CROATICA CHEMICA ACTA

CCACAA 81 (3) 443¿451 (2008)

ISSN-0011-1643
CCA-3263
Original Scientific Paper

Amorphization Effects on the Basic Sites of Nanometric

Magnesium Oxide

Neftalí Lenin Villarreal Carreño,a,* David Keyson,b Marcia Tsuyama Escote,b

Edson Roberto Leite,b Elson Longo,b Humberto Vieira Fajardo,c,* Luiz Fernando Dias Probst,c
Antoninho Valentini,d Miryam Rincón Joya,e and Paulo Sergio Pizanie

a
Instituto de Química, DQAI, Universidade Federal de Pelotas, CP-354, CEP-96010-900,
Capão do Leão, RS, Brazil
b
Departamento de Química, Universidade Federal de São Carlos, 13565-905, São Carlos – SP, Brasil
c
Departamento de Química, Universidade Federal de Santa Catarina, 88040-900 Florianópolis – SC, Brasil
d
Departamento de Química Analítica e Físico-Química, Universidade Federal do Ceará, 60455-760,
Fortaleza – CE, Brasil
e
Departamento de Física, Universidade Federal de São Carlos, 13565-905, São Carlos – SP, Brasil

RECEIVED DECEMBER 20, 2005; REVISED MAY 8, 2007; ACCEPTED JUNE 20, 2007

The paper reports the catalytic action of the basic sites of nanocrystalline particles of rare
earth-doped magnesium oxide in the aldolization reaction between acetone and methanol leading
to the C–C bond formation of an a,b-unsaturated compound (methyl vinyl ketone), also forming
methyl ethyl ketone and isopropyl alcohol. Undoped and doped MgO samples were prepared by
high-energy mechanical milling of commercial Mg, Y and Ce oxide powders. Catalytic activity
Keywords and surface basicity of these compounds were strongly influenced by doping and the time of me-
magnesium oxide chanical milling (amorphization process). Such milling leads to the formation of nanocrystalline
amorphization materials. Influence of mechanical processing of these compounds was investigated by means of
catalysts N2 adsorption (BET), X-ray diffraction (XRD), TEM, CO2 chemisorption and room temperature
photoluminescence photoluminescence emission. Strong changes of polar groups such as hydroxyl groups on the
aldol condensation surface of the solid were directly related to the photoluminescence emission observed.

INTRODUCTION morphology and precursor sources, affect the surface

uniformity of product oxides and thereby the activity of
Several catalytic processes are promoted by rare earth-
these materials.1–4
doped magnesium oxides, and effects of rare earth oxide
addition in the amorphization process have been also re- The basicity and basic strength distribution (weak,
ported. Processing features of the preparation methods, strong and intermediate strength basic sites) of magne-
such as annealing temperature and time, gas environment, sium oxide promoted by rare earth doping are well known,

* Authors to whom correspondence should be addressed. (E-mail: neftali@[Link]; hfajardo@[Link])

