6036 J. Phys. Chem.

B 1999, 103, 6036-6046

r-Alumina-Supported Nickel Catalysts Prepared with Nickel Acetylacetonate. 1. Adsorption

in the Liquid Phase

R. Molina, M. A. Centeno, and G. Poncelet*,

Unite de Catalyse et Chimie des Materiaux DiVises, UniVersite Catholique de LouVain, Place Croix
du Sud 2/17, 1348 LouVain-la-NeuVe, Belgium, and Departamento de Quimica Inorganica y Instituto de
Ciencias de Materiales de SeVilla-CSIC, UniVersidad de SeVilla, P.O. Box 878, 41071 SeVilla, Spain
ReceiVed: February 15, 1999; In Final Form: May 15, 1999

Nickel acetylacetonate was used as a precursor for the preparation of Ni/Al2O3 catalysts with metal content
between 0.4 and 3 wt %. The nature of the interactions between the metal complex and the support has been
investigated by X-ray photoelectron (XPS) and infrared (IR) spectroscopies. The spectral features point to
modifications of the precursor in the adsorbed state. IR results indicate that the interaction between acetylacetone
and the support involves coordinately unsaturated (cus) Al3+ sites, hydroxyls of the support surface, and
probably also basic oxygens. A model for these interactions is proposed. Monolayer coverage is achieved at
a Ni loading of about 0.8-1.0%. Piling in multilayers occurs at higher content.

Introduction Supported Ni catalysts prepared with nickel acetylacetonate

The mechanism of ligand substitution in transition metal
acetylacetonates adsorbed on the surface of dispersed oxides is
of prime importance to the understanding of the processes of
catalyst activation on a molecular level.1 The nature of the
interaction between those metal precursors and supports has been
investigated in both vapor2-7 and liquid phases.8-13 Supported
metal oxide catalysts prepared with metal acetylacetonates are
obtained in two steps: irreversible adsorption of the complex
on the support and decomposition of the adsorbed complex.
At the adsorption step, the interaction may take place via
hydrogen bonding or involve a ligand exchange mechanism,
depending on a number of factors such as configuration
(spherical, planar) and stability of the metal complex, nature of
the metal and its coordination, nature of the support surface,3,8-12
and orientation of the acac ligands with respect to the surface
hydroxyl groups of the support.10
The carbon/metal ratio of the supported complex has been
used as an aid to assess the type of interaction mechanism.6,7,10-12
For stable complexes, the carbon/metal ratio of the adsorbed
complex is similar to that of the precursor, while adsorbed
unstable complexes present lower carbon/metal ratios and their
structures differ from that of the parent complex. van Veen et
al.9 investigated the reactivity of transition metal acetylacetonates
with respect to the reactive surface groups of -Al2O3. The
authors came to the following conclusion: (i) complexes that
are stable in acid and base as, for example, Pt(acac)2, Pd(acac)2,
and Co(acac)3, only react with coordinately unsaturated surface
(cus) Al3+, with a transfer of acac ligands to Al3+; (ii) complexes
that decompose in a base but not in an acid, for example, MoO2-
(acac)2 and VO(acac)2, react with both coordinately unsaturated
(cus) Al3+ sites and basic OH groups of the support; (iii)
complexes that are sensitive to acid react to a small extent with
acidic OH groups, for example, Fe(acac)3, or they do not react
at all, as Ru(acac)3.
* Corresponding author. E-mail: poncelet@cata.ucl.ac.be.
Universite Catholique de Louvain.
Universidad de Sevilla.
10.1021/jp9905427 CCC: $18.00 1999 American Chemical Society
Published on Web 07/02/1999
have been scarcely investigated, most studies dealing principally
with catalytic reactions14-19 and/or metal particle size measure-
ments.20,21 The few studies of the interaction of nickel acetyl-
acetonate with oxide supports (silica, alumina) prepared in the
liquid phase are those of van Veen et al.8,9 who concluded that
no well-defined chemisorption (in a well-defined way) occurred
because of the formation of a precipitate. In recent studies, Ni-
(acac)2/-alumina6,7,22 and Ni(acac)2/silica6 have been prepared
by vapor-phase deposition (VPD), and the reaction of the metal
complex with surface hydroxyl groups has been investigated.
The main objective of the present study is to complement
the information on Ni(acac)2/alumina compositions prepared in
the liquid phase. The results obtained for Ni(acac)2/R-Al2O3
systems are discussed in relation with the adsorption mechanism
and monolayer formation. The thermal decomposition of the
adsorbed species will be treated in a separate article.23
Experimental Section
A commercial R-Al2O3 prepared by calcination of a transition
alumina (from Rhone-Poulenc) was supplied by (former)
Catalysts and Chemicals Europe. Small amounts of and
transition phases were identified in the X-ray diffraction pattern.
The nitrogen BET surface area was 42 m2 g-1 with a total pore
volume of 0.21 cm3 g-1. The weight loss between 500 and 1000
C amounted to 0.082%, which corresponds to 1.28 1018 OH
m-2. The 27Al MAS NMR spectrum showed two signals at 11.5
ppm (octahedral Al) and 63.8 ppm (tetrahedral Al), in a
proportion of 82-18%.24
Prior to the adsorption experiments, alumina was calcined at
500 C for 16 h in air in order to remove adsorbed water.
Required amounts of nickel acetylacetonate (fraction less than
100 m, from Merck) were dissolved in benzene (highest purity,
from UCB) under stirring for 15 min before addition of the
calculated weight of alumina (fraction less than 100 m). The
solution/alumina ratio was 2.1 mL g-1 (10 times the total pore
volume). The slurry was stirred at room temperature for 48 h.
After filtration, the solid was washed several times with pure
benzene (total volume: 25 mL g-1) and dried at room
R-Alumina-Supported Ni Catalysts J. Phys. Chem. B, Vol. 103, No. 29, 1999 6037

