4000

catalysts. These results agree with the expected basicity Wavenumber cm−1
trend for these catalysts, namely that CaO is more basic than,
2.5
MgO,10 but they do not correlate with their tested catalytic
activity.11 Both MgO and the mixture show similar basicity
but different catalytic activities; thus, basicity plays a role 2.0 1450 3500 3715
Absorbance Units
but it is not unique with regard to the activity of the assayed 8
catalysts. 1.5

Reactive atmosphere simulation

The DRIFTS spectra of all fresh solids (curve 1 in Figs 1, 2
and 3) show almost the same species, namely: unidentate car-
bonates (1420 and 1510 cm1 ), hydroxyls (several bands over
3645 cm1 ) and adsorbed water (wide band at ¾3500 cm1
and a shoulder at 1635 cm1 ). After degasification for 1 h
at 1033 K the IR spectra (curve 2 in Figs 1, 2 and 3) show
negligible presence of carbonate and OH groups. Carbonate
bands are more evident in CaO than in MgO, whereas the
opposite is true for OH bands.
After cooling to room temperature and exposure to and
adsorption of CO2 , solids are carbonated and hydrated
(curve 3 in Figs 1, 2 and 3). The lesser presence of the
OH groups is attributed to masking by the wide band
of hydration. In fact, subsequent heating of the samples
eliminates absorbed water (loss of the shoulder at 1635 cm1
and narrowing of the band at 3500 cm1 ) and allows the
appearance of an OH band at 3700 cm1 (curves 4 and 5
in Figs 1, 2 and 3). Similarly, the intensity of the carbonate
bands diminishes with heating, showing CO2 departure.
At 723 K (curve 6 in Figs 1, 2 and 3), all solids show the
appearance of new bands, more intensive for the mixture and
CaO at 1790, 2130, 2500, 2580, 2840 and 2950 cm1 . The solids
also show weakening of the bands at 1410 and 1500 cm1
(unidentate carbonate) and 3500 and 3640 cm1 (water and
OH groups). Both changes are more evident for CaO and the
mixture (Figs 2 and 3, curves 6 and 7), samples for which
the presence of these species is displayed already at 423 K
(curve 4 in Figs 2 and 3, respectively). The new bands at
1390 and 1550 cm1 (Fig. 2, curve 7) suggest that, during
gasification, unidentate carbonate on CaO is transformed
into the bidentate species. Other new bands correspond
to: formate species (1380, 1550 and 2840 cm1 ), carboxylic
groups with hydrogen bridge20 (C O at 1790 cm1 and O–H
at 2500 cm1 ); or aldehydic groups20 (C O at 1790 cm1
and C–H at 2900 cm1 ). All these species would be formed
1.0 1780 2500
2860
0.5
9
10
11
0.0
1000 1500 2000 2500 3000 3500 4000
Wavenumber cm−1
Figure 1. The DRIFTS spectra of pure MgO after
degasification plus in situ CO2 and H2 O treatment: (1) sample
as received, N2 at room temperature (RT); (2) after cleaning
with N2 at 1033 K for 1 h; (3) after CO2 elimination and N2 at
RT for 10 min; (4) after heating to 423 K in N2 for 30 min;
(5) after heating to 573 K in N2 for 30 min; (6) after heating to
723 K in N2 for 30 min; (7) after heating to 873 K in N2 for
30 min; (8) after heating to 1033 K in N2 for 30 min; (9) after
adsorption of CO2 at 1033 K for 10 min; (10) after being
subjected to N2 C H2 O at 1033 K for 5 min; (11) after being
subjected to N2 C H2 O at 1033 K for 15 min.
by liberation of CO2 and CO, subsequent readsorption of
the latter (2130 cm1 ) and reaction with adsorbed OH or
water.12,17 – 19 For the MgO, these transformations are noticed
only at 723 K (curve 6, Figs 1 and 3) and not at the higher
temperatures of 873 and 1033 K (curves 7 and 8, respectively,
in Fig. 1), where only OH groups remain. For the mixture,
these bands are found up to 723 K (curve 6, Fig. 3) and
disappear at 873 and 1033 K (curves 7 and 8, Fig. 3). For CaO
these new bands are observed up to 873 K and they are not
found at 1033 K (curve 10, Fig. 2), thus displaying the greater
stability of formates, carboxylic and aldehydic species on
CaO than in MgO or the mixture.
It may be observed also that carbonates almost disappear
at 873 K in MgO but they remain in the CaO and the
mixture up to 1033 K (curve 8, Figs 2 and 3), whereas