444 N. L. V. CARREÑO et al.

but these surface properties are strongly influenced by coupled to a cooled GaAs photomultiplier and a conven-
preparation conditions, rare earth promoter and also by tional photon counting system. The 488 nm lines of an ar-
its concentration.5–8 gon ion laser were used as excitation light. The maximum
High-energy mechanical milling is a well-known output power of the laser was kept within 200–300 mW and
process employed in the preparation of nanostructured cylindrical lenses were used to prevent sample overheating.
All measurements were taken at room temperature.
metals and alloys, which has now become quite popular
in ceramic materials processing.9 The objectives of mill- The N2 adsorption isotherms at liquid N2 temperature
and CO2 adsorption isotherms at 27 °C were determined
ing include particle size reduction, mixing or blending,
with an Autosorb-1C instrument (Quantachrome Instru-
and particle morphology changes.10
ments, USA). Samples were first heated and degassed at
With the aim to prepare nanostructured metal oxide, 300 °C, then maintained at that temperature for 1 h. Deter-
this paper presents the results observed in the high-en- mination of the specific surface area of the samples was
ergy mechanical milling process applied in the prepara- done by the BET method. The amount of irreversible CO2
tion of nanostructured MgO. To follow changes in the ma- uptake was obtained from the difference between the total
terial properties due to the amorphization process, CO2 CO2 adsorption on the catalyst and another CO2 adsorption
adsorption and photoluminescence emission were carried series determined after evacuation of the catalyst sample
out. In addition, the catalytic activity of the basic sites for 20 minutes, at the same temperature.
on the aldolization reaction between acetone and metha-
nol, leading to the C–C bond formation for the synthesis Catalytic Measurements
of an a,b-unsaturated compound (methyl vinyl ketone),
Gas-phase catalytic vinylation of acetone to methyl vinyl
was monitored. This catalytic reaction can be used as a ketone (MVK) was carried out in a fixed-bed continuous
probe to evaluate changes in the catalyst surface due to flow reactor made of stainless steel, at atmospheric pres-
the preparation process.11 sure (300 ºC) and loaded with 0.1 g of catalyst. Catalysts
Catalytic syntheses of a,b-unsaturated compounds were first heated in a flow of helium up to 350 ºC and then
(via aldol condensation) are economically attractive ow- maintained at that temperature for 1 h. The reaction gas
ing to their applications as raw materials for many syn- was composed of acetone and methanol in a 1:2 mole ratio.
thetic organic processes.12 The total flow rate of the reaction gas was 60 cm3/min,
with He as carrier gas. Products were analyzed by gas chro-
matography (SHIMADZU 14B GC instrument), with a
EXPERIMENTAL flame ionization detector and a CBP1 column, for 4 hours
time-on-stream.
Sample Preparation
MgO powders (E. Merck, Germany), pure and mixed with
CeO2 or Y2O3 (E. Merck, Germany) at mole ratios 5:95 and RESULTS AND DISCUSSION
10:90, were obtained by the conventional mixed-oxide Crystalline Phase Characterization
method. They were mechanically milled, using a high-en-
ergy attrition mill (Szegvari Attritor System 01HD). The Figure 1 shows the typical patterns of MgO, pure and
rotation speed was fixed at 500 rpm, using ZrO2 milling doped with CeO2 (mole fraction, x = 10 %) and Y2O3 (x
spheres with 2.0 mm diameter, dispersed in an isopropyl al- = 5 and 10 %), subjected to several mechanical milling
cohol solution at room temperature. Experiments were con- times. Peaks of the samples mechanically milled for 1
ducted individually at the same rotation speed for different hour were indexed as belonging to MgO, CeO2 and
milling times (1, 20, 40 and 80 h). Y2O3 according to the literature.13 The figures also dis-
play the behavior of the crystalline structure when the
Characterization compounds were subjected to higher milling times, t. The
evolutions were observed by the X-ray diffraction mea-
Powder characterization by X-ray diffraction (XRD) of
undoped and doped MgO samples was performed in a
surements taken after the period t. A typical example is
D5000 XRD Siemens diffractometer, equipped with a shown in Figure 1a, displaying the patterns of pure MgO
graphite monochromator and using Cu-Ka radiation, 2q obtained after different milling times. First, it is impor-
ranging from 10 to 75o. The measurements were performed tant to note that the patterns for samples milled for more
in order to analyze the structural evolution as the time of than 20 hours revealed not only reflections belonging to
mechanical milling was increased. For the transmission MgO but also to the additional magnesium hydroxide
electron microscopy (TEM) study, performed using a 200 (Mg(OH)2) phase formation due to the milling process
kV Model CM200 from Philips, Holland, a drop of the (Figure 1a). Peaks of Mg(OH)2 became more intense as t
powder suspension was deposited on a carbon-covered increased, and after 80 hours of milling time the XRD
nickel grid. suggested the Mg(OH)2 as the main phase. From these
Photoluminescence spectra measurements were per- diffractograms, we have estimated the full maximum at
formed using a U1000 Jobin-Yvon double monochromator half width FWHM of the reflection at 2q ≈ 42° to verify

