Superficies y Vacío 33 (2020) 1-8.

© Sociedad Mexicana de Ciencia y Tecnología de Superficies y Materiales

Pt/Ga-SBA-15 composites synthesis and characterization

R. Hernández Morales, J. G. Pacheco Sosa *, J. G. Torres Torres,

H. Pérez Vidal, M. A. Lunagómez Rocha, D. De la Cruz Romero
División Académica de Ciencias Básicas, Universidad Juárez Autónoma de Tabasco (UJAT)
Cunduacán, Tabasco, 86690, México.

J. Escobar Aguilar#
Instituto Mexicano del Petróleo
G. A. Madero, Cd. de México, 07730, México

M.C. Barrera
Facultad de Ciencias Químicas-Centro de Investigación en Recursos Energéticos y Sustentables, Universidad Veracruzana
Coatzacoalcos, Veracruz, 96538, México
(Received: September 23rd, 2019; Accepted: March 16th, 2020)

Pt (0.5, 1 and 1.5 wt%) was impregnated by incipient wetness on SBA-15 and corresponding Ga-modified (3, 5, 10 and 20
wt%) composites. Gallium nitrate was incorporated directly during the mesoporous siliceous network synthesis. Materials
were characterized by N2 physisorption, X-ray diffraction, Fourier transformed infrared spectroscopy, scanning electron
microscopy and transmission electron microscopy. SBA-15 had surface area greater than 800 m²/g that decreased by Ga
incorporation in binary materials. It seemed that tetrahedral gallium was well-incorporated into mesoporous silica walls. Pt
dispersion slightly diminished (as to that on SBA-15) by augmenting Ga concentration in composites. Corresponding pore
size maxima shifted to lower diameters (as to that of non-impregnated supports) after platinum loading suggesting Pt
crystals inside pores of SBA-15 and Ga-modified carriers. Large cubic platinum crystals were observed over all prepared
materials probably due to sintering (during calcining at 500 °C) of metallic particles weakly interacting with the carriers
surface. After materials annealing (500 °C under static air) metallic platinum was evidenced (by XRD) pointing out to
noble metal reduction that could be facilitated by decomposition of organic remains from Si alkoxide used during supports
synthesis which presence was ascertained by FTIR.

Introduction matrix SBA-15 surface itself is not particularly adequate to

disperse deposited active phases mainly due to its inertness
Siliceous mesoporous materials have received much [7], and very low acidity. Indeed, that pure siliceous solid
attention due to their multiple potential applications in consists of an electronically neutral framework that lacks
adsorption phenomena and catalysis. The mesoporous Brønsted acidity [8]. Thus, a considerable number of efforts
molecular sieve SBA-15 (Santa Barbara Amorphous) has been focused on functionalizing that rather inert siliceous
exhibits interesting characteristics as high surface area (600- surface. Some previous reports have found that Ga-addition
1000 m2/g), thick walls (3-6 nm) and significant to SBA-15 materials could render solids of weak Lewis
hydrothermal stability [1]. Also, Pluronic P123 structure- acidity [9], which amount increased with gallium content in
directing surfactant (non-ionic poly(ethylene glycol)-block- binary formulations, although Brønsted sites creation has
poly(propylene glycol)-blockpoly(ethylene glycol), average also been identified by Ga incorporation into mesoporous
molecular mass ∼ 5800 Da [2]), used during its synthesis is networks [10]. Abscence of strong acid sites could be
cheap, biodegradable and non-toxic [3]. Silica precursors reflected in enhanced stability (in the liquid-phase acylation
like tetra-alkoxysilane, fumed silica and water glass could be of benzoyl chloride with anisole, for instance [9]), as
used during SBA-15 synthesis but some of those SiO2 carbonaceous deposits deposition could be relieved, as to
sources are either expensive or toxic [4]. Thus, low cost eco- those formed over more acidic surfaces (those of zeolites, for
friendly silica precursors are essential to curtail costs of example). However, acidity (type, number and strength) of
SBA-15 manufacturing at large scale. For instance, using prepared composites clearly depend upon method of gallium
sugar leaf ash as low cost raw material for SBA-15 synthesis component introduction [11], which offered possibility of
has been reported [5]. Also, cheap sodium metasilicate has obtaining binary solids of tailor-made surface properties.
been utilized to that end [6]. For sake of simplicity, however, One important variable during preparation of SBA-15-based
tetraethyl orthosilicate (TEOS) is probably the most used materials modified by inorganic additives is the synthesis
silica source during lab-scale fundamental investigations on pH. For instance, gallium precursors remain in cationic form
those ordered matrices. That type of siliceous structured under acidic conditions used during SBA-15 synthesis
solid has been studied as catalysts support due to its uniform (commonly below pH 1). Under those circumstances Ga
mesoporous network that could facilitate interaction of introduction into the mesostructured solid walls seems to be
deposited active phases with bulky molecules to be difficult to achieve. Also, at low pH Ga 3+ cations could
transformed. However, as that of any other SiO2-based neither polymerize nor condense [12]. Also, under strongly
* [email protected], # [email protected]

