Journal of Catalysis 305 (2013) 1–6

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Influence of base strength on the catalytic performance of nano-sized

alkaline earth metal oxides supported on carbon nanofibers
A.M. Frey a, J. Yang a,1, C. Feche b, N. Essayem b, D.R. Stellwagen a, F. Figueras b, K.P. de Jong a,⇑, J.H. Bitter a,⇑
a
Inorganic Chemistry and Catalysis, Department of Chemistry, Utrecht University, Universiteitsweg 99, 3584CE Utrecht, The Netherlands
b
Institut de recherches sur la catalyse et l’enviroment de Lyon, 2 avenue Albert Einstein, F-69626 Villeurbanne Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Nano-sized (3 nm) alkaline earth metal oxides supported on carbon nanofibers were prepared by a facile
Received 25 January 2013 impregnation and heat treatment method of the corresponding nitrates. These supported catalysts
Revised 26 March 2013 showed a significant improved activity for the aldol reaction and transesterification compared to the
Accepted 24 April 2013
respective bulk materials which did not show any appreciable activity. A linear correlation was found
Available online 24 May 2013
between the initial reaction rate and the strength of the basic sites as determined by CO2 calorimetry
indicating the importance of the base in the rate determining step of the reactions.
Keywords:
Ó 2013 Elsevier Inc. All rights reserved.
Nano-sized alkaline earth metal oxides
Carbon nanofibers
Solid base catalysts
Base strength
Transesterification
Aldol reaction

1. Introduction Though a number of groundbreaking papers appeared on

Base catalysts draw increasing interest mainly due to the
growing biomass field and related conversions such as transesteri-
fication and aldol condensations [1–3]. Solid base catalysts offer
several advantages with respect to their homogeneous counter-
parts such as easy regeneration, easy separation as well as being
less corrosive [4–6]. The drawback of bulk solid bases is the low
number of sites per unit mass. Supporting a solid base as nano-
sized particles will, however, overcome this drawback [7,8]. The
activity of solid bases is determined by the number and the base
strength of the sites. Here, we will report on the preparation,
characterization, and catalytic actions of monodispersed supported
alkaline earth metal oxides (MO). This allows us to investigate the
role solely of base strength on base-catalyzed reactions.
Bulk MgO, CaO, SrO, and BaO have been investigated as base
catalysts for conversion such as isomerization reactions [9,10],
Claisen–Schmidt condensations [11,12], Knoevenagel condensa-
tion [13], Michael additions [14], Tishchenko reactions [15], aldol
condensations [16], and transesterification reactions [17] (for more
details we refer to a landmark review of Corma and Iborra [1]).
⇑ Corresponding authors.
E-mail address: j.h.bitter@uu.nl (J.H. Bitter).
1
Present address: Laboratory of Physical Chemistry and Colloid Science, Wageningen
University, Dreijenplein 6, 6703 HB Wageningen, The Netherlands.
supported solid base catalysts [18,19], a comprehensive study on
the independent influence of the number and strength of basic
sites is, to the best of our knowledge, lacking.
Haneda et al. studied alkaline earth metal oxides supported on
Co3O4 for direct NO decomposition [20]. It was found that the
alkaline earth metal oxide interacted closely with the support,
forming mixed oxides being the catalytic active species, e.g.,
SrCoO2.5+d. Catalytic conversion depended on the number of base
sites and their strength, though the latter was not quantified.
Vasefir and Parvari used c-alumina-supported alkaline earth
metal oxides and c-alumina-supported cobalt for mercaptan oxi-
dation [21]. The number of base sites for the MO varied with that
of MgO being significantly higher than for the other supported
oxides. Both the number of active sites and the base strength
was considered to be important for the catalytic performance. It
was assumed that the base strength increased down the group
though it was not quantified.
TPD and calorimetry of CO2 are powerful tools to analyze num-
ber and strength of base sites [22,23,18]. TPD reveals the amount of
adsorbed CO2 by evaluating the peak area in the TPD trace. The po-
sition of the TPD peaks is indicative for the strength with which
CO2 was bonded to the surface, i.e., indicative for the base strength.
Chen et al. used this tool to study the influence of the calcination
procedure on the amount and strength of basic sites in MO on
c-Al2O3 [24]. Irrespective of the calcination temperature, the peak