Croat. Chem. Acta 81 (3) 443¿451 (2008)

AMORPHIZATION EFFECTS ON THE BASIC SITES OF NANOMETRIC MgO 445

n c n n
n MgO (a) n MgO (b)
c Y O
+ Mg(OH)2 n
2 3
+ Mg(OH)2 c
n c c
c
1h
I / a.u.
1h

I / a.u.
+
20 h 10 h
+
40 h 20 h
+ + +
+ + 40 h
80 h 80 h
20 30 40 50 60 70 20 30 40 50 60 70
2θ / degree 2θ / degree

c
n ϕ (d)
nMgO (c)
c Y O n MgO
2 3
+ Mg(OH)2 n ϕ CeO2 ϕ
c ϕ
c
c c ϕ n
1h ϕn
1h
10 h 10 h
I / a.u.

I / a.u.
20 h 20 h
+ 40 h
40 h
+ 80 h
80 h
20 30 40 50 60 70 20 30 40 50 60
2θ / degree 2θ / degree

Figure 1. XRD patterns obtained from a) undoped; b) Y (x = 10 %), c) Y (x = 5 %), and d) Ce (x = 10 %) doped MgO powders milled
for different times.

this point. We have obtained average FWHM values Based on these data, we have calculated the lattice
close to 0.6° and, using the Scherrer relation, the average parameters by using the Fullprof refinement program.17
grain size close to 10 nm for these samples.14 For this, we have assumed the samples to be a mixture
The X-ray diffraction patterns of MgO doped with of oxides of Mg and of R (R = Ce and Y) and, in some
Y2O3 and CeO2 disclosed similar results (see Figures cases, we have also added Mg(OH)2.18 The values of lat-
1b-d). However, we have not observed the presence of tice parameters obtained for MgO, MgO-Y2O3 (10 %)
the Mg(OH)2 phase for the samples doped with CeO2. In and MgO-CeO2 (10 %) are listed in Table I. These val-
addition, such patterns also revealed that the content of ues are in good agreement with those of a = 4.21, 10.604
the MgO amorphous phase seemed to be related to the and 5.411 Å reported for the MgO, Y2O3 and CeO2, re-
concentration of rare earths. In fact, comparing Figures spectively, in the literature.13
1b and 1c, we verify that the fraction of crystalline According to the experimental results and a quan-
MgO, after 20 h of milling, was higher for the sample tum mechanics study earlier reported by several authors,
with 5 % than for the sample with 10 % of Y2O3. We be- water vapour is chemically adsorbed on the surface of
lieve that this behavior was associated with the abrasive MgO, resulting in magnesium vacancies.19–21 In this
characteristics of the rare earth oxides.15,16 process, one water molecule interacts with one MgO

TABLE I. Calculated lattice parameters of MgO powders, pure and doped with Y and Ce, subjected to different times of milling

Milling time / h: 1h 20 h 40 h 80 h
a/Å
MgO aMgO 4.214(2) 4.216(3) 4.206(4) 4.22(1)
aMg(OH)2 – 3.121 3.115 3.091
MgOY 10 % (a) aMgO 4.223(1) 4.223(1) 4.216(4) 4.225(3)
aY2O3 10.617(2) 10.617(3) 10.607(7) 10.664(5)
MgOCe 10 % (a) aMgO 4.2222(7) 4.216(1) 4.23(1) 4.22(5)
aCeO2 5.4157(6) 5.408(1) 5.415(1) 5.414(1)
(a) xY and xCe is 10 %.