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acidic environment, gallium could hardly be incorporated Pt impregnation

into SBA-15 framework due to unfavored condensation Pt (0.5, 1.0 and 1.5 wt%) was deposited over SBA-15 and
reaction between gallium hydrate cations and cationic corresponding Ga-modified composites by pore-filling
silicate oligomer. As low pH (~1) is required to promote impregnation using chloroplatinic acid (H2PtCl6 hydrate,
silica precursors condensation there could be a compromise Aldrich, 99.9 wt%) as precursor salt. Impregnated solids
between obtaining high-quality hexagonally ordered SBA- were left aging for 24 h at room temperature to allow Pt ions
15 and proper gallium incorporation into the mesostructured diffusion through composites porous network. Materials
matrix. For the former enough hydrogen bonding is needed were further annealed at 500 °C (6 h, 2 °C/min heating rate).
whereas electrostatic interaction between the surfactant and After annealing under mentioned conditions residual Cl -
the galliosilicate oligomer could be favored at higher pH from Pt salt could be totally eliminated. Indeed, Miura et al.
[13]. Thus, defining optimal conditions for Ga-modified [15], found essentially not chloride residue (as determined
SBA-15 preparation remains an ongoing challenge. by X-ray fluorescence) after calcination at 500 °C of Pt/SiO2
Regarding gallium-modified siliceous mesoporous samples obtained from H2PtCl6 impregnation. Various
matrices used as catalysts support of metallic phases Ni/Ga prepared materials were identified by Pt(y)/Ga(x)-SBA-15
(1-3 wt%)-MCM41 has been prepared and tested in methane key where y stands for impregnated Pt wt% on composites.
dry reforming [14], finding that Ga incorporation was
reflected in decreased number of both strong and medium Materials characterization
basic sites. Also, carbon deposition under reaction conditions Textural properties of various prepared materials were
diminished with gallium addition. However and in spite of determined by N2 physisorption (-198 °C) by using a
their interesting properties, to the best of our knowledge, the Micromeritics Tristar II 3020 equipment. Studied solids
effect of Ga addition at various concentrations on the were previosuly degassed during 4 h (300 °C) to eliminate
properties of SBA-15 binary solids intended to be used as adsorbed species. Surface area and pore size distribution
metallic Pt support has not been addressed in the open distribution (PSD) of various studied solids were determined
literature. In this work, Ga-modified SBA-15 matrices at by BET (Brunauer-Emmett-Teller) and BJH (Barret-Joyner-
various gallium loadings (3, 5, 10 and 20 wt%) were Halenda, desorption data branch) methods, respectively.
prepared by directly adding corresponding nitrate during Structural order of samples was studied by powder X-ray
TEOS-based SBA-15 synthesis. Pt was deposited (0.5, 1 and difracction utilizing a Bruker D8-Advance diffractometer
1.5 wt%) by pore-filling impregnation on obtained (CuKα radiation, λ = 1.5418 Å) at 35 kV accelerating
composites to assess the effect of Ga addition on platinum voltage, 25 mA and 0.020° steps. Samples were analyzed by
dispersion. Materials were characterized through several Fourier transformed infrared spectroscopy (FTIR) with a
physicochemical instrumental techniques to elucidate their Shimadzu IRAffinity-1 apparatus in the 340-4000 cm-1 range
textural, structural and surface properties. at 2 cm-1 resolution and 40 scans. Acquired data were
processed by using IRsolutionTM software. Wafers were
Experimental prepared by mixing samples (at 5 wt%) to be studied with
KBr (Sigma Aldrich, FTIR grade). Particles morphology was
Material synthesis observed by scanning electron microscopy (SEM) in JEOL
Ga-modified SBA-15 JSM-6010LA apparatus at 20 kV accelerating voltage, high
SBA-15 mesoporous materials were synthesized following vacuum and at various magnifications. Obtained
a well-known preparation protocol [1]. Thus, triblock micrographs were processed by using InTouchScopeTM
copolymer Pluronic P123 (OE20OP70OE20 non-ionic software. Materials were characterized by high-resolution
surfactant, Sigma-Aldrich, 98 wt%, 19.2 g) was diluted in transmission electron microscopy (HR-TEM) carried out in
450 ml of water and 300 ml of HNO3 (0.5 M, Meyer, 70 JEOL 2100 field emission electron microscope operating at
wt%) solution were further added. The transparent mixture 200 kV with LaB6 filament (spherical aberration coefficient,
was kept under vigorous stirring for 24 h at 35 °C. Tetraethyl Cs = 0.5 mm). Micrographs were taken in bright field mode.
orthosilicate (TEOS, Sigma-Aldrich, 98 wt%, 40 ml) was Prior to analysis powdered samples were ultrasonically
used as Si source. After TEOS addition the obtained sol was dispersed in isopropyl alcohol and then some drops of
kept under stirring (600 rpm, ~62 rad/s) for 24 h. Then, the obtained suspension were supported on lacey carbon coated
sol was submitted to hydrothermal treatment at 80 °C for 72 copper grids (3.05 mm of diameter).
h. The obtained gel was filtered, washed with distillated
water and dried at room temperature. In order to prepare Ga- Results and discussion
modified samples Ga(NO3)3·H2O (Sigma-Aldrich, 99.9
wt%) was simultaneously added with TEOS. The amount of Textural properties
gallium salt utilized corresponded to various Ga contents (3, SBA-15 and corresponding Ga-modified solids (excepting
5, 10 and 20 wt%) in binary solids. All solids were finally the material with the lowest Ga content) had type IV N2
calcined at 500 °C for 6 h (2 °C/min heating rate) to obtain adsorption isotherms (Figure 1a) with H1 hysteresis as
mixed oxide composites. Various prepared materials were defined by the International Union of Pure and Applied
identified by Ga(x)-SBA-15 key where x stands for Ga wt% Chemistry (IUPAC) [16] those isotherm profiles being
in composites. typical of mesostructured matrices containing cylindrical
pores of uniform section [17]. Hysthereses loop shape of