TABLE 1: Chemical Analysis Data

Ni(acac)2 supplied wash solution
(mol/(g Al2O3)) Ni/solid Ni uptake (ppm/(g Al2O3))
sample Ni acac (%) (%) C (%) C/Nia Ni Al
0.4 85 168 0.45 90.2 0.9 8.3 0.14 0.24
0.8 169 335 0.82 82.6 2.0 10.9 0.14 0.87
1.0 209 414 1.00 81.7 2.2 9.5 0.14 b
1.6 361 716 1.59 75.0 3.2 9.5 5.61 1.81
3.0 682 1350 2.92 73.0 5.9 9.7 9.13 2.33
Al2O3 <0.01 0.1
Al2O3 + benzene 0.1 0.08
Hacac/Al2O3 3880 0.6 190
Ni(acac)2 19.35 39.8 9.9
a
C/Ni ratio determined after subtraction of blank (0.1% for Al2O3 + benzene). Not determined.
b

temperature. Different amounts of complex corresponding to

0.4, 0.8, 1.0, 1.6, and 3.0 wt % Ni were supported on alumina.
For comparison purposes, Ni-free samples were prepared as
follows: (i) an amount of 5 g of alumina was treated with 10
mL of benzene and (ii) a quantity of 2 mL of pure acetylacetone
(from Merck, designated below as Hacac) was dissolved in 10
mL of benzene containing 5 g of support. The preparation
conditions and postadsorption washing were similar to those
used for the preparation of the supported samples.
Since this study was exclusively centered on the adsorption
step, nonimpregnated and impregnated solids dried only at room
temperature will be presently considered.
The Ni and Al content of the solids and the washing solutions
was determined by inductively coupled plasma spectroscopy
(ICPS) on samples dried at room temperature. Carbon was
converted to CO2 and collected in a solution of barium
perchlorate. The perchloric acid released was determined by
coulometric titration (Coulomat 702 Strohlein apparatus).
XPS measurements were carried out with a Vacuum Genera-
tors ESCA 3MK II spectrometer equipped with a Tracor
Northern TN1710 signal averager and a Mg anode as an X-ray
source operated at 14 kV with a current beam of 20 mA. The
peaks of C 1s, O 1s, Al 2p, Al KLL, and Ni 2p3/2 levels were
analyzed, referencing the respective binding energies (BE) to
the C 1s line (at 284.8 eV) of adventitious carbon. Good fits of
the peak decompositions were obtained with the software least-
squares fitting program using a Gaussian/Lorentzian ratio of
85:15. The experimental sensitivity factors of Wagner et al.25
were used for the calculation of the atomic concentration ratios.
The nature of the surface-active centers of the support has
been examined by infrared spectroscopy of adsorbed CO2,
ammonia, and pyridine on wafers obtained by compression. The
sample was outgassed in an IR cell at 500 C for 14 h prior to
admission of the probe molecule, and spectra were recorded
after outgassing at room temperature and heating to 300 C.
The impregnated solids and the pure precursor were also
analyzed by this technique (Bruker IFS-88 spectrometer), both
in diffuse reflectance (DRIFT) and conventional transmission
modes. In the first case, the spectra were recorded on powder
samples, while for transmission IR, wafers were prepared by
compression of the samples. The pure metal precursor was
diluted in KBr.
Results
Adsorption. Pure Ni(acac)2 is emerald-green, and its benzene
solution develops an intense green coloration. In the presence
of the support, decoloration of the solution occurred, the support
turning from white (sample with 0.4 wt % Ni) to light-green
(sample with 3% Ni). The wash solutions were greenish only
for Ni amounts in excess of 1 wt %, with a slightly more
Figure 1. Ni uptake (in mol/(g of solid)) vs time (170.6 mol Ni-
(acac)2 supplied per gram of support).
sustained coloration for the samples with 3% Ni complex. For
Ni content of 1% and less, the wash solution was colorless.
To establish the influence of the washing, samples impreg-
nated with Ni(acac)2 (1.6% Ni) were washed several times with
a total volume of either 25 or 250 mL of benzene per gram of
solid to remove the unadsorbed nickel complex. The Ni content
of the solids was not modified even after an exhaustive washing,
which suggests that nickel-support interactions stronger than
physisorption occurred at the adsorption step.
Figure 1 shows the time dependency of the amount of Ni-
(acac)2 adsorbed on the alumina (for the same amount of Ni-
(acac)2 per gram of support, namely, 170.6 mol/(g Al2O3) or
0.8% Ni). An amount of 81% of the Ni precursor (138 mol)
was adsorbed within the first hour. The amount adsorbed
reached a maximum after about 12 h, with a stable value after
48 h (88% adsorbed). This 12 h contact time was adopted to
prepare the series of catalysts with different amounts of Ni. The
results of the chemical analyses of the solids dried at room
temperature and of the wash solutions for samples with different
nickel content are given in Table 1.
Figure 2 shows the amount of Ni fixed on the support versus
the Ni found in the wash solution (expressed in g L-1). Up to
1% Ni, nearly all of the metal complex was adsorbed. For higher
amounts, part of the nickel complex was not adsorbed, which
increased with the amount of Ni acetylacetonate supplied. The
variation of the percentage of Ni retained on the solid as a
function of the amount of Ni present in the impregnation solution
is illustrated in Figure 3. This figure includes the results obtained
with 0.1 and 0.2 wt % Ni, where more than 95% of the Ni was
adsorbed.16 It is clear that the proportion of Ni retained on the
support decreased with increasing amounts of nickel complex
in solution.
6038 J. Phys. Chem. B, Vol. 103, No. 29, 1999
Figure 2. Amount of Ni on the solid (in g g-1) vs amount of Ni in the
wash solution (in g L-1).
Figure 3. Percentage of Ni retained on the support (%) vs Ni supplied
(mol/(g of support)).
On the other hand, the C/Ni ratios (Table 1) of the
impregnated solids did not significantly differ from that of pure
Ni(acac)2. Only a slight difference was observed for the sample
with 0.4% Ni. For the support treated with acetylacetone, Hacac/
Al2O3, the C content was 0.59% compared with 23% corre-
sponding to the initial C content (calculated for 1.94 g of Hacac
added to 5 g of Al2O3). The quantities of Al released from the
support in the wash solution for the different samples are given
in Table 1. The effect of the amount of acac groups on the
dissolution of this element, including the systems Al2O3/benzene
(blank) and Hacac/Al2O3, is shown in Figure 4. The inset in
the figure corresponds to the Ni(acac)2-impregnated supports.
Both Al in solution and acac groups were normalized to the
weight of the support. Obviously, the amount of Al in the wash
solution increased with the amount of acac groups. These
amounts were much lower for Ni(acac)2/Al2O3 than for Hacac/
Al2O3. The support treated with pure benzene released a
negligible amount of Al.
X-ray Photoelectron Spectroscopy. The binding energies
(BE) and the full widths at half-height maximum (fwhm) of
the C 1s, O 1s, and Ni 2p3/2 peaks of representative samples
are given in Table 2. The corresponding spectra of the C 1s
peak are shown in Figure 5. For all the samples, including the
support, decomposition of the C 1s peak was best achieved with
Molina et al.
Figure 4. Effect of the amount of acac groups (mol/(g of support))
on the dissolution of Al (in ppm/(g of support)).
Figure 5. XPS spectra of the C 1s peak of (a) Al2O3, (b) Al2O3 calcined
at 1200 C, (c) Hacac/Al2O3 and for Ni(acac)2/Al2O3 with (d) 0.4, (e)
1.0, (f) 1.6% Ni, and (g) pure Ni(acac)2.
three components. Imposing one, two, or four components was
unsatisfactory. For the Ni(acac)2-impregnated samples, no
constraint was imposed.
A detailed analysis of contamination carbon and of its use
as a standard for the calibration of the binding energies was
made by Barr et al.26 The peak at (284.8 eV has been attributed
to C linked to C or H, while peaks near 286.5 and 289 eV have
been assigned to -C-O and -CdO (in OdC-O-C or
OdC-OH), respectively.27-30 A shoulder at 286.4 eV in the C
1s peak of [Ni(acac)2]3 was assigned to the two carbonylic
carbons.29 Barr et al.26 emphasized that if not all CxHy and
carbon compounds are supposed to have a singular binding
energy, there is evidence for a systematic change of the C 1s
BE with the complexity of the other organic compounds present
in the environment. It was thus interesting to apprehend, in our
systems, possible variations of these carbon species induced by
the presence of acetylacetonate and to use the changes of the
shape of the C 1s peaks to infer, in a qualitative manner, a
possible modification of the complex precursor occurring upon
adsorption. Since Ni(acac)2 contains the three types of carbon
bonds mentioned above, a modification of these bonds might
exist as a function of the precursor loading, especially for the
C 1s peaks of carbon engaged in -C-O and -CdO bonds.
As shown in Figure 5, the asymmetrical profile of the C 1s
peak in pure Ni(acac)2, with a distinct shoulder at around 287
eV, became more symmetrical in its adsorbed state. The
R-Alumina-Supported Ni Catalysts J. Phys. Chem. B, Vol. 103, No. 29, 1999 6039