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 1031–1041
 Catalytic cooperation at the interface of CaO/MgO catalysts 1035

1480 3646 1510 3700

2500
1420

2860
1635
1790
3700

2580
2126 5
5
1110 2840 2950 3650
1640 1790 3300 3530 3730 3740
1234 2500 2580
3790

Absorbance Units
4 1420 1550 4 1
3670 1
Absorbance Units

1075 2 2
3650 1070 3490 3550
3 2950
3 1140 3730
3

4 2 3
2 1470
4
5
1 5
1 1390 6
3170 3680
3550 6
1150 7
7 0
0 1000 1500 2000 2500 3000 3500 4000
1000 1500 2000 2500 3000 3500 4000
Wavenumber cm −1
Wavenumber cm −1
4 1145
4 1410 1505 1440
1490 3700
1120 1550
8 1410 8
1435 3
3 1360

Absorbance Units
1783
Absorbance Units

1142 2500
2580 1790 2500
1582 2124 2850 2580
2950 2
2 1313 2860
3540 2120 2950 3520
3170

9
9 1
1 10
10
11
11 0
0 1000 1500 2000 2500 3000 3500 4000
1000 1500 2000 2500 3000 3500 4000
Wavenumber cm −1
Wavenumber cm −1
Figure 3. The DRIFTS spectra of a 10% CaO C 90% MgO
Figure 2. The DRIFTS spectra of pure CaO after
mixture after degasification plus in situ CO2 and H2 O
degasification plus in situ CO2 and H2 O treatment; (1) sample
treatment. (1) sample as received, N2 at room temperature
as received, N2 at room temperature (RT); (2) after cleaning
(RT); (2) after cleaning with N2 at 1033 K for 1 h; (3) after CO2
with N2 at 1033 K for 1 h; (3) after CO2 elimination and N2 at
elimination and N2 at RT for 10 min; (4) after heating to 423 K
RT for 10 min; (4) after heating to 423 K in N2 for 30 min;
in N2 for 30 min; (5) after heating to 573 K in N2 for 30 min;
(5) after heating to 573 K in N2 for 30 min; (6) after heating to
(6) after heating to 723 K in N2 for 30 min; (7) after heating to
723 K in N2 for 30 min; (7) after heating to 873 K in N2 for
873 K in N2 for 30 min; (8) after heating to 1033 K in N2 for
30 min; (8) after heating to 1033 K in N2 for 30 min; (9) after
30 min; (9) after adsorption of CO2 at 1033 K for 10 min;
adsorption of CO2 at 1033 K for 10 min; (10) after being
(10) after being subjected to N2 C H2 O at 1033 K for 5 min;
subjected to N2 C H2 O at 1033 K for 5 min; (11) after being
(11) after being subjected to N2 C H2 O at 1033 K for 15 min.
subjected to N2 C H2 O at 1033 K for 15 min.

at this latter temperature MgO and the mixture retain
a band representative of hydroxyl groups. Carbonates
in MgO and the mixture are of the unidentate type
whereas in CaO the carbonates could be of the bidentate
type (1300 and 1600 cm1 ) but masked by the symmetric
and asymmetric O–C–O vibration bands of the bidentate
formate species (1380 and 1610 cm1 ). This is supported
further by considering that splitting of the carbonate ion
asymmetric stretching band (at 1415 cm1 )15 is 100 cm1
for the unidentate carbonate species and 300 cm1 for the
bidentate carbonate.12,14 – 18
Steam and CO2 pretreatment at gasification conditions
were possible during DRIFTS analysis of the samples, giving
the spectra shown by curves 9–11 in Figs 1, 2 and 3. All
samples exposed to CO2 generated bands representative of
carbonate, formate, carboxylic acid and aldehydic species,
whose intensity varied in the order CaO > mixture > MgO.
As stated, carbonates in the MgO and the mixture are of
the unidentate type, whereas those in the CaO would be of
the bidentate type, thus explaining its greater stability on
it.12 When exposed to steam, all species formed from CO2
adsorption in MgO disappeared immediately; the unidentate
species remained in the mixture but disappeared slowly with
time of exposure to steam. All species formed in CaO were
much more stable, remaining absorbed for up to 30 min of
exposure (not shown in the figures).
Differences also were found in the stability of formates,
carboxylic acid and aldehydic species, which may be
explained by differences in the stability of carbonate species
formed in the solids by adsorption of CO2 . The higher
stability of carbonates generates a slower release of CO2 and
CO from CaO; this in turn promotes the presence of formates,