Croat. Chem. Acta 81 (3) 443¿451 (2008)

446 N. L. V. CARREÑO et al.

analyses also showed that the particles did not exhibit a

homogeneous form. Figure 2c presents the HRTEM im-
age of Ce-doped MgO (x = 10 %), milled for 40 h, illus-
trating the cleavage of crystalline planes (marked by
dark arrows).15

Chemical Structures Characterized by

Photoluminescence
It is known that crystalline oxides exhibit photolumines-
cence emission at low temperature (–5 to –70 °C). Re-
cently Leite et al.9 reported intense visible photolumine-
scence emission at room temperature in amorphous
nanostructured PbTiO3 powders, prepared by the poly-
meric precursor method. The results pointed to the rela-
tion between the ratio of amorphous phase and the inten-
sity of photoluminescence emission. High-energy me-
chanical milling can modify particle structure, resulting
in localized states in an interfacial region between the
crystalline and amorphous regions. The presence of
these localized states is believed to be responsible for the
photoluminescence emission obtained. Since the photo-
luminescence property is associated with the structural
disorder of a solid material,23 the presence of these lo-
calized states due to the milling process can promote the
photoluminescence emission of a solid at room tempera-
ture.
The photoluminescence technique has received great
attention in several characterization studies of solid sur-
faces.24–28 Therefore, the changes in properties promoted
in the MgO samples due to the milling process and the
influence of CeO2 and Y2O3 were also followed by
photoluminescence emission, at room temperature.
Figure 2. TEM images of MgO powders: a) Y-doped (xY = 10 %) Figure 3 represents the photoluminescence emission
milled for 1 h, b) Y-doped (x = 10 %) milled for 80 h, and spectra of undoped and Y-doped (x = 5 and 10 %) magne-
HRTEM images Ce-doped (xCe = 10 %) milled for 40 h. sium oxide after different milling times (1, 40 and 80 h).
It shows broad photoluminescence emission spectra,
molecule, forming magnesium hydroxide. Since our which are typical of amorphous powders.9,29–30 The
powders are mechanically milled in an isopropyl alcohol spectra exhibit maximum emissions between 515 and
solution at room temperature, such conditions would fa- 540 nm, and the intensity of all samples shows their de-
vor the process of Mg(OH)2 formation. Thus, we believe pendence on the milling time; as can be seen, Figure 3a
that the water molecule dissociation at the active sites of displays negligible photoluminescence emission of the
the MgO crystal surface would occur more easily with MgO starting powder (unmilled).
the mechanical milling process, which leads to the for- The mechanism that led to higher photolumine-
mation of defects and vacancies on the MgO surface and scence intensities in our samples is not clearly under-
the existence of OH groups adsorbed on Mg2+.22 stood, but it may be associated with the increase of the
defect center promoted by the milling process, trans-
forming a previously crystalline structure into an amor-
Microstructure Characterization phous system.
Decrease in particle size was confirmed by TEM analy- Addition of rare earths caused a decrease in the
sis. Figures 2a and b show the Bright-Field (BF) TEM photoluminescence intensity of MgO; such behaviour
images of Y-doped MgO (x = 5 %) milled for 1 and 80 may be attributed to charge disproportionation due to the
h. Random variation in the size of nanocrystalline parti- rare earth doping.
cles was observed. Decrease in the mean particle size upon It has been reported that the photoluminescence in
an increase of the milling time was observed. BF-TEM MgO-based materials is related to the relaxation lumi-

Croat. Chem. Acta 81 (3) 443¿451 (2008)

AMORPHIZATION EFFECTS ON THE BASIC SITES OF NANOMETRIC MgO 447

observed), and especially the role of hydroxyl groups on

the cleavage of silica bonds. These observations indi-
cated dependence of the photoluminescence intensity on
the amount of hydroxyl groups. In another study, Yoshi-
da et al.34 investigated the photoluminescence emission
spectra from hydroxyl groups on magnesium oxide,
which were centered at 520 nm. These hydroxyl groups
are directly related to photoluminescence emission and
can mask the emission from Mg-O ion pairs on the sur-
face. Properties of hydroxyl groups on the surface may
also be influenced by the coordination state. The type of
coordination affects the surface properties, such as ba-
sicity and surface band-gap.34,35
Increase and decrease in the intensity of photolumi-
nescence are correlated with small electronic and struc-
tural perturbations in the chemical surroundings of MgO
active sites, which are strongly affected by the milling
process.

