J Mater Sci: Mater Electron (2018) 29:2159–2169

DOI 10.1007/s10854-017-8128-3

Study of the characteristics, properties and characterization

of new ­SiO2/TiO2/Sb2O5 ternary oxide obtained by the sol–gel
process
Bruna Teixeira da Fonseca1 · Eliane D’Elia1 · José Márcio Siqueira Júnior2 ·
Sanair Massafra de Oliveira1 · Kelly Leite dos Santos Castro1 ·
Emerson Schwingel Ribeiro1

Received: 14 July 2017 / Accepted: 23 October 2017 / Published online: 1 November 2017
© Springer Science+Business Media, LLC 2017

Abstract SiO2/TiO2/Sb2O5 ternary oxide was prepared surface, where the SiTiSb-B presented more acid sites on
by the sol–gel method in two different proportions, and the surface.
were characterized by X-ray fluorescence (XRF), analysis
of the specific surface area by BET and the average pore
size and pore volume by BJH method, thermogravimetric 1 Introduction
analysis (TGA), scanning electron microscopy (SEM) and
electron dispersive spectroscopy (EDS) analyses, powder In the last years, the sol–gel process has been employed to
X-ray diffraction (XRD), X-ray photoelectron spectroscopy obtain oxides mixture of the type S ­ iO2/MxOy, ­SiO2/MxOy/
(XPS) and other spectroscopic technics (FT-Raman, FT-IR, NxOy, where M ­ xOy or N ­ xOy can be A ­ l2O3, ­TiO2, ­Nb2O5,
UV–Vis–NIR and DRS). The ternary oxides showed high SnO, ­ZrO2, ­Sb2O3, ­Sb2O5, ­V2O5 [1–11]. The sol–gel process
surface area 758 and 529 m2 g−1 for SiTiSb-A and SiTiSb-B, is an important methodology to obtain materials with high
respectively. The binding energy values for the Sb 3d and chemical stability, purity, controlled porosity, high uniform-
Ti 2p levels show the insertion of Sb and Ti atoms in the ity for the distribution of the metal oxides on its surface
silica matrix, confirming the high dispersion of the met- ­(MxOy or ­NxOy) and combining the mechanical properties
als presented in SEM, both in the bulk and on the surface. of the silica matrix with the chemical properties of the bulk
The thermogravimetric analysis (TGA) showed weight loss metal oxides [3, 4, 7, 12–15].
of 23% for both ternary oxides. The crystallographic data The different characteristics mentioned above for the
showed an increase of the crystalline order with the increase oxide mixture and the presence of the Lewis and Brønsted
of the temperature of the thermal treatment. The anatase acid sites on its surface makes these materials interesting
phase as well as a small content of the rutile phase of ­TiO2 for various applications, as adsorption of interest molecules
were identified by FT-Raman. The Raman spectrum cor- [15, 16], in pre concentration systems of metallic ions [17,
roborated with the DTA and XRD of the SiTiSb-B which 18], heterogeneous catalysis [19–21], for dye remediation or
showed a slight decrease in the degree of crystallinity. Opti- adsorbent in aqueous solution [5, 22], in the development of
cal band gap values are dependent on the content of oxides. new chemically modified electrodes [15, 19, 23, 24], among
The pyridine adsorption studies showed the presence of others.
Lewis and Brønsted acid sites on the SiTiSb ternary oxide Our research group has been developing several ternary
oxides in recent years, and these have been applied for the
development of new chemically modified electrodes [15,
* Emerson Schwingel Ribeiro 25–27], in preconcentration systems of metallic ions [7, 17,
emersonsr@iq.ufrj.br 28–30].
1 In 1999, Gonçalves et al. developed the ­SiO2/TiO2/Sb2O5
Instituto de Química, Universidade Federal do Rio de
Janeiro - UFRJ, CT, Bloco A, Cidade Universitária – Ilha ternary oxide [1]. The authors first describe the synthesis
do Fundão, CEP 21941‑909 Rio de Janeiro, RJ, Brazil ­SiO2/TiO2 binary oxide by the sol–gel process, and in a
2
Instituto de Química, Universidade Federal Fluminense – second step, the ­SiO2/TiO2 was added in an aqueous solu-
UFF, Valonguinho, CEP 24020‑150 Niterói, RJ, Brazil tion of Sb (V) (prepared from ­SbCl5) to modify its surface