0021-9517/$ - see front matter Ó 2013 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcat.2013.04.019
2 A.M. Frey et al. / Journal of Catalysis 305 (2013) 1–6
position in the TPD was located at increasing temperatures when
going down the group of alkaline earth metal oxides showing that
the base strength increased down the group.
Calorimetry of CO2 adsorption is able to reveal the strength of
base sites. For example, Horiuchi et al. used this technique to
investigate the basicity of ceramics based on c-Al2O3 and MO
[25]. The heat of CO2 adsorption was found to increase with
decreasing electronegativity of the investigated metals in the
materials, showing that the base strength increased down a group.
In this study, we have investigated the influence of base
strength on catalytic activity for supported alkaline earth metal
oxide containing the same number of active sites per unit mass.
MO were supported on carbon nanofibers (CNF) staring from the
cheap and widely available nitrate precursors. Carbon nanofibers
have been used as support to suppress support/metal oxide inter-
actions as often seen for traditional oxide support as discussed
above [20]. Bulk MOs prepared from the same precursors were
included for comparison. After preparation, the materials were
characterized by CO2-chemisorption, CO2-calorimetry, XRD, and
TEM. Biomass-related processes as the transesterification and the
self-condensation reaction of acetone to diacetone alcohol (DAA)
as example of an aldol reaction were chosen as test reaction
(Scheme 1).
2. Materials and methods
2.1. Preparation of the catalysts
2.1.1. Bulk metal oxides
The bulk metal oxides were prepared from the nitrate-precur-
sors, magnesium nitrate hexahydrate (Acros, 99+%), calcium
nitrate tetrahydrate (Sigma–Aldrich, 99%), strontium nitrate (Sig-
ma–Aldrich, p.a.), and barium nitrate (Fluka, p.a.) by heat treat-
ment at 700 °C for 2 h (10 °C min 1) in stagnate air.
A high surface area MgO (230 m2 g 1) from Stream Chemicals
was stored under N2 and used without any activation procedure.
2.1.2. Alkaline earth metal oxide supported on carbon nanofibers
Oxidized carbon nanofibers (CNF) (pore volume 0.7 ml g 1)
were prepared from syngas at 550 °C and 3 bars overpressure using
a 5 wt% Ni/SiO2 catalyst as described in detail elsewhere [7]. 2.5 g
CNF was dried overnight at 120 °C, followed by evacuation for half
an hour. The desired metal was introduced to the support by incip-
ient wetness impregnation using an aqueous solution of the metal
nitrate salt. The loadings were 3.4 wt% MgO, 4.8 wt% CaO, 8.8 wt%
SrO, and 13 wt% BaO on CNF. These loadings result in equimolar
amounts of metal oxide in the catalysts. In case of BaO, three
impregnations with barium nitrate were needed to obtain the high
Scheme 1. (a) Self-condensation of acetone to diacetone alcohol and (b) transesterification of triacetin with methanol.
loading. After impregnation, the samples were equilibrated for
12 h followed by drying in stagnant air for 12 h at 120 °C. The sam-
ples (25–150 lm fraction) were heat treated in 30 ml min 1 N2 at
600 °C for 3 h (5 °C min 1) immediately prior to the catalytic test.
2.2. Catalyst testing
2.2.1. Self-condensation of acetone to diacetone alcohol
The self-condensation of acetone was carried out at 0 °C in a
200-ml double-walled thermostatted batch glass reactor using
100 g of acetone as reactant, 6 g of iso-octane as an internal stan-
dard, and 1 g of catalyst. Prior to the experiment, the reactor was
flushed with nitrogen and during the entire experiment a nitrogen
atmosphere was kept over the reaction to avoid exposure to air.
The reaction mixture was mechanically stirred with 1700 rpm.
Aliquots of 1 ml solution were taken at specific times during a total
of 24 h. The samples were filtrated through hyflo (Sigma Aldrich) in
order to remove traces of catalyst before GC analysis.
2.2.2. Regeneration test
The first catalyst test was performed as described above. After
24 h of test, the catalyst was isolated by centrifugation and decan-
tation and washed with 3 30 ml acetone and 2  30 ml heptane