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 1031–1041
1036 N. Alarcón et al.

carboxylic groups or aldehydes in CaO. These compounds
remain as long as there is CO2 to be freed from the solid.
For the other catalysts, the species formed (formates, etc.) are
short-lived because removal of unidentate carbonate is faster
under the reaction conditions. Therefore, it is concluded
that the presence of the relatively stable bidentate carbonate
species generates the lower activity of CaO compared with
the mixture. This carbonate restrains the formation of the
formate species, which is known to be an intermediate in the
shift reaction mechanism.19
Furthermore, naphthalene gasification not only occurs
by way of the shift reaction but also through naphthalene
pyrolysis and later gasification of the carbonaceous matter
deposited on the catalysts, carbonaceous matter being
recognized as compounds with C–(C, H) and/or C–O–C
species. Therefore, the influence of the different carbonate
species formed and their relative stability should be analysed
in this regard.
Analysis by XPS
Table 1 shows the surface composition of fresh and used
samples resulting from XPS analysis, as expressed by binding
energies (BE) and atomic percentage (at.%) of the elements
in the catalyst surface layers.
Binding energies were associated with the different
elements according to the following:26
(1) For C 1s, the BE of ¾284.8 eV corresponds to graphitic
and/or aliphatic carbon (C–C, C–H), the BE of
¾286.3 eV is related to carbon in ethers and/or alcohols
(C–OR, C–OH, C–O) and the BE of ¾290 eV corre-
sponds to both carbonate species (CO3 2 ) as well as
–C( O)–O–(carboxylic acid, ester) groups.27 (In what
follows concerning the XPS results, the C 1s peaks at
284.8 and 284.6 eV will be considered as representatives
of carbonaceous matter deposited on the solids.)
(2) Generally, the O 1s spectrum for most solids represents
three oxygen species:28 – 32 O2 , OH and water absorbed
with binding energies of 530, 531.6 and 532.7 to 533.2 eV,
respectively. The value of 531.6 eV is attributed29 – 31 both
to OH and CO3 2 groups. The binding energy values
between 532.7 and 533.2 eV usually are attributed to
adsorbed or hydration water30 but they may represent
O 1s from C–OH and/or C–O–C groups. Thus, as
observed, the O 1s peaks of OH and hydration water
are displaced from the O2 by 1.1–1.5 eV and >3 eV,
respectively.
As seen from Table 1, the curve fitting of the O 1s
spectrum for fresh catalysts (pure oxides and the mixture)
shows only one peak at ¾531.5 eV. Owing to the preparation
of these catalysts, this peak relates to the presence of either
hydroxides or carbonates, the latter probably originating
during storage. Other results of Table 1 show the following:
(1) The Mg 2s binding energies from MgO changed slightly
during catalytic gasification (88.8 vs. 89.1 eV, BE D
0.3 eV, before and after the reaction). This change
probably is due to deposition of carbonaceous matter
on the solid. Alternatively, some of the Mg may be found
as carbonate, as shown by the 4.4 at.% for the C 1s
peak (¾290 eV), which is attributed to carbonate species
in the used MgO catalyst. The O 1s peak [Fig. 4(a)]
shows the appearance of a new oxygen species at lower
binding energies (530.3 eV), suggesting the presence of
magnesium as Mg–O, a product from the removal of
carbonates and hydroxyl groups. (Fresh MgO catalyst
is prepared as a mud and, as such, contains hydroxyl
groups and carbonates, the latter from storage.) This is
confirmed further by the reduction of both O 1s from
51 to 31.6 at.% and carbonate (C 1s at 289.8 eV) from
8.0 to 4.4 at.%. The other peak at 532.4 eV may be due
to the deposition of carbonaceous matter (C–OH and
C–O–C groups, among others) and/or to hydration of
the sample in the reactive atmosphere. Carbonaceous
matter deposition on the solid may explain a change of
binding energy in the O 1s curve-fitted peak. In fact,
carbonaceous matter is the only species that could be