13
Vol.:(0123456789)
2160 J Mater Sci: Mater Electron (2018) 29:2159–2169

with ­Sb2O5. However, the development of the S ­ iO2/TiO2/ The ternary oxides were thermally treated at temperatures
Sb2O5 ternary oxide in one-step synthesis to obtain the metal of 473, 673, 873, 1073 and 1273 K for 8 h and the samples
oxides ­TiO2 and ­Sb2O5 totally dispersed in the silica matrix were analyzed by powder X-ray diffraction (XRD), Raman
has not been described. scattering analyzes and diffuse reflectance spectroscopy in
In this work, we describe the study of the characteristics, the UV–Visible region.
properties and characterization using various techniques of The crystallinity of the thermally treated powders was
new ­SiO2/TiO2/Sb2O5 ternary oxide obtained by the sol–gel analyzed by powder X-ray diffraction (XRD). A Bruker AXS
process in one-step synthesis. D8 Advance instrument (Cu Kα1,α2 radiation, 40 kV and
40 mA) operating in a Bragg–Brentano θ/θ configuration
was used for this purpose. The diffraction patterns were col-
2 Experimental lected in a flat geometry with steps of 0.02° and accumula-
tion time of 3 s per step. The X-ray powder diffraction data
2.1 Reagents and solutions were refined following the Rietveld method with the TOPAS
Academic V.5© software.
Tetraethylorthosilicate (TEOS, 98%), antimony(V) pen- The X-ray photoelectron spectroscopy (XPS) analysis
tachloride (97%) and titanium(IV) butoxide (97%) were were performed on the Omicron nanotechnology instrument
purchased from Sigma-Aldrich (Saint Louis, MO, USA), (Germany), in ultra-high vacuum, using an Mg X-ray source
ethanol (99.8%), HCl (37% v/v) and ­H NO 3 (95% v/v) (Κα = 1253.6 eV), with power given by emission of 16 mA,
were purchased from Vetec (Duque de Caxias, RJ, Brazil), at a voltage of 12.5 kV. Survey spectra were obtained with
and ultra-pure Milli-Q water was used at work (resistiv- 50 eV analyzer pass energy and 0.5 eV step size. The high-
ity > 18.2 MΩ cm−1, 25 °C, M
­ illipore© Milli-Q© purification resolution spectra were obtained with 40 eV pass energy in
system, Billerica, MA, USA). the analyzer and 0.08 eV steps. The binding energies were
referred to the carbon 1 s of high oriented pyrolytic graphite
2.2 Instrumentation (HOPG) level, set as 284.6 eV. The peak fitting was per-
formed using the ­CasaXPS© software.
The ­SiO2, ­TiO2 and ­Sb2O5 contents in the ternary oxides Solid-state FT-Raman spectra of the thermally treated
were determined by using X-ray fluorescence (XRF) on a samples were recorded by a Bruker MultiRam spectrom-
model S8 TIGER—Bruker (Tokyo, Japan). The samples eter at room temperature with a germanium detector, main-
were analyzed in He with an X-ray source of Rh operating at tained at liquid nitrogen temperature, using the 1064 nm
30–60 kV of voltage range, according to the measure region. Nd–YAG laser line with a resolution of 2 cm−1 in the region
The analysis of the specific surface area (­ SBET) of the of 1200–70 cm−1 and 256 scans at a laser power of 100 mW.
ternary oxides were performed on a Quantachrome Model The samples were measured in the hemispheric bore of an
Nova 1200e (Boynton Beach, USA) instrument and deter- aluminum sample holder.
mined by using the BET (Brauner, Emmett and Teller) The determination of the value of optical band gap of
multipoint method by submitting the samples to previous the thermally treated samples was performed through the
activation at 393 K in vacuum for 24 h. The BJH (Bar- Kubelka–Munk function [F(R)] of data interpretation from
rett–Joyner–Halenda) method was used to obtain the average the diffuse reflectance spectroscopy (DRS) obtained in Cary
pore size and volume. 5000 Varian UV–Vis–NIR Spectrophotometer, with wave-
The thermogravimetric analysis was performed on a Shi- lengths between 190 and 950 nm and magnesium oxide as
madzu DTG-60 (Kyoto-Japan), in the range of 293–1173 K, reference.
with temperature scan rate of 5 K min−1 and argon flow rate The acidic properties of the ternary oxides were veri-
of 50 mL min−1. fied using pyridine as a probe molecule to detect Lewis
For the scanning electron micrographs (SEM) and elec- and Brønsted acidic sites in the samples. Drops of pyridine
tron dispersive spectroscopy (EDS) analyses, the sample were added in the ternary oxides and the samples were dried
was dispersed on double-sided conductive tape on a copper under high vacuum at different temperatures (room tempera-
support and coated with gold before the experiment. SEM ture, 373 and 423 K). After dried, the samples were analyzed
images were acquired using a JEOL model JSM 6460-LV by infrared spectroscopy, obtained with pellets containing
(Tokyo, Japan) or FEI model Magellan 400 HXR scanning 12% of the ternary oxide and 88% of KBr.
electron microscope at an acceleration voltage of 3.0, 5.0 or
10.0 kV according to the analyzed ternary oxide, and ×150 2.3 Synthesis of the SiTiSb ternary oxides
magnification. For EDS analyses, the EDS Noran System
Six model 200 (Waltham, USA) was linked to JSM 6460- The ­S iO 2/TiO 2/Sb 2O 5 ternary oxides were prepared in
LV equipment. two mass percentage proportions, designed by SiTiSb-A