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Figure 1. N2 adsorption isotherms (at -198 °C) and pore size distribution (BJH profiles), corresponding to (a) and (b) pristine SBA-15 and Ga-modified
supports at various gallium contents; (c) and (d) Pt(1.0 and 1.5 wt%)/SBA-15; (e) and (f) SBA-15 modified with 20 wt% Ga and corresponding Pt impregnated
(1.0 and 1.5 wt%) solids.

Ga(3)-SBA-15 was intermediate between H1 and H2-type Conversely, samples with Ga at 10 and 20 wt% had SBET
probably by influence of some Ga2O3 segregated domains. completely similar to corresponding bSBET ones strongly
Textural characteristics of various prepared solids (mixed suggesting abscence of clogged pores due to well-dispersed
supports and corresponding Pt-impregnated materials) are Ga phases integrated to mesoporous siliceous matrix.
shown in Tables 1 and 2. Pristine mesoporous SBA-15 had Unaffected shape of adsorption isotherms in those cases
typical texture with 819 m2/g surface area (SBET), pore supported that assumption (Figure 1a). In this line, gallium
volume (Vp) of 1.05 cm3/g and average pore diameter (from inclusion (in tetrahedral coordination) into siliceous SBA-15
corresponding PSD, Figure 1b) of 5.55 nm. Those properties well-ordered mesoporous structure has been identified (by
71
nicely corresponded to expected values for SBA-15 matrices Ga NMR spectroscopy) by others [19] when studying
(500 < SBET < 1300 m2/g, 0.82 < Vp < 1.69 cm3/g) commonly modified SAB-15 materials at various Ga contents and
reported in the literature for such type of mesostructured prepared through different synthesis methodologies. Launay
SiO2 [18]. et al. [19], also reported better incorporation of gallium at
However, all Ga-modified solids at various contents had higher content in SBA-matrices where in samples at Si/Ga of
decreased surface area as to that of pristine SBA-15. Fifth
Table 2. Textural properties of Pt supported on SBA-15 and various
column of Table 1 shows theoretical surface area of Ga-SBA-15 materials prepared.
composites considering incorporation of essentially non-
porous Ga2O3 component in SBA-15 matrix (bSBET), pointing Sample
SBET Vp a
Dp bSBET
S /bS
out to that in samples of the lowest Ga content gallium oxide (m2/g) (cm3/g) (nm) (m2/g) BET BET
domains could be partially plugging well-ordered 3.89,
mesoporous siliceous network. Pt(0.5)/SBA-15 684 0.86 815 0.84
5.60
Table 1. Textural properties of SBA-15 and various Ga-SBA-15 materials 3.89,
Pt(1)/SBA-15 609 0.68 811 0.75
prepared. 4.80
SBET Vp a
Dp b
SBET 3.89,
Sample SBET/bSBET Pt(1.5)/SBA-15 642 0.84 807 0.80
(m2/g) (cm3/g) (nm) (m2/g) 5.40
SBA-15 819 1.05 5.55 - - 3.89,
Pt(1.5)/Ga(3)-SBA-15 633 0.53 581 1.00
Ga(3)-SBA-15 590 0.57 3.89, 5.5 786 0.75 4.00
Ga(5)-SBA-15 676 0.92 5.80 764 0.88 Pt(1)/Ga(20)-SBA-15 562 0.62 4.7 580 0.97
Ga(10)-SBA-15 681 0.89 5.79 709 0.96
Ga(20)-SBA-15 586 0.79 5.42 599 0.98 3.9,
Pt(1.5)/Ga(20)-SBA-15 518 0.54 577 0.90
a
From BJH plot, desorption branch data. 5.2
b a
Theoretical value considering well-dispersed non-porous Ga2O3 phase From BJH plot, desorption branch data.
b
component. Theoretical value considering well-dispersed non-porous Pt deposition.

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Nevertheless, the former binary solid also had additional

maximum at lower diameter (~3.89 nm) suggesting
deposition of gallium domains insides SBA-15 pores.
The lower closing partial pressure of hysteresis loop of
corresponding N2 physisorption isotherm as to that of
pristine silica support (Figure 1a) was in full agreement with
aforementioned finding. Following the same way of
reasoning, alike shifts in hystheresis closing of
Pt-impregnated SBA-15 (Figure 1c) strongly suggested
presence of noble metal particles inside pristine siliceous
porous matrix [20]. After Pt loading on SBA-15 surface area
and pore volume importantly diminished (~20%, Table 2).
As those losses were much higher than expected considering
deposition of non-porous phases that could indicate low
platinum dispersion that provoked partial pore plugging of
siliceous networks. Accordingly, Kumar et al. [21] reported
that Pt impregnation (1.3 wt%) by pore filling on SBA-15
could render supported solids of rather large particle size
(~21 nm) provoking significantly decreased texture by
occluded porosity. Corresponding pore size distributions
profiles (Figure 1d) showed contributions from smaller pores
as to those of non-impregnated siliceous carrier that could be
rationalized by considering presence of some Pt crystals
inside the carrier porous network.
The SBET of sample of the highest Ga content was just
slightly affected by Pt deposition (Figure 1e and Table 2)
suggesting decreased plugging of carrier pores. Also, very
defined shift of PSD to lower diameters (see hysthereses loop
closing in isotherms shifted to lower P/P0 values and
corresponding pore size profiles, (Figure 1f) strongly
suggested Pt crystals inside pores of that Ga-modified SBA-
15 composite.