Table 1. Analysis by XPS atomic percentage and binding energies (in eV) for fresh and used MgO, CaO and 10% CaO C 90% MgO
physical mixture samples

MgO 10% CaO C 90% MgO CaO

Fresh Used Fresh Used Fresh Used
Element BE at.% BE at.% BE at.% BE at.% BE at.% BE at.%

C 1s 284.8 10.2 284.8 19.4 284.8 9.1 284.8 18.6 284.8 17.7 284.8 26.3
C 1s 286.3 3.2 286.3 10.7 286.3 2.6 286.3 7.7 286.3 2.5 286.3 17.1
C 1s 289.8 8.0 289.8 4.4 289.5 4.2 290.2 3.3 289.4 16.9 290.5 15.3
O 1s 531.6 51.0 530.3 11.5 531.2 51.0 530.1 5.6 531.2 49.9
O 1s 532.4 20.1 532.0 30.9 532.4 32.7
Mg 2s 88.8 27.6 89.1 33.8 88.4 32.7 89.0 32.8
Ca 2s 438.9 0.5 439.5 1.2 438.5 13.0 439.7 8.6
Ca/Mg 0.02 0.04
Ca/C 0.03 0.04 0.35 0.15
Mg/C 1.3 1.0 2.0 1.10
C/CO3 2a 2.7 7.8 3.8 9.00 2.2 3.84
a
C D total carbon; CO3 2 D C 1s at 290 eV.

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 1031–1041
 Catalytic cooperation at the interface of CaO/MgO catalysts 1037

Fresh (a) Used

10000 5000

8000 4000

Electron Counts
Electron Counts

6000 3000

4000 2000

2000 1000

0 0

538 536 534 532 530 528 526 538 536 534 532 530 528 526
Binding Energy (eV) Binding Energy (eV)
(b)
10000 6000

8000 5000

Electron Counts
Electron Counts

4000
6000
3000
4000
2000
2000
1000

0 0
538 536 534 532 530 528 526 538 536 534 532 530 528 526
Binding Energy (eV) Binding Energy (eV)
(c)
4000
10000

8000 3000
Electron Counts
Electron Counts

6000
2000

4000
1000
2000

0 0

538 536 534 532 530 528 526 538 536 534 532 530 528 526
Binding Energy (eV) Binding Energy (eV)
Figure 4. The XPS spectra of O 1s for fresh and used samples: (a) MgO; (b) CaO; (c) 10% CaO C 90% MgO.

formed after reaction that is different from the existing
species in the fresh catalyst.
(2) A significant variation of Ca 2s (from 438.5 to 439.7 eV,
BE D 1.24 eV) in CaO was found, a change attributed
to the deposition of carbonaceous matter on the solid
and to the presence of hydration water. This is clear
also from Fig. 4(b), where just one O 1s peak is evident
at 532.4 eV. Contrary to MgO, this solid does not show
the presence of O2 at the surface. As in the previous
discussion, changes in binding energy evidence mainly
the deposition of carbonaceous matter, but also a certain
amount of carbonate must be considered for that change
(15.3 at.% for C 1s at 290.5 eV).
(3) Small BE changes occurred for Ca 2s and Mg 2s (0.67 eV
and 0.60 eV, respectively) in the 10% CaO C 90% MgO
mixture with respect to the fresh sample. In spite of
this, the binding energies of Mg 2s and Ca 2s in the
mixture used are identical with the values shown by
these metals in the pure used solids, i.e. 89.0 eV for Mg 2s
and 439.5 eV for Ca 2s. This suggests that both metals are
found in the mixture under the same conditions as for the
pure used oxides, namely, carbonaceous matter (89.0 eV)
covers part of the Mg, which also shows partial degrees
of carbonation and hydration (O 1s peak at 532.0 eV);
another percentage of the Mg is found as oxide (O 1s
peak at 530.1 eV) [Fig. 4(c)]. This is not the case for Ca