Chemisorption of CO2
Recently, Varga et al.4 reported a promising catalytic ap-
plication of copper oxide dispersed in MgO by mechani-
cal milling. This material exhibited high basicity values,
parallel with the MgO content of samples and milling
time. Other observations in these catalysts suggest an ir-
regular change of the surface area with the increase of
the milling time. A similar behavior was also observed in
the present work in the doped MgO samples, as illus-
trated in Table II.
The CO2 adsorption isotherms are very sensitive to
the presence of polar groups or ions on the surface of the
solid, such as hydroxyl groups.36,37 Carbon dioxide ad-
sorption was used to determine changes in the properties
Figure 3. Photoluminescence spectra of a) undoped; b) Y (x = 10 of the catalysts (basic site) due to the amorphization pro-
%) and c) Y (x = 5 %) doped MgO powders subjected to different
cess. The results based on isotherms (illustrated in Fig-
milling times.
ure 4) show that the CO2 adsorption capacity of MgO is
affected by the doping and by the mechanical milling
nescence of defect centers, once the progress of cracks treatment. In general, the results show that the mechani-
causes bond breaking and nuclear motion, and promotes cal milling treatment contributes to higher CO2 adsorp-
release of atoms and ions from the lattice sites, resulting tion capacity. This suggests that the milling process pro-
in formation of defects.27,28 Moreover, movement of dis-
locations mechanically excites the defects.
Anpo et al.31,32 studied the photocatalyzed isomeri- TABLE II. Specific surface areas (a) of undoped, Y- and Ce-doped
MgO milled powders as a function of milling time(a)
zation of butene on MgO catalysts previously degassed
at high temperature. These catalysts exhibit photolumi- Milling time / h : 1h 40 h 80 h
nescence at 340–450 nm, which was associated with a/ m2 g
coordinatively unsaturated surface ions. The authors’ re- MgO 136 187 346
sults suggest a correlation between the photoluminescence (b)
MgOY 5 % 130 215 114
response and the coordination number of oxygen ions.
MgOY 10 % (c) 80 250 88
In the past decade, Kawaguchi33 reported the effect (b)
MgOCe 5 % 129 57 104
of OH content on the fractoluminescence and photo-
MgOCe 10 % (c) 144 106 114
luminescence spectra of silica glasses. This author also
discussed the formation and excitation processes of oxy- (a) Specific surface area, a, of samples was done by BET method.
gen deficient centers (responsible for the luminescence (b) xY and xCe is 5 %; (c) xY and xCe is 10 %.

Croat. Chem. Acta 81 (3) 443¿451 (2008)

448 N. L. V. CARREÑO et al.

TABLE III. Acetone conversions and selectivities (at 300 °C) of Ce-doped MgO milled samples (a),(b)

Sample Conversion / % Selectivity / %

MVK MEK IPA CCP
MgOCe 5 % 1 h (c) 9.7 33.0 4.1 30.1 32.8
MgOCe 5 % 40 h (c) 14.0 24.4 4.7 30.1 40.8
MgOCe 5 % 80 h (c) 13.5 26.2 5.5 29.1 39.2
MgOCe 10 % 1 h (d) 11.0 30.1 4.4 32.5 33.0
MgOCe 10 % 40 h (d) 15.4 25.0 6.4 44.5 24.1
MgOCe 10 % 80 h (d) 11.1 27.8 5.1 40.9 26.2
(a) The values were determined by means of acetone conversion during 4 h of reaction time.
(b) Symbols: MVK, methyl vinyl ketone; MEK, methyl ethyl ketone; IPA, isopropyl alcohol; CCP, cracking and condensation products.
(c) xCe = 5 %; milling times 1, 40 and 80 h.
(d) xCe = 10 %, milling times 1, 40, 80 h.