X-ray diffraction
A wide signal identified in the 15-35° 2θ range observed in
diffractograms of all studied samples corresponded to
amorphous silica constituting SBA-15 walls [22], Figure 2a.
No reflexions related to Ga2O3 defined domains were
identified on any binary support (Figure 2a) pointing out to
abscence of defined gallium oxide crystals. Although
existence of well-dispersed oxidic gallium domains
(undetectable by XRD) could not be ruled out that fact
suggested good integration of Ga3+ species into the walls of
Figure 2. Wide-angle X-ray diffraction patterns of SBA-15, Ga-modified mesoporous tetrahedral silicon oxide network [23].
SBA-15 at various gallium contents and corresponding Pt-impregnated Conversely, reflections due to Ga2O3 crystals has been
solids. (a) SBA-15 and Ga-modified binary supports; (b) Pt-impregnated on reported [23] in the case of samples where gallium was
pristine SBA-15; (c) Pt-impregnated on Ga(20)-SBA-15.
deposited at 10 wt% (through corresponding nitrate as salt
5 and 10 (very similar composition to our materials with 5 precursor) by post-synthesis impregnation on SBA-15
and 10 Ga wt%) the latter solid had higher Ga proportion matrix.
incorporated in the mesoporous tetrahedral matrix. Probably Pt impregnated solids showed three main reflections at 2θ
at enhanced Ga3+ concentration there could be better values of 39.8, 46.1 and 67.8° assigned to interplanar
adjustment of the hydrolysis rates of the Si and Ga starting distances of (111), (200) and (220) face-centered cubic
materials [19]. metallic platinum facets (PDF 01-087-0640), Figures 2b and
With the sole exception of binary solid at the lowest 2c. Unexpectedly, no supported PtOx species were found. In
gallium content PSD profiles of Ga-modified solids (Figure the opposite, metallic Pt0 was evidenced.
1b) showed maxima at around 5.8 nm (Table 1) similar to Finding reduced platinum in calcined samples (see sub-
that of parent SBA-15 pointing out to efficient integration of section Pt impregnation) supported on SBA-15 has been
Ga3+ into walls of siliceous mesoporous network. reported (as determined by XPS analysis) in the past by
others [24], although no explanation was advanced in that

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Table 3. Crystal size (as determined by Scherrer formula using Pt(111)

reflection) of various Pt-impregnated materials prepared.

Crystallite size
Sample
(nm)
Pt(0.5)/SBA-15 7.78
Pt(1)/SBA-15 8.58
Pt(1.5)/SBA-15 18.85
Pt(1)/Ga(3)-SBA-15 16.39
Pt(1.5)/Ga(3)-SBA-15 23.33
Pt(1)/Ga(5)-SBA-15 20.64
Pt(1.5)/Ga(5)-SBA-15 24.04
Pt(1)/Ga(10)-SBA-15 18.77
Pt(1.5)/Ga(10)-SBA-15 26.69
Pt(1)/Ga(20)-SBA-15 21.77
Pt(1.5)/Ga(20)-SBA-15 23.93

case. Organic remains that could be present in our mixed Figure 3. FTIR spectra of pristine SBA-15 and Ga-modified supports at
materials could play a determining role on that fact. Indeed, various gallium contents.
organic residua from Si alkoxides used during SBA-15 and
corresponding Ga-modified solids synthesis usually could role on noble metal dispersion. Further work is needed on
remain occluded in calcined materials [25]. Those organic this point to elucidate the reason behind observed behavior.
species could contribute to Pt reduction during high- Finally, it seemed that due to the presence of organic remains
temperature annealing. Indeed, organic compounds had been (that could contribute to impregnated platinum reduction
sucessfully applied by others as noble metals reductants [26]. during annealing conditions under air) the reduction step
According to Scherrer formula and by using the most under H2 flow (at 300-400 °C) [27,28] could be avoided