followed by drying at 120 °C for 18 h in stagnant air. After this
procedure, the catalyst was heat treated in 30 ml min 1 N2 at
600 °C for 3 h (5 °C min 1) immediately prior to the second catalyst
test. The same procedure was carried out before the third activity
experiment.
The concentration of diacetone alcohol in the aliquots was mea-
sured using a Chrompack CP 9001 gas chromatograph equipped
with a CP-SIL-5 column and an FID detector in all types of catalytic
experiments. Traces of by-products were identified with a
Shimadzu GCMS-QP2010. Since only traces of by-products were
observed, the initial catalytic activity was expressed as
1 1
mmolacetone converted mmolMO h over the first 15 min of the reaction
where mmolacetone converted was defined as 2 mmolDAA formed.
2.2.3. Transesterification
The transesterification reaction was carried out in N2 atmo-
sphere at 60 °C in a 100-ml round-bottom flask using 10 g triacetin,
11.7 ml methanol, 0.3 ml toluene as internal standard, and 100 mg
of catalyst while stirring at 500 rpm. Aliquots of 0.2 ml solution
were taken at specific times during a total of 3 h and diluted with
1 ml dicholoromethane. The samples were filtrated through a
micropore filter in order to remove traces of catalyst before GC
analysis. The triacetin concentration was measured on a Shimadzu
GC 2010 with a CP8822 column equipped with an FID detector, and
1 1
the activity was expressed as mmoltriacetin converted mmolMO h .
 A.M. Frey et al. / Journal of Catalysis 305 (2013) 1–6
2.3. Characterization
The N2-physisorption experiments were performed at 196 °C
on a Micrometrics Tristar Surface Area and Porosity analyzer. The
measurements were used to determine pore volumes and specific
surface areas of the catalysts using BET theory.
A number of base sites were evaluated using volumetric CO2
adsorption (Micromeritics ASAP 2010C) at 0 °C. The samples were
dried in situ at 450 °C in vacuum for at least 20 h prior to measure-
ments. Prior to vacuum drying, all samples had been heated to
600 °C in nitrogen for 3 h under similar condition as before the
catalytic tests. Adsorption isotherms were obtained by plotting
CO2 uptake versus the absolute pressure. The total number of ba-
sics sites was determined by extrapolation the linear part of the
isotherm (100–250 mbar) to zero bar pressure.
The heat of adsorption of CO2 at 30 °C was measured for the
supported samples in a Tian–Calvet calorimeter after a pretreat-
ment at 450 °C in vacuum for 2 h [26,27].
Powder X-ray diffraction (XRD) was measured using an Enraf–
Nonius CPS 120 apparatus with Co Ka radiation (k = 1.789 Å).
The supported samples were examined with transmission
electron microscopy (TEM) using an FEI Tecnai 12 or in an FEI
Technai 20F. The samples were placed on holy carbon grid, and
both bright field and dark field TEM images were recorded.
3. Results and discussion
3.1. Characterization
Table 1 displays selected properties of the supported alkaline
earth metal oxides under study.
All bulk samples had very low specific surface areas, 0–2 m2 g 1
in accordance with literature [1], whereas supported catalysts had
surface areas of about 150 m2 g 1 which is close to that of the sup-
port. The amount of CO2 adsorbed on the supported catalysts (at
0 °C) was similar for all samples (165  15 lmol CO2 gcat1 ) which
shows that the number of accessible base sites per gram of catalyst
is comparable.
TEM was used to investigate the particle size of the supported
MOs (Fig. 1).
Fig. 1a–d displays bright field images in which next to the oxide
(white arrows) only short fibers are visible. A more comprehensive
TEM study (not shown) indicated that also longer fibers 0.5–1 lm
are present. The metal oxide particles are more visible in dark field
mode as shown in Fig. 1e.
Fig. 2 displays the particle size distribution in the different cat-
alyst base on TEM analysis. The average particle size of the oxides
was 2.7 nm for MgO, 3.0 nm for CaO, 3.1 nm for SrO, and 3.6 nm for
BaO with a narrow size distribution as shown in the figure.
The increase from 2.7 nm for MgO to 3.6 nm for BaO correlates