TABLE 2: Binding Energies (BE, in eV) and Full Widths at Half-Maximum (fwhm Values in Brackets in eV)
C 1s Ni 2p3/2
sample C1 C2 C3 O 1s mp sat. Ct (%) (C2 + C3)/Ct
Ni(acac)2 284.8 286.8 290.0 531.7, 536.3 856.0 860.7 64.46 0.40
[2.68] [2.55] [4.30] [2.66], [2.18] [2.85] [6.78]
1.6% 284.8 286.7 288.8 530.9 856.0 861.7 20.10 0.28
[3.34] [2.29] [3.79] [3.12] [4.21] [6.19]
1.0% 284.8 286.4 289.0 530.9 856.3 862.1 19.02 0.31
[3.41] [2.15] [3.08] [3.14] [4.43] [5.50]
0.4% 284.8 286.5 289.0 530.9 855.8 861.6 16.88 0.31
[2.93] [2.34] [4.33] [3.09] [4.46] [6.44]
Hacac/Al2O3 284.8 286.7 289.1 531.0 11.60 0.30
[2.72] [2.30] [2.81] [3.22]
Al2O3a 284.8 286.3 289.3 530.9 11.88 0.31
[2.72] [2.21] [3.03] [3.15]
Al2O3 284.8 286.5 289.6 531.1 27.33 0.18
[2.59] [2.13] [2.99] [2.98]
a
C/Ni ratio determined after subtraction of blank (0.1% for Al2O3 + benzene).

Figure 6. O 1s peak of (a) Ni(acac)2 and of samples with nickel content Figure 7. Ni 2p3/2 peak of (a)/Ni(acac)2 and of Ni(acac)2/Al2O3 with
of (b) 1.6, (c) 1.0, and (d) 0.4% Ni. metal content of (b) 0.4, (c) 1.0, and (d) 1.6%.