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 1031–1041
1038 N. Alarcón et al.

in the mixture, which is found as carbonate, hydrated,
covered with deposited carbonaceous matter (O 1s peak
at 532.0 eV) but not as oxide.
Another significant feature from the XPS results is that
the atomic concentration of Mg 2s in the mixture remains
constant during reaction (32.7 vs. 32.8 at.%). This suggests
that Ca does not contaminate Mg in the mixture, namely, no
(or very little) atoms transfer among the oxides that would
explain a synergistic effect by surface contamination.
It should be pointed out that only the two Mg-containing
samples (pure MgO and the mixture) show a percentage of
oxygen bonded in the M–O form (O 1s at 530 eV). The O 1s
peak from the pure CaO does not show such an oxygen bond
(see Fig. 4).
Curve fitting of the C 1s peak (total carbon, Table 1
and Fig. 5) shows that the total atomic percentage of
graphitic/aliphatic carbon (C–C and C–H at 284.8 eV) and
ether/alcohol bonds (carbonaceous matter C–OR, C–OH
and C–O at 286.3 eV) varied for the catalyst assayed. The
contribution of the carbon pertaining to carbonates and
carboxylic groups (at ¾290 eV) also changed with the
catalysts. For both cases, the values increased in the order:
10% CaO C 90% MgO mixture < MgO < CaO. This took
place for both fresh and used samples; hence, the total
carbon content follows the same trend.
Table 1 shows that, after gasification, a significant
reduction of the peak attributed to carbonates (C 1s at
¾290 eV, from 8.0 to 4.4 at.%) occurred only for MgO.

Fresh Used
(a)
6000
12000
5000
10000
Electron Counts
Electron Counts

4000 8000

3000 6000

2000 4000

1000 2000

0 0

295.0 292.5 290.0 287.5 285.0 282.5 280.0 295.0 292.5 290.0 287.5 285.0 282.5 280.0
Binding Energy (eV) Binding Energy (eV)

5000 (b)
5000

4000 4000
Electron Counts
Electron Counts

3000 3000

2000 2000

1000 1000

0
0
295.0 292.5 290.0 287.5 285.0 282.5 280.0 295.0 292.5 290.0 287.5 285.0 282.5 280.0
Binding Energy (eV) Binding Energy (eV)

6000 (c) 6000

5000 5000
Electron Counts

Electron Counts

4000 4000

3000 3000

2000 2000

1000 1000

0 0

295.0 292.5 290.0 287.5 285.0 282.5 280.0 295.0 292.5 290.0 287.5 285.0 282.5 280.0
Binding Energy (eV) Binding Energy (eV)
Figure 5. The XPS spectra of C 1s for fresh and used samples: (a) MgO; (b) CaO; (c) 10% CaO C 904% MgO.

Copyright  2001 John Wiley & Sons, Ltd. Surf. Interface Anal. 2001; 31: 1031–1041