with the increase in unit cell size of 30% when going from MgO to
BaO [28]. Therefore, all samples contain the same number of
surface atoms per oxide particle. As the molar loading of the oxides
was the same, the number of accessible base sites per gram of
Table 1
Loading, specific surface area, initial activity, CO2 uptake, and initial heat of adsorption for the investigated samples.
Catalyst BET (m2 g 1
) Heat of CO2 ads. (kJ mol
a b
MgO/CNF 138 105 /107
CaO/CNF 143 120a/106b
SrO/CNF 166 162a/121b
BaO/CNF 141 193a/132b
a
Initial heat of CO2 adsorption (0–5 lmol/gcat).
b
Average heat of CO2 adsorption (10–50 lmol/gcat).
c 1
Initial rate is calculated as mmol converted reactant molecules per mmol MO in the sample per h
3
catalyst was also the same, which is in agreement with the CO2
sorption data.
In order to study the base strength of the active sites, micro cal-
orimetry was applied. The curves showing the differential heat of
CO2 adsorption on the supported alkaline earth metal oxides are
displayed in Fig. 3.
For the supported MO samples, the initial differential heat of
CO2 adsorption increased from 105 to 193 kJ mol 1 (0–5 lmol of
adsorbed CO2 gcat1 , Table 1), when going from MgO to BaO. For bulk
materials, a similar trend in the initial heat of adsorption has been
reported though in a narrower range, i.e., 120–160 kJ mol 1 [29].
The strongest base sites of SrO/CNF and BaO/CNF (Table 1, Fig. 3)
are comparable in strength to the super basic sites present in bulk
LaMgO, CsY, and NaN3/NaY [27,30]. In our materials, these strong
base sites are, however, only found for a limited number of sites
while the majority of the base sites displayed a lower differential
heat of CO2 adsorption, 100–130 kJ mol 1, at higher CO2 coverages.
The trend in basicity for these sites is the same as for the strong ba-
sic site, i.e., BaO/CNF > SrO/CNF > CaO/CNF  MgO/CNF.
The crystalline phases present in the samples were investigated
by XRD analysis of materials which had been exposed to air during
preparation and XRD measurement. The diffractograms after
subtraction of the background are displayed in Fig. 4 for the sup-
ported materials.
For the supported samples, the XRD patterns were dominated
by diffraction peaks originating from CNF. For MgO/CNF and CaO/
CNF, no additional diffraction peaks were observed. For SrO/CNF
and BaO/CNF, diffraction peaks with low intensity were observed
as indicated with marks in the figure. These could be ascribed to
traces of the respective metal carbonates. Carbonate formation is
due to reaction between the oxide and CO2 in the atmosphere
before or during the XRD measurement. Since no reflection repre-
senting oxides are found, it is likely that the metal oxides on the
carbon nanofibers were amorphous and or too small to be
detected, while the carbonate of the heavier alkaline earth metal
oxides are more crystalline. For carbon nanofiber samples, an
in situ XRD study was performed following the decomposition of
the nitrates and the formation of the oxides. Due to the partial
amorphous nature of the oxides (Fig. 4), higher loadings of the
alkaline earth metal were in order to increase the likelihood of
observing the phases. The results are found in the Supplementary
material S1. For the sample with higher loadings, it was found that
exclusively oxide (Mg, Ca, and Sr) or amorphous phase (in the case
Ba) is present after the heat treatment. No carbonate is thus
observed after the activation procedure if the samples are not ex-
posed to the air. It is, however, interesting to note that the forma-
tion of the oxides on the CNF goes via a carbonate route for Ca, Sr,
and Ba.
3.2. Catalytic activity
The catalytic activities of the bulk and supported materials in
the self-condensation of acetone to DAA are shown in Fig. 5. The
thermo dynamical calculated equilibrium concentration of DAA
1
) CO2 uptake (lmol gcat1 ) Rate acetone (h 1
) c
Rate triacetin (h 1
) c
180 16 180
154 62 211
174 122 313
168 232 458
, evaluated over the first 15 min reaction time.
4 A.M. Frey et al. / Journal of Catalysis 305 (2013) 1–6