progressive modification of the C 1s peak profile with increasing
amounts of complex is more evident when the total carbon (Ct
in Table 1) and the surface carbon content (Table 2) of the
samples are considered. Indeed, the (C2 + C3)/Ct ratios, with
C2 standing for -C-O and C3 for -CdO, decreased from 0.40
(for nickel acac) to 0.28-0.31 for the impregnated samples.
As mentioned above, no good fit was obtained when the BE
values obtained for pure Ni(acac)2 were imposed in the
decomposition of the peaks of the impregnated samples. It is
seen in Table 2 that there was no important change of the
binding energy of the C2 component of the C 1s peak, whereas
for C3, a shift of about 1 eV between the pure and the supported
precursor was observed. These observations are consistent with
a modification of the precursor when it is adsorbed on the
support.
The BE and fwhm values of the O 1s peak are presented in
Table 2. For the sake of illustration, Figure 6 shows the spectrum
of the O 1s peak of a few samples. Pure Ni(acac)2 showed a
main peak at 531.7 eV and a weak one at 536.3 eV. In the
spectra of the impregnated samples, the second peak at 536.3
eV was absent while the main peak broadened and shifted by
about 0.7 eV, indicating a decrease of the BE of oxygen-carbon
(C-O or CdO) and/or oxygen-nickel (in acac group). As for
the C 1s peak, these features point to a modification of Ni-
(acac)2 when it is supported on alumina. This hypothesis
assumes that a change of the charge around Ni would also occur.
The XPS spectra of the Ni 2p3/2 level of Ni(acac)2 and the
impregnated samples (0.4, 1.0, and 1.6% Ni) are shown in Figure
7, and the BE and fwhm values are given in Table 2. The BE
of the main peak (856 eV) was similar in all the samples and
in agreement with the values reported for Ni(acac)2 and assigned
to Ni(II).29-31 On the other hand, there was a difference in the
BE of the satellite peak by about 1.0-1.4 eV between the pure
and adsorbed complex. Also, the main peak and the satellite
peaks of the pure and adsorbed complex exhibited differences
in both the fwhm value and the peak profile. While an important
increase of the fwhm of the main peak was observed between
pure and supported Ni(acac)2, both a change of the peak profile
and a decrease of the fwhm of the satellite peak were noticed.
These changes again are consistent with a modification of the
precursor after its adsorption on the support and perhaps also
with the formation of at least one different nickel species as
may be suspected from the asymmetry in the right-hand side
of the peak.
Surface Sites of the Support: IR Spectroscopy of Ad-
sorbed Probe Molecules. The spectrum of the support out-
gassed at 500 C showed three bands at 3752, 3734 (shoulder),
and 3690 cm-1. According to Knozinger and Ratnasamy,32 a
maximum of five different OH configurations can be expected
for -alumina, ranging from basic terminal OH coordinated to
a single tetrahedral Al3+ ion to acidic bridging OH coordinated
to three Al3+ ions in octahedral insterstices, their actual
occurrence and proportions depending on the relative contribu-
tions of the different crystal faces. The band at 3690 cm-1
(Figure 8a) probably corresponds to a type III configuration
(OH linked to three Al3+ ions in octahedral position). A band
at 3734 cm-1 in R-alumina has been assigned by Morterra et
6040 J. Phys. Chem. B, Vol. 103, No. 29, 1999
Figure 8. Infrared spectra of R-alumina support after (a) outgassing overnight at 500 C, (b) adsorption of CO2, (c) outgassing at room temperature
(10-3 bar), (d) room temperature (10-5 bar) and outgassing at 10-5 bar for 20 min at (e) 100 C, (f) 200 C, and (g) 300 C.
al.33 to OH attached to Al in octahedral coordination and that
at 3750-3755 cm-1 to OH coordinated to a single tetrahedral
Al3+ ion.
The IR spectra after adsorption of CO2 at room temperature
(100 mbar) and after outgassing at different temperatures on
R-alumina previously heated under vacuum at 500 C for 14 h
are shown in Figure 8. Morterra et al.34 defined five species,
A-E, characterized by bands at about 1655, 1440, and 1225
cm-1 (species A); at 1570-1610) and 1350-1385 cm-1 (species
B); at 1660-1675 and near 1345 cm-1 (species C); around 1710
and 1310 cm-1 (species D); and above 1730 (1755 and 1810
cm-1) with a diffuse shoulder below 1300 cm-1 (species E).
According to these assignments, the bands at 1652, 1440,
and 1227 cm-1 would characterize surface hydrogen-carbonate
species (species A), the formation of which requires the presence
of tetrahedral Al.32 AlIV was observed in the 27Al MAS NMR
spectrum, and small amounts of transition alumina were
identified by XRD. The bands at 1606 and 1350 cm-1 may be
assigned to species B (symmetrical and asymmetrical CO2
stretches of at least one monodentate species formed on basic
oxygens). The one at 1585 cm-1, which shows a similar
evolution upon outgassing, is tentatively attributed to the same
species. The shoulder near 1700 cm-1 probably corresponds to
species D, attributed to a bidentate carbonate. The formation
of this species is favored by a high dehydration degree.34 Figure
8 also shows that species A and D are less important and less
stable than species B, since an outgassing at room temperature
(10-3 bar for 10 min and then at 10-5 bar for another 10 min)
produced a significant loss of intensity of the corresponding
absorption bands, leaving those of species B relatively much
less affected. Species A and D were removed after an outgassing
at 100 C for 20 min, while species B needed an outgassing
above 250 C to be totally eliminated. The formation of
monodentate species B (CO2 on basic oxygens) and their higher
resistance to evacuation indicate a relatively high basicity of
these centers.
Molina et al.
In the OH stretching region (Figure 8, right), the adsorption
of CO2 produced a clear perturbation of the high-frequency band
at 3752-3740 cm-1 and that at 3690 cm-1, with the appearance
of a broad band centered at 3550 cm-1. These modifications
have been attributed to the formation of species A (hydrogen-
carbonate) involving isolated OH groups. Note also the simul-
taneous resurgence of the OH band and the diminution of those
characterizing species A (at 1652, 1440, and 1227 cm-1) upon
outgassing.
Adsorption of ammonia and pyridine performed under similar
conditions showed the complete disappearance of the OH bands.
In the case of ammonia, two bands apprearing at 1625 and 1240
cm-1 were assigned to the symmetrical and asymmetrical
deformation vibrations of ammonia coordinately held on un-
completely coordinated Al3+, indicative of Lewis acidity.35,36
Two other bands could be distinguished near 3390 and 3220
cm-1. Morimoto et al.37 reported that such bands appear when
hydrogen bonding with hydroxyls is the only interaction with
the surface. The spectra of adsorbed pyridine showed bands at
1614, 1595, 1578, 1491, 1449, and 1444 cm-1. According to
the results of Morterra et al.38 on R-alumina (containing small
amounts of -alumina), the bands at 1595 and 1614 cm-1 could
be assigned to Py species coordinated to octahedral and
tetrahedral Al sites, respectively. Those at 1449 and 1444 cm-1
would indicate the presence of two types of Lewis sites with
slightly different acid strengths. As for ammonia, these bands
were barely observed after an outgassing at 150 C.
Infrared Spectroscopy of the Adsorbed Complex. Pure
metal acetylacetonates have been extensively investigated by
infrared spectroscopy, and the main spectral features have been
compiled by Nakamoto.39 Alumina-supported Mn+(acac)n, un-
supported and supported Hacac, and Al(acac)3 have also been
examined, recordings of pure metal complexes allowing band
assignment. The frequencies (in wavenumbers) of the absorption
bands of Al(III) and Ni(II) acetylacetonates taken from the
R-Alumina-Supported Ni Catalysts J. Phys. Chem. B, Vol. 103, No. 29, 1999 6041

TABLE 3: IR Absorption Frequencies of Metal Acetylacetonates (cm-1)

Al(acac)3 Hacac Hacac/Al2O3 Ni(acac)2 predom modes
(39) (40) (41) (41) (obsd) (41) (39) (obsd) (39)
1620 1613 1613 (CdC)
1590 1595 1585 1580 1590 1598 1595
1545 1548 1526 1613 1598 1565 (CdO)
1530 1534 1533 1533
1466 1466 1455 1455 1517 1515 1514 1517 (CdC) + (CH)
1465, 1453 1455 1453 1464, 1453
1387 1429 1418 1425, 1404 1390 1398 1425, 1404 d(CH3)
1365 1378 1355 1366, 1335 1367 1361 n(CH3)
1288 1292 1280 1298 1291 1256 1261 1291 (CdC) + (C-H3)
1244 1263 1263
1191 1193 1185 1168 1156 1190 1198 1201 (C-H)
1154
1028 1029 1023 1020 1059 1015 1020 1024 r(CH3)
1018 1010 998
935 937 931 954 968 931 (C-H3) + (CdO)
912 919 924 929
773 776 774 779 (C-H)
772 768 767 764 766
685 686 688 668 666 677 ring def + (M-O)