13
J Mater Sci: Mater Electron (2018) 29:2159–2169 2161

and SiTiSb-B. The general procedure was: 7.0 mL of a under vacuum (­ 10−5 Pa) for 6 h at 363 K to evaporate the
6.0 mol L−1 HCl solution was added to 230.0 mL of a 50% solvents of the washing step and stored.
(v/v) ethanol/TEOS solution. The mixture was stirred for
3 h at 353 K to initiate the pre-hydrolysis. After that, the
titanium(IV) butoxide (dissolved in 50.0 mL of ethanol) 3 Results and discussion
was added drop by drop at the mixture, followed by 7.0 mL
of a 6.0 mol L−1 HCl solution. The mixture was stirred for 3.1 Structural characterization of SiTiSb ternary
1 h at 353 K. Next, the antimony(V) pentachloride (dis- oxides
solved in 50.0 mL of ethanol) was added drop by drop and
the mixture was stirred for 30 min at 353 K. In addition, The XRF analysis was carried out to assess the efficiency of
15.0 mL of a 6.0 mol L−1 HCl solution was added, and the the sol–gel synthetic route proposal in this work. The results
mixture was stirred for 20 h at 353 K. A previous study of obtained for the ­TiO2 and S­ b2O5 amounts in percentage by
the group showed that in the case of synthesis of materials mass (wt.%) incorporated in the SiTiSb ternary oxides, were
with antimony V precursors it is important to proceed the 16.9 wt.% of ­TiO2 and 4.1 wt.% of ­Sb2O5 for SiTiSb-A and
addition slowly of the antimony pentoxide, not to form 27.2 wt.% of ­TiO2 and 7.3 wt.% of S ­ b2O5 for SiTiSb-B.
phase segregation or islands. This procedure of slowly and Regarding the synthesis, the method showed a low percent-
sequent addition of the precursors is necessary to guar- age of antimony oxide obtained after the purification of the
antee the hydrolysis process occurs simultaneously with ternary oxides, somewhat lower than expected, probably
the incorporation of the metals in the silica matrix. The owing to the reaction medium pH, which was not favorable
addition of acid at each step accelerates the hydrolysis and to the complete hydrolysis of antimony(V) pentachloride.
prevents any precipitation of oxides before incorporation. It is important to say that is extremely difficult to obtain
The solvent was slowly evaporated at 363 K until a gel ternary oxides in the desired proportions because of the dif-
has formed, and was subsequently heated for 4 h in an ferences between the hydrolysis processes of the precursors
oven at 363 K. The obtained gel was grounded and then in the same reaction media. However, the sol–gel process is
dried under vacuum ­(10−5 Pa) at 363 K. The resulting par- a method extremely useful and reproductive for the synthesis
ticles were washed with ethanol in a Soxhlet extractor for of the oxide mixture.
24 h to remove any oxide that was not incorporated at The crystallographic data of the SiTiSb-A and SiTiSb-B
the silica matrix and precursors residues besides possi- systems were evaluated using values of unit cell parameters,
ble contaminants of the material. To increase the materi- crystallite size and merit figures of Rietveld refinements,
als purity, it was washed with 100.0 mL of a 0.1 mol L−1 which are summarized below (Tables 1, 2). It was observed
­HNO3 solution, followed by some ethanol, ultra-pure water for SiTiSb-A, an increase of the crystalline order with the
and ethanol again. Finally, the ternary oxide was dried rise of the temperature of thermal treatment, besides a
decrease of the volume of the unit cell and increase of the

Table 1  Crystallographic Sample a = b (Å) c (Å) Vol (Å3) Rwp (%) Gof Size (nm)
data of the SiTiSb-A samples:
uncalcined and thermally SiTiSb-A 3.806563 9.537933 138.204 1.77 1.28 10.89
treated in the range of 473–
SiTiSb-A-473 3.807252 9.530158 138.141 2.74 1.08 17.91
1273 K
SiTiSb-A-673 3.805993 9.525613 137.984 2.73 1.09 21.57
SiTiSb-A-873 3.793812 9.517891 136.991 2.77 1.09 28.88
SiTiSb-A-1073 3.787514 9.538042 136.826 3.83 1.33 33.75
SiTiSb-A-1273 3.787952 9.542838 136.926 3.18 1.15 58.32