intense Pt (111) reflection corresponding crystal size for simplifying then the catalyst activation procedure.
solids with SBA-15 and Ga-modified ones as carrier were
estimated, Table 3. Platinum crystal size on pristine siliceous FTIR spectroscopy
support increased from 7.78 to 18.85 nm with Pt loading Broad bands centered around 3453 and 1633 cm-1 were
from 0.5 to 1.5 wt%. Others have reported [20] similar values attributed to stretching vibrations of surface hydroxyl groups
to the last one when studying samples with 4 wt% platinum and water [29] and to deformation vibration of adsorbed un-
attributing that to low interaction of deposited species with dissociated H2O molecules coordinated to surface centers
silanol groups on silica surface. Due to that, in addition to [30], Figure 3. Shoulder at 3685 cm-1 in all spectra could be
low Pt dispersion after impregnation significant metallic related to surface silanol groups [31]. Absorptions at 2970
particles sintering during high-temperature annealing could and 2857 cm-1 related to -CH3 degenerated stretching mode
take place. Also, low noble metal dispersion could justifiy and -CH2 stretching symmetrical vibrations, respectively,
significant SBET loss of SBA-15-supported samples, much indicated organic remans from Si alkoxides used during
larger to those expected considering noble metal loading (see support synthesis [25]. As mentioned in previous section,
column 6 of Table 2). In these cases, Pt crystals dimensions those organic remains could contribute in reducing deposited
were clearly big enough to plug some pores (Dp ~ 5.8 nm, platinum species supported on the prepared composites.
Table 1) of the pristine siliceous carrier. Peak at around 10814 cm-1 corresponded to Si-O-Si
Ga addition in SBA-15 matrix was detrimental on Pt asymmetric stretching vibration meanwhile bands at ~803
dispersion as to that on SBA-15 carrier, Table 3. For and 458 cm-1 were originated by symmetric stretching and
materials at 1 wt% Pt loading crystal size increased from deformation modes of aforementioned bonds.
8.58 (on pristine siliceous support) to 21.77 nm in the solid Band at 967 cm-1 was related to Si-OH stretching vibrations
of the highest Ga content. Although that could be ascribed to [29]. No infrared absorptions corresponding to Ga 2O3
much lower SBET of binary supports as to that of pristine defined domains could be stablished (Figure 3), in agreement
SBA-15 (for instance, 586 versus 819 m2/g for material with with that found by XRD (Figure 2a). Band at 458 cm-1 in
20 wt% Ga and pristine mesoporous solid, respectively, studied spectra could be related to Si-O-Si bending
Table 1) it was clear that gallium modification did not vibrations [32].
favorably altered surface properties of mixed oxides
obtained. In the opposite to that found, incorporation of Scannig electron microscopy
gallium in tetrahedral network in SBA-15 matrix resulted in SBA-15 morphology exhibited particles of around 3-4 μm
improved vanadium species dispersion, being that attributed in diameter formed by numerous agglomerated hexagonal
to better anchorage of those species on a more acidic support platelets of 800-1000 nm (not shown), completely similar to
(as compared to pristine silica-based one) [23]. It is worth that previously reported [33]. Smooth platelets of very short
noting that Ga incorporation method used in mentioned length in axial direction were evidenced. In full agreement,
investigation (gallium impregnation at various loadings on a others [34] identified alike morphology for SBA-15 prepared
pre-formed siliceous matrix) probably could play a decisive under similar conditions as to those used in the present