However, when calcium-containing substances (CaO or
10% CaO C 90% MgO) were utilized as gasification catalysts,
carbonate diminishes significantly less than for MgO (C 1s at
¾290 eV, from 16.9 to 15.3 at.% for CaO and from 4.2 to 3.3
at.% for the mixture). Furthermore, the mixture shows the
smallest content of carbonates of the three solids assayed.
As shown in Table 1 for all solids, the species represented
by peaks at 284.8 and 286.3 eV (which would correspond
only to deposited carbonaceous matter) increased in the
used samples compared with the respective fresh samples.
The order of the deposited content is as follows: 10% MgO C
90% CaO < MgO < CaO.
For MgO, the Mg 2s atomic concentration increase after
reaction is explained only by a decrease in carbonate content
as the total carbon increases. In addition, from Table 1 it is
observed that the atomic concentration of oxygen diminishes.
These results show that carbonates formed on the MgO
surface are of the unidentate type, because of their instability
at the reaction temperature, which is in agreement with other
results in the literature10,12,13 and with our DRIFTS results
shown above.
During reaction, the oxygen content (at.%) of the three
solids diminished less for the mixture than for the pure
oxides (variations in O 1s of 19.4, 17.2 and 14.5 at % for MgO,
CaO and 10% CaO C 90% MgO, respectively). This decrease
may occur in two ways:
(1) In MgO, by elimination of hydroxyls and carbonate
groups or adsorbed water; in CaO and the mixture,
mainly by elimination of hydroxyl groups and adsorbed
water and less by carbonate elimination because the latter
varies little during reaction.
(2) From deposition of carbonaceous matter on the solid
surface, thus screening oxygen atoms.
Because the solids were subjected to a reactive atmo-
sphere containing steam and CO2 , the elimination of
hydroxyl and carbonate groups or adsorbed water from
the surface is less probable (as shown by the DRIFTS spectra
of solids treated with steam and CO2 at the reaction temper-
ature). Thus, the decrease of the oxygen content should be
attributed mainly to carbonaceous matter deposition.
Carbonate release and carbonaceous matter deposition
also explain the appearance of two O 1s peaks during analysis
of used MgO and 10% CaO C 90% MgO, as shown in Table 1
and Figs 4(a) and 4(b). The O 1s detected at the highest
BE (532.4 eV) could be attributed to oxygen bonds with
carbonaceous material, whereas the O 1s peak at 530.3 eV
would represent the metal (Ca or Mg)–O bond. For CaO,
the atomic concentrations of Ca 2s and O 1s decreased
during gasification, showing that carbon deposition takes
place on both types of atoms. Alternatively, oxygen may
diminish by elimination of hydroxyl groups. Most probably,
the phenomena described above originate the displacement
of the corresponding BE towards higher values (438.5 to
439.7 eV, BE D 1.2 eV for Ca 2s; and 531.2 to 532.4 eV,
BE D 1.2 eV for O 1s). As shown, lower displacements
were observed for the Ca 2s and Mg 2s peaks in the
mixture (438.9 to 439.5 eV, BE D 0.6 eV for Cn 2s; and
88.4 to 89 eV, BE D 0.6 eV for O 1s). During reaction, the
Copyright  2001 John Wiley & Sons, Ltd.
Catalytic cooperation at the interface of CaO/MgO catalysts 1039
latter is attributed to a smaller deposition of carbonaceous
matter on the Ca of the mixture than on the same metal
in pure CaO. On the other hand, Mg does not suffer
from the deposition of carbonaceous matter, as shown by
the unchanged atomic composition of Mg 2s. The smaller
deposition of carbonaceous matter is more evident if the
atomic percentage of Ca 2s is compared for the mixture
(increased from 0.5 to 1.2 at.%) and for pure CaO (diminished
from 13.0 to 8.6 at.%). The Ca/C ratio remains constant in
the mixture for fresh and used catalysts (0.03 to 0.04 at.%,
in spite of carbonaceous matter deposition during reaction).
On the contrary, in pure CaO the Ca/C ratio decreased
from 0.35 to 0.15 at.%. This result suggests that the Ca
shows a different behaviour in the mixture than in pure
CaO. This shows a change of calcium behaviour in relation
to carbonate formation and carbonaceous matter deposition
when in contact with magnesium. In the mixture, magnesium
would inhibit carbonaceous matter deposition and carbonate
formation.
Interpretation of the synergistic effect
The absence of new phase formation and of any mutual
chemical contamination between MgO and CaO in the mix-
ture strongly suggests that the oxides in the mixtures behave
as separate oxides. The consequence is that the synergistic
effects have to be explained as catalytic cooperation between
the two oxides in good contact.
The mixture behaves more like MgO than CaO and
this suggests that some type of site exists in CaO that is
of a different nature than the sites present in MgO and
in the mixture. These differences might be responsible for
the different activity of the mixture, being similar to those
in MgO but somehow modified in quantity or strength
by the presence of CaO. The differences in carbonate
formation observed during CO2 adsorption make clear the