OH
H3C CH CH3

H2

O CH3 O O O O
H3C C CH 3 H C H
H3C C CH2 C OH H3C C CH3 H3C C CH CH2
CH3 + O O
H3 C OH H C H
H3C O CH3 H3C OH H C O CH3

O
H3C C CH2 CH3

Scheme 1. Formation of main reaction products in aldol condensation between methanol and acetone.

motes easier access of the CO2 molecule to the adsorp- Catalytic Studies
tion sites of Mg and O. These observations indicate that
the basicity is dependent on the milling time, the rare The aldolization reaction between methanol and acetone
earth promoter and its concentration. was studied for each powder sample to acquire more in-
formation about their basicity properties. This route al-
lowed catalytic C–C bond formation for the synthesis of
a,b-unsaturated compounds (methyl vinyl ketone) by us-
Mg
Total CO2 adsorption / (mmol m–2)

6
MgY5 ing methanol (as a vinylating agent) for the vinylation of
5
MgY10 acetone to methyl vinyl ketone (MVK), also forming me-
MgCe5
MgCe10
thyl ethyl ketone (MEK) and isopropyl alcohol (IPA), see
4 Scheme 1.12 Despite formation of undesirable secondary
products (from condensation and cracking processes) dur-
3
ing the catalytic conversion of acetone (Figure 5 and Ta-
2 ble III), this reaction was taken to be sensitive to the sur-
face characterization of alkaline earth oxide (MgO).
1
The acetone conversion results obtained with MgO,
0 MgOY (x = 5 %) and MgOY (x = 10 %) show a relation
0 20 40 60 80
between the surface area and catalytic activities; the
Milling time / h
higher the surface area, the higher is acetone conversion.
Figure 4. Total amounts of CO2 adsorption capacity, uptake at On the other hand, samples doped with CeO2 show-
27 °C of undoped and doped MgO samples. ed higher acetone conversion in catalysts with a lower

Croat. Chem. Acta 81 (3) 443¿451 (2008)

AMORPHIZATION EFFECTS ON THE BASIC SITES OF NANOMETRIC MgO 449

The aldolization reaction was used as a probe and

allowed monitoring of the basic sites of all samples. It
showed varied selectivity in the aldolization reaction. In
this process, considerable amounts of isopropyl alcohol
and methyl vinyl ketone were formed. According to the
data collected in Figure 5, all samples milled for 1 h led
to values of MVK selectivity close to the value found
for the MgO starting sample. All these samples display
values of total and irreversible CO2 adsorption lower
than the ones obtained for the samples milled for 40 h,
which favoured IPA selectivity.
Scheme 2 illustrates the simultaneous events that
occur during the aldolization reaction; hydrogena-
tion/dehydrogenation and dehydration. Thus, the role of
the basic site strength is to abstract one proton of the ace-
tone molecule to form a carbanion, and this intermediate
compound provides the conditions for the C–C bond for-
mation by the condensation process. The carbanion may
react with the intermediate product of methanol
dehydrogenation, via nucleophilic attack, to give MVK.
The MEK molecule is formed during the reaction of a
second methanol molecule with carbanion. This C–C
bond also occurs via nucleophilic attack; otherwise, the
hydrogenation of acetone molecule leads to IPA. These
pathways were previously discussed by several au-
thors,38–40 who suggested that the catalytic properties of
inorganic magnesium oxide with weak basic sites often
differ from those of oxides with stronger basic sites.
These results indicate that the chemical and physical
properties of milled MgO samples are dependent on and
related to modifications of catalytic basic surfaces.
The herein reported analyses and characterizations
of the active surface sites on milled MgO powders pro-
vide more information about the catalytic phenomena
promoted by surface basicity and hydroxyl groups.