Fig. 1. TEM images of (a) BaO/CNF, (b) SrO/CNF, (c) CaO/CNF, (d) MgO/CNF, and (e) HAADF of MgO/CNF.

Fig. 2. Particles size distribution and average particle size measured in TEM (a) MgO/CNF, (b) CaO/CNF, and (c) SrO/CNF (d) BaO/CNF.
 A.M. Frey et al. / Journal of Catalysis 305 (2013) 1–6
Fig. 3. Differential heat of CO2 adsorption for MgO/CNF, CaO/CNF, SrO/CNF, and
BaO/CNF versus the accumulated amount of CO2 adsorbed on the material.
Fig. 4. XRD of alkaline earth metal oxides on CNF.
Fig. 5. Catalytic performance of the samples for acetone self-condensation (1 g of
catalyst, 100 g acetone 0 °C, N2 atmosphere). Equilibrium concentration of diace-
tone alcohol is 1.4 M at this temperature.
at 0 °C is 1.4 M [31]. The selectivity toward DAA in all cases was
higher than 95% calculated from the intensity of the peaks in the
FID chromatograms evaluating the flow of carbon in the gas
stream. The traces of by-products were identified as mesityl oxide
and products related to coupling of 3 acetone molecules with
different degrees of dehydration. However, due to the high selec-
tivity toward DAA, the catalytic performance can be evaluated as
the formation of DAA versus time.
For the bulk materials, only BaO, the most active one (initial
rate <0.1 h 1), is included in the figure. Clearly, the bulk materials
were at least an order of magnitude less active compared to the
5
Fig. 6. Initial rate versus initial heat of CO2 adsorption for the strongest base sites
for the alkaline earth metal oxides supported on CNF.
Fig. 7. Reuse of CaO/CNF in the self-condensation of acetone to diacetone alcohol.
The sample was washed with acetone/heptane and heat-treated in N2 at 600 °C for
3 h (5 °C min 1) between the tests.
supported materials. The low conversion of the bulk materials is
attributed to their low specific surface area (Table 1) as will be dis-
cussed later.
From Fig. 5, it is clear that the activity of the supported catalysts
increases from MgO to BaO. The initial activity expressed as mol
product molecules converted per mol metal oxide, MO, per time
(evaluated over the first 15 min of the reaction) increased as
MgO/CNF (16 h 1) < CaO/CNF (62 h 1) < SrO/CNF (122 h 1) < BaO/
CNF (232 h 1). In the transesterification reaction, a similar pattern
in catalytic behavior was found: MgO/CNF (156 h 1) < CaO/CNF
(183 h 1) < SrO/CNF (271 h 1) < BaO/CNF (398 h 1). With the num-
ber of base sites being similar for all supported catalysts (see Table
1), the variation in catalytic activity can be directly correlated with
the differences in base strength. This is expressed in Fig. 6.
Fig. 6 shows the relation between the initial heat of CO2 adsorp-
tion, a measure for base strength, and the initial activity for both
the aldol condensation and the transesterification of triacetin. A
positive correlation between the initial heat of CO2 adsorption
and the initial rate of reaction for supported MOs is apparent from
the figure. For the self-condensation of acetone to diacetone alco-
hol, this is in accordance with a mechanistic study [32] where
the rate determining step was found to be the C–C coupling though
it was suggested that a higher enolate concentration on the surface
due to the presence of stronger base sites in the catalyst would
increase the rate of the overall reaction. The mechanism of the
base-catalyzed transesterification and the corresponding rate
determining step is still unclear [33]. However, the fact that we
have shown the positive influence of base strength on the reaction
rate might support the hypothesis that methanol adsorption/
deprotonation is rate determining [34].
Stability and regeneration possibilities for the supported mate-
rials were investigated for the aldol reaction. CaO on CNF was cho-
sen as a case study. The results are shown in Fig. 7.
6 A.M. Frey et al. / Journal of Catalysis 305 (2013) 1–6

catalyst particles. A positive correlation between the heat of CO2

adsorption and the catalytic activities in the self-condensation of
acetone to diacetone alcohol as well as the transesterification of
triacetin with methanol were established. This clearly shows the
importance of base strength. Compared to bulk MO catalyst with
low specific surface area, the supported nano-sized MO were or-
ders of magnitudes more active showing the impact of the number
of base sites. The highly active supported alkaline earth metal oxi-
des could be regenerated at reused with only minor loss in activity.

Appendix A. Supplementary material

Fig. 8. Use and reuse of high surface area bulk MgO. The sample was washed with Supplementary data associated with this article can be found, in
acetone/heptane and heat-treated in N2 at 600 °C for 3 h (5 °C min 1) between the the online version, at http://dx.doi.org/10.1016/j.jcat.2013.04.019.
tests.

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