differences existing between the basic sites of MgO and
those present in CaO. It is well known12 – 14 that, according
to their type, carbonates behave differently during the
reaction. For unidentate carbonate formation, adsorption
occurs through the bond of the carbon atom from the
CO2 molecule with an oxygen atom of the solid catalyst,
thus leaving free a metallic atom. Bidentate carbonate
formation, after adsorption, proceeds through the bond of
the carbon atom from the CO2 molecule with the basic
oxygen of the solid and, simultaneously, by bonding of an
oxygen atom from CO2 with the metallic atom from the
catalyst. The more stable bidentate carbonate, formed on
the surface of pure CaO, would deactivate their sites and
then inhibit steam dissociative adsorption over them, which
is a necessary step for the occurrence of both deposited
carbon gasification as well as the shift reaction involved in
the gasification mechanism.6,19 This would not be the case
when pure MgO or the mixture are used as catalysts, where
exposure of the free cation to steam favours its adsorption
and subsequent formation of hydroxyl groups in sufficient
amounts to proceed with gasification. Then, cooperation in
the 10% CaO C 90% MgO mixture is evidenced by the fact
that MgO allows the more basic sites of CaO to be cleared
and freed from carbonates and deposited carbon. It could be
Surf. Interface Anal. 2001; 31: 1031–1041
1040 N. Alarcón et al.
suggested that MgO would be responsible for the existence of
OH groups near the CaO sites, thus avoiding the formation
of stable bidentate carbonates, where carbonates formed
over the mixture are of the unidentate type as opposed
to the bidentate type formed on CaO (Fig. 3). The rapid
decomposition of the unidentate species contributes to the
formation of intermediate compounds such as formates,
carboxylic groups or aldehydes. Reaction with steam easily
removes these compounds, particularly formates.
The present results allow some speculation. In fact, we
cannot exclude that some type of migration of some chemical
species could be useful in explaining the observed effects.
Spillover species can play at least two roles: creating active
sites or reacting with some compounds on the surface. As
an example, migration of OH groups could be involved at
the interface between MgO and CaO; OH species formed
on MgO could migrate onto the surface of CaO by a
spillover process. This OH species could react on the surface
of CaO, thus creating sites that allow the formation of
unidentate carbonate on it and consequently decreasing the
formation of carbonate, as discussed above. However, the
migration of hydrogen species also could be involved. In
this case, atomic hydrogen could react with the precursors
of carbonaceous matter, inhibiting its formation. Phenomena
of this nature have been demonstrated previously in the
literature by isotopic exchange of H, OH and O species
during several reactions involving metals, oxides, alumina,
zeolites, etc.33 – 38 However, although these phenomena could
be involved in the mixtures, at the stage of the present
research such explanation is only speculation and requires
more experimental confirmation.
CONCLUSIONS
The analysis of CaO, MgO and a 10% CaO C 90% MgO
mixture by DRIFTS and XPS showed no correlation between
basicity and catalytic activity. However, carbonate formation
and carbonaceous matter deposition over the catalyst surface
were observed, the latter occurring mainly over the surface
oxygen atoms. The formation of formates, carboxylic and
aldehydic groups as intermediate species during gasification
reactions also was observed.
Depending on the sample, different types of carbonates
are formed during the steam gasification of naphthalene
reaction conditions. For MgO and the 10% CaO C 90% MgO
mixture, carbonates formed are of the unidentate type and
they showed lower stability in the presence of steam. For
CaO bidentate-type carbonates are formed, which showed a
higher thermal stability even when steam was present.
No indication of a contamination phenomenon between
the metal components forming the oxides was observed
during the catalytic reaction. Then, the synergistic effect
observed in the steam gasification of naphthalene on
the 10% CaO C 90% MgO catalyst could be explained by
catalytic cooperation between separated MgO and CaO
oxides. The MgO is responsible for inhibition of bidentate
carbonate formation and carbonaceous matter deposition
over the calcium oxide surface, promoting on it the formation
of unidentate carbonates.
Copyright  2001 John Wiley & Sons, Ltd.
Acknowledgements
The support of FONDECYT-Chile (Grant no. 1980474) and a
fellowship granted by the Andes Foundation to one of the authors
(N.A.) are gratefully acknowledged. The XPS and DRIFTS analyses
were carried out at the Unité de Catalyse et Chimie des Matériaux
Divisés, Université Catholique de Louvain, Belgium. The authors
acknowledge financial support from the National Foundation for
Scientific Research (FNRS, Belgium).
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