CONCLUSIONS
Analyzing the physical and chemical properties of doped
and undoped milled MgO nanostructured powders, one
can notice that these materials display properties that
Figure 5. Ketone conversions and selectivity (at 300 °C) for sam- differ from those of the same unmilled materials. The
ples of milled powders of undoped MgO and doped MgO-Y2O3. photoluminescence and CO2 chemisorption analyses of
The values were determined by means of acetone conversions alkaline-earth oxides were associated with the monitored
during 4 h of reaction. structural perturbations in hydroxyl groups and in active
basic sites. Structural perturbations are directly related
to the type of defects on the nanocrystalline surfaces that
surface area. This result corroborates the behavior of are promoted by the amorphization process. The results
samples in CO2 adsorption and in the XRD profile. They confirm the ability of the high-energy mechanical mill-
showed higher CO2 adsorption and the Mg(OH)2 peak ing method to modify the catalytic basic properties or
presence. basic strength on catalyst surfaces. Thus, new weak ba-
The results of acetone conversion observed for all sic sites and stronger basic sites are formed during the
samples indicate that an important requisite to improve milling. Consequently, the sensitivity and selectivity of
the activity is to increase the number of OH groups on alkaline-earth oxides may be improved for the catalytic
the catalyst surface. process.

Croat. Chem. Acta 81 (3) 443¿451 (2008)

450 N. L. V. CARREÑO et al.

Scheme 2. Formation of isopropyl alcohol (IPA), methyl vinyl ketone (MVK) and methyl ethyl ketone (MEK) over MgO milled powders via
dehydrogenation and dehydration processes.

The aldolization reaction requires a surface able to 9. E. R. Leite, L. P. S. Santos, N. L. V. Carreño, E. Longo, C.
promote the catalysis of hydrogenation/dehydrogenation A Paskocimas, J. A. Varela, F. Lanciotti Jr., C. E. M. Campos,
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14. E. W. Nuffield, X-Ray Diffraction Methods, John Willey and
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SA@ETAK

Amorfizacijski efekti na bazi~na mjesta nanometarskih ~estica magnezijeva oksida

Neftalí Lenin Villarreal Carreño, David Keyson, Marcia Tsuyama Escote,

Edson Roberto Leite, Elson Longo, Humberto Vieira Fajardo, Luiz Fernando Dias Probst,
Antoninho Valentini, Miryam Rincón Joya i Paulo Sergio Pizani

Opisana je kataliti~ka aktivnost bazi~nih mjesta nanokristalnih ~estica magnezijeva oksida dopiranog ele-
mentima rijetkih zemalja na stvaranje veze C–C u a,b-nezasi}enom spoju (metil-vinil-keton). Nedopirani i do-
pirani uzorci MgO pripravljeni su visokoenergijskim mehani~kim mljevenjem komercijalnih pra{kastih uzora-
ka magnezijeva, itrijeva i cerijeva oksida. Na kataliti~ku aktivnost i povr{insku bazi~nost tih spojeva izrazito
utje~u dopiranje i vrijeme mehani~kog mljevenja (proces amorfizacije). Mljevenje dovodi do stvaranja nano-
kristalnih materijala. Utjecaj mehani~ke obrade spomenutih spojeva istra`en je adsorpcijom N2 (BET), difrak-
cijom rentgenskih zraka, mikroskopijom TEM, adsorpcijom CO2 i fotoluminescencijom pri sobnoj temperaturi.
Velike promjene polarnih grupa, poput hidroksilne, na povr{ini krutine direktno su povezane s opa`enom foto-
luminescencijom.

Croat. Chem. Acta 81 (3) 443¿451 (2008)