658 654 639 630 656 661 (C-H3) + (M-O)

621
577 596 529 582 579 590
574 510 562 563
490 492 472 475 440 452 (M-O)
425 429 423 427 426
416 420

literature and the frequencies of unsupported Ni(II) acetyl-

acetonate and Hacac/Al2O3 observed in this work are listed in
Table 3.
The IR spectra of the impregnated supports, pure Ni(acac)2
(as KBr pellet), Hacac/R-Al2O3, and the support were recorded
between 4000 and 400 cm-1. Between 1250 and 400 cm-1
(Figure 9), the DRIFT spectra of the Ni(acac)2- and Hacac-
impregnated solids were similar to that of alumina and different
from that of the pure nickel compound because of the
predominant optical properties of alumina in this spectral region.
With increasing amounts of nickel acetylacetonate, there was
an important modification of the broad band of Al2O3 centered
at about 1034 cm-1. For the sample with 3% Ni, several bands
corresponded to those of the pure complex (at 1201, 1024, 931,
and 426 cm-1). New bands appeared at 1159 [(C-H)] and
920 cm-1 [(C-CH3) + (CdO)] with a maximum intensity
for the sample with 0.8% Ni. Those bands were barely visible
in the spectrum of the 3% Ni sample and absent for the pure
complex. Since these new bands were also observed in the
spectra of supported and unsupported Hacac (Table 3), it was
inferred that acac ligands were removed from the Ni precursor.
The band at 1159 cm-1 was better resolved in the transmission Figure 9. Drift spectra of (a) Al2O3 and Ni(acac)2/Al2O3 with metal
spectra because of the less predominant influence of the optical content of (b) 0.4, (c) 0.8, (d) 1.0, (e) 1.7, and (f) 3.0% and (g) pure
Ni(acac)2.
properties of alumina. The band at 1201 cm-1 [(C-H)] found
in pure Ni(acac)2 was detected in the sample with 0.4-0.8%
and 426 cm-1) of the unsupported complex could hardly be
Ni and developed with increasing Ni content. A band at 965-
970 cm-1 for the Hacac/Al2O3 system was also found for the dsitinguished because alumina as well absorbs in this region.
impregnated samples. It was absent in the spectrum of the pure In Cu(acac)2/SiO2, Mitchel et al.42 reported that the apparent
complex. This again is consistent with a loss of acac ligands intensities of the absorptions in the range 1000-600 cm-1 fell
from the precursor. to zero at concentrations below monolayer coverage. Since the
Bands in the range 700-590 cm-1 are sensitive to the nature Cu(acac)2 absorptions in this region are active in hydrogen-
of the metal.39 A band at 688-676 cm-1 has been assigned to bonding solvents, the authors came to the conclusion that the
coupled M-O stretching and ring deformation of the organic apparent disappearance of these bands must be due to some
moiety, and another one at 630-660 cm-1 to coupled M-O mechanism specific to an interaction with the support surface.
stretching and C-CH3 bending vibrations. Bands between 500 Two bands at 456 and 433 cm-1 found only for multilayer
and 400 cm-1 were attributed to M-O stretching vibrations adsorption were assigned to out-of-plane vibrations of the lone
slightly coupled with C-CH3 stretching vibrations. In the spectra ring-bonded hydrogen atom. A similar phenomenon cannot be
of Figure 9, the different bands (at 792 and 774, 677, 661, 590, ruled out in our system.
6042 J. Phys. Chem. B, Vol. 103, No. 29, 1999
Figure 10. Drift spectra of (a) alumina, (b) Hacac/alumina, and Ni-
(acac)2/alumina with metal content of (c) 0.4, (d) 0.8, (e) 1.0, (f) 1.7,
and (g) 3.0% and (h) pure Ni(acac)2.
The spectra of the pure Ni(acac)2 complex and the impreg-
nated samples between 1700 and 1250 cm-1 exhibited similari-
ties but also differences in band position and relative intensities,
as shown in Figure 10. Bands appearing between 1300 and 1250
cm-1 (C-C stretching and/or asymmetrical C-O stretching)
depend, to some extent, on the metal to which the acac ligand
is coordinated.9 A band at 1290 cm-1, absent in the spectrum
of pure Ni(acac)2, was found for the impregnated samples as
well as for Hacac/Al2O3, while that at 1263 cm-1 was common
to both unsupported and supported Ni(acac)2. A band at 1295
cm-1 was similarly observed by Babich et al.6 for both Ni-
(acac)2 and Hacac supported on -alumina. The absorption at
1290 cm-1 has been assigned, in agreement with these authors,
to the formation of Al(acac) species. The presence of this species
implies the removal of an acac ligand from the Ni complex
and its transfer on Al3+. The similar shape and relative intensity
of the band at 1290 cm-1 in all the impregnated samples suggest
that only a limited quantity of Al(acac) species are formed.
The bands between 1500 and 1350 cm-1 (at 1366, 1404,
1425, 1453, and 1466 cm-1) exhibited slight changes of the
relative intensity with increasing concentration of the complex,
in particular those at 1404 and 1466 cm-1. The spectrum of the
sample with 3% Ni was similar to that of pure Ni(acac)2. The
shoulder at 1425 cm-1, barely visible for the samples with low
Ni loadings, was clearly distinguished in the spectrum of the
sample with 3% Ni. The band at 1404 cm-1 corresponds to
the (CH3) mode, while that at 1466 cm-1 contains contributions
of (CdC) and (C-H) modes.40
Two important changes were noticed between 1700 and 1500
cm-1. The shape of the broad band of pure Ni(acac)2 centered
at about 1517 cm-1, with shoulders at 1512 and 1530 cm-1,
changed with the metal loading and shifted by about 15 cm-1
with decreasing Ni loading. The shoulder at 1595 cm-1 in pure
Ni(acac)2 gave rise to a well-defined band in the spectra of the
impregnated samples, while the contribution at 1613 cm-1 in
the spectrum of the pure complex appeared as a shoulder at
1620 cm-1 in all the impregnated supports.
Kohler et al.43 found, for Pt(acac)2/alumina, a change of the
relative intensities of the bands of the acac ligands. New bands
at 1609 and 1575 cm-1 were attributed to acetylacetonate in an
Molina et al.
enolate configuration. Lindblad et al.7 observed that the bands
at 1590 and 1515 cm-1 of pure Ni(acac)2 were shifted, in Ni-
(acac)2/alumina, to 1615 and 1535 cm-1, respectively. The
authors concluded that ring opening of acetylacetonate through
enol formation could be disregarded for the surface nickel
species. Babich et al.6 also reported that the chelate structure
of the acac ligands is retained after chemisorption of Ni(acac)2
on the support surface. The presence of a band at 1533 cm-1 in
the spectrum of the Hacac/Al2O3 and Al(acac)3 (Table 3), absent
in bulk Ni(acac)2, constitutes additional evidence for the reaction
of the acac ligand with Al3+ sites.
Finally, the band at 1657 cm-1 in the spectrum of pure Ni-
(acac)2 (Figure 10) is clearly observed for the sample with 3%
Ni and suspected in the spectrum of the sample with 1.6% Ni.