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incorporated to SBA-15 due to similar aforementioned

synthesis mechanism.
Interestingly, morphology of particles constituting the Ga
material of the highest heteroatom content (Figure 4c)
showed certain resemblance to that of mesoporous gallium
oxide phases prepared from gallium nitrate hydrate with non-
ionic tri-blockcopolymer F127 as structure directing agent
[37]. Indeed, it has been proposed [38] that the self-assembly
process could be controlled by the electrostatic charge
matching between the inorganic ions in solution (Ga3+), non-
ionic surfactants and inorganic counterions (NO3-). Gallium
hydroxo species could be assembled then through hydrogen
bonding with hydronium ion solvated neutral block co-
polymers (as Pluronic P123). Thus, under synthesis
conditions used in this work formation of mesoporous
gallium oxide domains could not be ruled out. Deeper studies
on this topic are obviously required.
Brigth spots due to platinum crystals were clearly
registered in micrographs of Ga-modified materials (Figures
4b and 4c) attesting noble metal particles of low dispersion.

Figure 4. SEM micrographs, 5000×, scale bar: 5 μm. (a) Pt(1.5)/SBA-15;

(b) Pt(1.5)/Ga(3)-SBA-15; (c) Pt(1.5)/Ga(20)-SBA-15.

investigation. No significant differences on morphology as

to that of pristine SBA-15 was observed after Pt
impregnation, Figure 4a.
However, Ga-modified materials seemed to be constituted
by smaller agglomerates of otherwise similar shape as to
those observed in the SBA-15 case, Figures 4b and 4c. It was
apparent that a good gallium proportion could be well-
integrated in tetrahedral silica matrix. In this line, to
efficiently incorporate aluminum into siliceous framework
the heteroatoms must be available as highly reactive species
during multidentate binding stage of mesoposorous SiO2
synthesis. Regarding Al-modified MCM-41 solids, it has
been claimed that [35] highly charged aluminum species
could be coordinated with surfactant molecules, other
cationic species or aqueous silicate oligomers being then
readily introduced into the silica framework. In full
agreement to that it has been found [36] that aluminum was
better integrated into MCM-41 frameworks when Al2(SO4)3
was used as salt precursor (as opposed to AlO(OH)). It could
be then that Ga3+ cations (from corresponding nitrate Figure 5. HR-TEM micrographs. (a) as prepared SBA-15, along pore axis
utilized, see sub-section Ga-modified SBA-15) were well- direction; (b) Ga(20)-SBA-15, perpendicular to pore axis direction.