A band in this region was assigned to ketenol tautomerism of
acetylacetonate.6
In summary, the spectral modifications in the 1250-700 cm-1
region and the appearance of new bands at 1159 cm-1 [C-H
or CH3 modes] and near 970 and 920 cm-1 [(C-CH3) +
(CdO) modes] are indicative of structural changes of the
original compound and more precisely of the loss of acac ligands
from the precursor molecule. Below 700 cm-1, the modifications
of the M-O and C-CH3 vibration modes were not clear. The
IR spectra in the region between 1700 and 1250 cm-1 also
provide evidence for the modification of the precursor when it
is supported on alumina. No ring opening of acetylacetonate
occurs, but instead, splitting of one acac group is very likely.
The spectrum of the Hacac/Al2O3 system (Figure 10b) indicates
that a reaction between Hacac and alumina occurs in the liquid
phase at room temperature, as is inferred from the presence of
characteristic bands in the acac region (at 1565-1568 cm-1 and
at 1290 cm-1). Those bands were clearly distinguished in
transmission mode. Since in Hacac/Al2O3 there is no other metal
than Al for acac to coordinate with, these bands must be due to
Al-acac entities. Hence, the presence of a similar band in the
Ni(acac)2/alumina samples points to an interaction of acac
ligands from the Ni complex with surface Al. The differences
between the supported and the unsupported complex appear
more clearly for the samples with 0.4 and 0.8% Ni and concern
principally the CdO, C-C, and C-H vibrations. This observa-
tion is consistent with the XPS results.
No important change was noticed in the IR spectral region
3000-1700 cm-1. Only variations of the intensity of the bands
due to the amount of complex were observed. No band appeared
at 1780-1800 cm-1, which, in agreement with Haukka et al.,5
rules out ring opening.
In the high-frequency region, differences according to the
amount of complex can be observed (Figure 11). The spectra
of the samples with 0.4-1.6% Ni and of Hacac/Al2O3 are
similar. They differ from those of unsupported Ni(acac)2 and
the sample with 3% Ni, both of show similar features. The OH
band at 3697 cm-1 in the spectrum of alumina was no longer
found after adsorption of the complex, providing unequivocal
evidence for the occurrence of an interaction between the
hydroxyls of the support and the nickel precursor. Pure Ni(acac)2
and the 3% Ni-loaded sample showed a band at 3245 cm-1 and
two distinct maxima centered near 3520 and 3420 cm-1. They
were no longer differentiated in the other samples. The broad
absorption between 3700 and 3000 cm-1 is probably associated
with the presence of hydration water (no outgassing treatment).
The band at 3076 cm-1 (region of the C-H stretching) was
observed in all the spectra, with increasing intensity as the
amount of the Ni complex increased.
R-Alumina-Supported Ni Catalysts
Figure 11. Drift spectra of (a) alumina, (b) Hacac/alumina, and Ni-
(acac)2/alumina with metal content of (c) 0.4, (d) 1.0, (e) 1.7, and (f)
3.0% and (g) pure Ni(acac)2.
Discussion
The experimental results provide strong indications that
interactions different from physical sorption between Ni(acac)2
and R-Al2O3 occur at the impregnation step. The discussion will
address three aspects in relation to possible interactions deduced
from (i) direct observations such as color change, chemical
analysis, adsorption data, and washing effect, (ii) spectroscopic
features (XPS and IR), and (iii) monolayer formation.
Direct Observations. Changes of the coloration observed
when solutions of metal acetylacetonates are brought in contact
with a support have been considered as an indication of the
coordination of the complex to the support with the release of
acac ligands.5,12,40 The color changes observed in the present
study, which were more clearly perceived at lower than at higher
Ni(acac)2 loadings, suggest the occurrence of a similar reaction
between precursor and support.
Washing with the pure solvent (benzene) is not solely
restricted to the removal of the excess acetylacetonate complex,
but it also shifts the equilibrium toward the formation of surface
species.44,45 Recently, Van Der Voort et al.12 examined, in the
case of VO(acac)2/SiO2, the influence of the number of
postimpregnation washings on the amount of metal retained by
the support. The amount of complex on the solid remained
unchanged after several washings, which led the authors to
conclude the existence of a strong complex-support interaction.
The similar observations made in this study allow one to infer
that nickel acetylacetonate is tightly bound to the support,
probably via a chemical reaction with the support and not a
physical deposition on the support. It is also consistent with
the adsorption results (Figures 2 and 3) showing that at low
complex loadings, practically all the Ni complex is retained on
the support even after exhaustive washing. The fact that some
Ni was found in the washing solution at higher loadings indicates
that only a limited amount of the complex may react with the
support. Moreover, the small amounts of Al found in the wash
solution suggest the formation of Al(acac)x species, since it is
related to the presence of acac groups and not to a solvent effect
(Figure 4). In agreement with Foger,46 it may be concluded that,
owing to these interactions, the shift of the equilibrium toward
J. Phys. Chem. B, Vol. 103, No. 29, 1999 6043
the formation of surface species and, hence, the final distribution
of the active phase are mainly determined at the impregnation
step, at least for low loadings of the metal complex.
Spectroscopic Evidence. Prior to the discussion of the
interaction between nickel acetylacetonate and alumina, the
Hacac/Al2O3 system will be considered first. The following
reaction between Hacac and coordinately unsaturated (cus) Al3+
sites has been proposed:9
[Al3+]s + Hacac f [Al(acac)x]s(3-x)+ + Al(acac)3 + [H]s
(1)
with s standing for surface species. [H]s is supposed to form a
hydroxyl group with an oxygen atom coordinated to cus Al3+.
This reaction has been widely accepted in the literature,6,7,12
even if its stoichiometry remains imprecise. Owing to the high
affinity of Hacac for Al3+ ions, the following reaction is likely
to occur: 9
Al-OH + Hacac f Al-acac + H2O (2)
This possibility, however, was ruled out by van Veen et al.9
mainly because (i) no band modification in the OH stretching
region was noticed and (ii) the OH-/F- exchange isotherms
for untreated and Hacac-treated Al2O3 were identical. In the
present study, the disappearance of the OH stretching band(s)
is consistent with the interaction of Hacac with OH groups
(Figure 11b). Additional evidence for the high affinity of the
acac anion for the Al3+ species, in line with published work,46
may be derived from both the effect of the acac ligands on the
dissolution of Al3+ species (Figure 4) and the IR bands showing
up principally at 1565-68 and 1290 cm-1 (Figure 10b). These
observations seem to indicate not only that reaction 1 is taking
place but also that reaction 2 is possible.
Although the supported and the pure metal complex showed
similar IR features, the spectral modifications discussed above
are consistent with the occurrence of interactions, at the
adsorption step, between the metal precursor and at least two
different surface sites: cus Al3+ sites (Lewis acid) with
formation of enolate; acidic surface hydroxyls.
As mentioned in Introduction, metal acetylacetonates may
interact with oxide supports via two main reaction mecha-
nisms:2-4,7,9-13 (i) hydrogen bonding between surface hydroxyl
groups and electrons of the acetylacetonate ring,
supportOH + (acac)M(acac) f
supportOH(acac)M(acac) (3)
(ii) ligand exchange involving the formation of a Hacac ligand
and a covalent bond,
supportOH + Mn+(acac)n f
supportOMn+(acac)n-1 + Hacac (4)
The Hacac produced may then react with cus Al sites as in eq
1.
In this study, samples dried at room temperature clearly
showed (Figure 11) the disappearance of the OH band upon
adsorption of the metal complex, which may equally be
accounted for by both mechanisms. However, if the mechanism
via hydrogen bonding is operating, no new IR band should
appear and the XPS features would hardly be accounted for.
The OH stretching bands at 3752 cm-1 (OH coordinated to
tetrahedral Al), and 3734 cm-1 (OH linked to octahedral Al)42
observed only when the support was heated at 500 C under
6044 J. Phys. Chem. B, Vol. 103, No. 29, 1999
vacuum, did not appear in the IR spectrum of Figure 10 probably
because of the rapid re-adsorption of water molecules that may
interact via hydrogen bonding, contributing to the large absorp-
tion between 3700 and 3000 cm-1. Therefore, it cannot be
ascertained that these hydroxyls also react with the metal
precursor, although both disappeared upon adsorption of probe
molecules. Beside, one may also expect that, owing to the high
thermal treatment to operate the -to-R phase transformation,
some among the five types of hydroxyls observed by Knozinger
and Ratnasamy32 for -alumina may have been irreversibly lost,
since they were not observed for the R-alumina.
The shifts of the C 1s peaks noted in the impregnated samples
relative to the pure complex, suggesting a decrease of the BE
of oxygen-carbon (-C-O or -CdO) and/or nickel-oxygen
(of the acac ligands), the absence of the second peak of the O
1s level at 536.3 eV in the impregnated support (present in pure
Ni(acac)2), the broadening of the main peak and its shift by
about 0.7 eV, and the modifications of the Ni 2p3/2 level equally
point to changes of the metal complex in its adsorbed state. In
addition, the appearance of new IR bands, which can only be
due to the reaction of acac ligands with Al3+ species, implies
the split of the molecule and the reaction of the second acac
group attached to Ni probably with surface OH groups (and/or
basic oxygens observed by IR-CO2) of the support. These
observations and the formation of the enolate on Al3+ species
(IR band at 1290 cm-1), the color changes of the impregnated
support, and the absence of Ni release upon exhaustive washing
are in favor of an adsorption mechanism involving covalent
bonding rather than a physical adsorption via H-bonding or
simple a precipitation.
If Ni-acac reacts with an OH group and/or a basic oxygen
of the support (observed by IR-CO2), it may be expected that
the change of one acac ligand for one oxygen of the support
(with electronegativity of 3.5) will produce a modification of
the charge around the nickel. Since the band shifts observed in
the spectral region 1700-1200 cm-1 were not large, the overall
change of charge after reaction must not be very important,
inasmuch as the existence of other Ni species with BE nearly
similar to those of Ni(acac)2 cannot be ruled out. This would
be consistent with the results of Grim and Matienzo47 for
inorganic and organometallic compounds of molybdenum, which
exhibited similar BE values despite different oxidation states
of Mo.
As mentioned above, the carbon/metal ratio may provide an
indication of the type of interaction mechanism.6,7,10,12 Lindblad
et al.7 showed that when solid Ni(acac)2 was vapor-phase-
deposited (VPD) on alumina pretreated at 200 and 800 C, the
C/Ni ratios were about 5 and 8, respectively. Since the IR band
of the isolated OH groups disappeared, the authors proposed
that an exchange reaction took place according to eq 4. Since
in VPD the temperature (200 C) was near the decomposition
temperature of Ni(acac)2 (230 C), the loss of a ligand was
favored over the associative adsorption, which may account for
a C/Ni ratio of 5. A C/Ni ratio of 8 would imply an additional
reaction between acac ligands and Al3+ sites of alumina, the
formation of those sites being favored by calcination at high
temperature.31 Babich et al.6 determined, from TG-DSC mea-
surements, an acac/Ni ratio of 1.7 (C/Ni ) 8.4) and also
suggested that the precursor is covalently bonded to the support,
Hacac evolving during chemisorption of Ni(acac)2 reacting with
cus Al3+ ions on the alumina surface.
The absence of a significant difference of the C/Ni ratio of
the impregnated solids relative to that of the metal precursor
(Table 1) indicates either that the complex is not decomposed
Molina et al.
(eq 3), and then only the IR OH stretching band should be
perturbed, or that the chemical reaction proceeds without loss
of acac ligands (eq 4), and in that case the Al(acac) species
should remain adsorbed on the support, which is consistent with
the very low amounts of Al found in the wash solution.
The surface reaction between Ni-acac and surface OH groups
and between split acac ligands and cus Al3+ sites with enolate
configuration may be represented by the general reaction
The formation of the enolate configuration is probably limited
to the amount of the cus Al3+ available on the surface. The
proton released could react with the acac groups in excess of
the cus Al3+ available, forming Hacac, which at room temper-
ature remain adsorbed on the surface. As was suggested by van
Veen et al.,9 Hads could form a hydroxyl group with an O atom
that was coordinated to cus Al3+ before the adsorption. Mass
spectrometric analyses of the gaseous effluent of a sample dried
at 120 C showed the presence of methane, acetone, and acac,
besides CO, CO2, H2O, and traces of benzene. Since the carbon
analyses were performed on room temperature dried samples,
similar C/Ni ratios for the impregnated solids and the precursor