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were identified in accordance with our XRD findings (Figure

2a).
Large cubic platinum crystals were found on SBA-15
(Figure 6a). Those particles could result from sintering
(particle migration-coalescence [40]) under annealing at 500
°C (see sub-section Pt impregnation) of noble metal particles
originally deposited on the external siliceous carrier surface.
They could be prone to sintering due to their weak interaction
with the ordered SiO2 surface.
Presence of those crystals large enough to partially plug
some pores of binary supports could explain surface area lost
of Pt(1.5)/SBA-15 much bigger than expected considering
noble metal loading (20% diminished SBET, as to that of
corresponding to bSBET, Table 2). Some small platinum
crystal inside mesoporous network were also observed in the
Pt(1.5)/SBA-15 sample, Figure 6b. Larger noble metal
particles were observed for Pt(1.5)/Ga(20)-SBA-15, Figure
6b, supporting that found through crystal size calculations
(Table 3) were enhanced noble metal crystallites size as to
those on pristine SBA-15 of similar loading was estimated.
Thus, no positive effect of Ga addition to SBA-15 matrices
on platinum dispersion was corroborated. Although surface
acidity could be incorporated to SBA-15 by gallium addition
those sites could be of rather mild acid properties [9] not
being strong enough to interact with supported noble metal
particles. Indeed, hydrocracking reactions that require strong
acidity were avoided on sulfided NiW/Ga-SBA-15 tested in
dibenzothiophene hydrodesulfurization [41] evidencing
absence of those sites.
In our case, platinum crystals sintering at the annealing
conditions used in the present work could not be precluded
presumably due to their weak interaction with those weak
acid surface sites. Interestingly some amorphopus inclusions
could be observed in Figure 6b pointing out to some
segregated gallium oxide domains. However, they were not
detectable by XRD (Figure 2a) due to their amorphousness.

Conclusions
Figure 6. HR-TEM micrographs of platinum-impregnated materials.
(a) Pt(1.5)/SBA-15; (b) Pt(1.5)/Ga(20)-SBA-15. Arrows: Platinum crystals. Pt (0.5, 1 and 1.5 wt%) was impregnated by incipient
wetness on SBA-15 and corresponding Ga-modified (3, 5,
High-resolution TEM 10 and 20 wt%) composites. Gallium nitrate was used to
The highly ordered honeycomb-shaped mesoporous incorporate Ga directly during the mesoporous siliceous
structure of siliceous pristine SBA-15 containing hexagonal network synthesis. SBA-15 had surface area greater than 800
cross sections with pores of around 6 nm (Table 1) was m²/g that decreased by Ga incorporation in binary materials.
evidenced in Figure 5a. That characteristic 2-D hexagonal It seemed that in most samples (but in the one of the lowest
symmetry (p6mm) was in full agreement with corresponding gallium content) a good proportion of tetrahedral Ga was
structural characterization of SBA-15 materials as presented well-incorporated into mesoporous silica walls. Pt dispersion
in previous works [32, 39]. Although our materials were not diminished (as to that on SBA-15) by augmenting Ga
characterized by low-angle XRD we considered that shape concentration in composites. Corresponding pore size
of corresponding N2 adsorption isotherms (Figure 1a) and maxima shifted to lower diameters (as to that of non-
studies by high resolution HR-TEM (Figure 5) clearly impregnated supports) after platinum loading suggesting Pt
evidenced the mesoporous ordered structure corresponding crystals inside pores of SBA-15 and Ga-modified carriers,
to SBA-15-type materials. That array was well- preserved in that effect being more evident in the latter. Large cubic
the composite of the highest Ga content (Figure 5b) in full platinum crystals (25-50 nm) were observed over all
agreement with the unaltered shape of corresponding N2 prepared materials probably due to sintering (during
physisorption isotherm, Figure 1a, as to that of pristine SiO2 calcining at 500 °C) of metallic particles weakly interacting
matrix pointing out to good incoporation of tetrahedral Ga3+ with the carriers surface. After materials annealing (500 °C
in silica framework. No defined segregated Ga2O3 domains under static air) metallic platinum was evidenced (by XRD)

7
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