are not surprising. In reported studies, these ratios were
established on samples previously heated or obtained by CVD
methods (at 200 C).
Monolayer Formation. The formation of a monolayer should
be in relation with the specific surface area and/or the number
of sites available at the surface of the support. The structure
proposed for the adsorbed complex allows one to estimate the
monolayer (saturation) coverage on the R-Al2O3 from its specific
area (42 m2 g-1) and the packing of a molecule of the nickel
complex. A value of 0.373 nm2 was established from the unit
cell parameters. To achieve monolayer coverage, 2.7 molecules
of Ni(acac)2 nm-2 (1.1 wt % of Ni) would theoretically be
required. This value is consistent with the very low amount of
Ni found in the wash solutions (Table 1) and the associated
color changes of the solids with 0.8-1.0 Ni %. In reported
studies, the area of the supported nickel species retaining one
acac ligand was estimated to be 0.45 and 0.47 nm2, with a
theoretical density of 2.2 (0.91% Ni) and 2.1 Ni atoms nm-2
(0.87% Ni), respectively.7,22 Babich et al.6 reported values of
2.0 Ni atoms nm-2 for silica and 1.3 Ni atom nm-2 for
-alumina, which stayed unchanged after prolonged contact
times or when an excess of the metal precursor was used at the
preparation step. The difference between the values of the
literature and ours may be accounted for by the different choice
of the predominant face considered for the calculation of the
packing of the precursor molecule. The theoretical density is
thus in reasonable agreement with the results of the cited
authors.7,22
In the dipping method (used in this work), mainly applied
when the precursor interacts with the support, the metal uptake
is governed by the concentration of the adsorption sites at the
support surface.46,48 In pure alumina, both acidic and basic sites
were observed by IR spectroscopy. As the OH groups constitute
reactive sites, an evaluation of the formation of a monolayer
involving those sites can be made. The hydroxyl density of the
support was 1.28 OH nm-2. Assuming that each OH participates
in a ligand exchange, they may account for 47 or 60% of the
theoretical Ni density calculated above, depending on the
packing value adopted. Obviously, sites other than the OH
R-Alumina-Supported Ni Catalysts
groups should be involved. It has been shown that the cus Al3+
sites on alumina, whose number increases with increasing
calcination temperature, also intervene in the adsorption process,
although a precise figure cannot be easily determined.32 The
amphoteric character of both alumina and Ni(acac)2 leads us to
admit that basic surface oxygens of the support could also take
part in the adsorption process. Such sites were observed by IR
spectroscopy of adsorbed CO2. Room-temperature CO2 adsorp-
tion measurements on alumina (made at the Department of
Inorganic Chemistry (Prof. E. Vansant), U. I. T.; Antwerp) gave
a total uptake of 2.61 cm3 g-1, half of it (8.4 1017 molecules
CO2 m-2, or 0.84 molecule nm-2) representing chemisorbed
CO2. Hence, the misfit between the OH density and the Ni
density (theoretical monolayer coverage) would represent the
contribution of the cus Al3+ and some basic sites.
From these considerations, it may be inferred that in the
systems with Ni loadings in excess of 1%, multilayers probably
start piling up, with approximatively two layers for the sample
with 1.6% and three layers for that with 3% Ni. As seen above,
these multilayers remain on the surface even after exhaustive
washing. For the sample with 3 wt % Ni, it seems clear from
the IR data that the initial configuration of the metal complex
is preserved, which is also coherent with the greenish coloration
of the impregnated solid and the higher amounts of Ni released
in the wash solution.
In summary, the results point to a model in which the
interaction between Ni(acac)2 and Al2O3 results in the coordina-
tion of nickel linked through one acac ligand to surface
hydoxyls, the formation of an enolate by adsorption of one acac
ligand on surface cus Al3+ sites, and, in a lesser proportion,
adsorption on the surface of Hacac and/or Hads. Basic surface
sites are probably also involved. These different surface species
may be represented as in the scheme given below, based on
the internal consistency of the results, the general agreement
with recent results for the same system obtained via vapor-phase
deposition,6,7 and with other oxide-supported metal acetyl-
acetonates prepared in the liquid phase, as for example, Pd-
(acac)2/alumina.49,50
Conclusions
The adsorption in the liquid phase of nickel acetylacetonate
on commercial R-alumina has been studied. The existence of
metal precursor-support interactions has been deduced from
qualitative analysis (color change of the solution and of the
solid), adsorption kinetics, and washing data. The spectroscopic
results (IR and XPS) support the hypothesis, providing evidence
for modifications involving electronic changes of the precursor
in its adsorbed state.
A model for the interaction between Ni(acac)2 and alumina
involving a ligand exchange mechanism at the adsorption step
is proposed in which a reaction with both OH groups and Al3+
sites occurs. This reaction is limited to the number of sites
available on the surface. It is also suggested that basic surface
oxygens probably constitute adsorption sites. The validity of
the model proposed is supported by (i) the presence of Ni in
the washing solution only for the metal loadings in excess of
J. Phys. Chem. B, Vol. 103, No. 29, 1999 6045
monolayer coverage, (ii) the spectroscopic results, in particular
the IR data showing the reaction with OH groups of the support,
the formation of Al(acac) species, and the absence of ring
opening of the organic moiety, and (iii) the C/Ni ratios, which
are coherent with the stoichiometry of the overall reaction. It
has been also established that the reaction between Hacac and
alumina occurs by not only interaction with cus Al3+ but perhaps
also with surface OH groups of the support.
A theoretical density of 2.7 molecules of Ni(acac)2 nm-2 has
been estimated for the formation of a monolayer (around 0.8-
1% Ni), a value that is in qualitative agreement with the IR
observations but higher than values reported for similar catalysts.
For higher metal content, piling in multilayers is likely.
Acknowledgment. R.M. gratefully acknowledges Colcien-
cias, Colombia, for a doctoral grant. The authors are indebted
to Prof. E. Vansant, Universitaire Instellingen, Antwerpen, for
the CO2 sorption measurements, and Prof. P. Grobet, Centrum
voor Oppervlaktechemie en Katalyse, K.U. Leuven, for the
27Al MAS NMR analysis.
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