Table 2  Crystallographic Sample a = b (Å) c (Å) Vol (Å3) Rwp (%) Gof Size (nm)
data of the SiTiSb-B samples:
uncalcined and thermally SiTiSb-B 3.802372 9.525689 137.723 1.81 1.22 20.03
treated in the range of 473–
SiTiSb-B-473 3.802355 9.521345 137.659 2.85 1.07 21.32
1273 K
SiTiSb-B-673 3.802101 9.519221 137.610 2.90 1.07 21.85
SiTiSb-B-873 3.795137 9.525268 137.193 3.06 1.14 17.13
SiTiSb-B-1073 3.789717 9.527089 136.828 3.11 1.14 23.06
SiTiSb-B-1273 3.787528 9.539650 136.850 3.25 1.13 31.4

13
2162 J Mater Sci: Mater Electron (2018) 29:2159–2169

SiTiSb-A This other phase (rutile) is tetragonal crystal system of the

A
473 K space group (136) P42/mnm, inorganic crystal structure data
673 K base ICSD#167953 [32]. It is observed the halo centered
873 K
1073 K between 20° and 27° in 2θ, which is due to the presence of
A
R
A A
A
A A
1273 K ­SiO2 (Fig. 1).
Intensity (A.U)

A A
A
In addition, the growth of the crystallites when there is
an increase in the ­TiO2 content is lower and the variation
with the temperature becomes narrower (Table 2). Thus,
both SiTiSb-A (0.21 for T ­ iO2/SiO2) and SiTiSb-B (0.41 for
­TiO2/SiO2) have the tetragonal phase of anatase; and this is
the only phase up to 1073 K for both (Figs. 1, 2). However,
the calcination of the samples at 1273 K shows the pres-
ence of 1.9% of the rutile phase for the SiTiSb-A and 4.8%
for the SiTiSb-B, which leads us to conclude that a higher
20 30 40 50 60 70 80 90 100 proportion of ­TiO2 hinders the growth of the crystallite and
2θ facilitates the formation of this phase.
The BET analyses revealed that the specific surface area
was 758 m2 g−1 for SiTiSb-A and 529 m2 g−1 for SiTiSb-B.
Fig. 1  XRD for the SiTiSb-A samples: uncalcined and thermally
treated in the range of 473–1273 K. The peaks marked with the letter The BJH method revealed an average pore size of 14.3 Å
A and R refer to the anatase and rutile phase of ­TiO2, respectively. for SiTiSb-A and 12.5 Å for SiTiSb-B, which indicates
(Color figure online) that these ternary oxides are microporous; and the aver-
age pore volume was 0.543 cm−3 g−1 for SiTiSb-A and
0.330 cm−3 g−1 for SiTiSb-B. These values reflect a good
A SiTiSb-B accessibility to active sites and are similar to those reported
473 K in literature for others mixed oxides obtained using sol–gel
673 K processes [4, 5, 12, 13]. However, the BET analyses show a
873 K
1073 K
lower surface area and pore volume for SiTiSb-B, which is a
ternary oxide that contains smaller amount of S ­ iO2, indicat-
Intensity (A.U)

A
R A A 1273 K
A A A A
A A
ing that the greater amount of ­TiO2 and ­Sb2O5 are of high
R influence on these parameters (surface area and pore size)
and probably hardens the structure due to the formation of a
dense layer and/or the coalescence of pores [7, 8]. Although,
both SiTiSb-A and SiTiSb-B have high surface area, and the
structural characteristics enable the ternary oxides to be used
as electrochemical sensors or heterogeneous catalysts in the
future, for example.
The thermal stability of SiTiSb ternary oxides was evalu-
20 30 40 50 60 70 80 90 100 ated by thermogravimetric analysis (Fig. 3). The thermo-
2θ gravimetric analysis of the ternary oxides shows a similar
behavior under heat and well-defined thermal events asso-
Fig. 2  XRD for the SiTiSb-B samples: uncalcined and thermally
ciated with the weight loss of 23% for both ternary oxides,
treated in the range of 473–1273 K. The peaks marked with the letter until 423 K there is a weight loss of approximately 15%
A and R refer to the anatase and rutile phase of ­TiO2, respectively. related to the water loss from hydrated SiTiSb ternary oxides
(Color figure online) [17–19]. The continuous weight loss of approximately 8%
between 423 and 873 K is related to the attached or encap-
size of the crystallite (Table 1; Fig. 1). The data shown in sulated organic matter in the pores of the ternary oxides, and
Tables 1 and 2 and Figs. 1 and 2 are consistent with the ­TiO2 also of structural water from the silanol (–Si–OH) groups
(anatase) tetragonal crystal system of the space group (141) to the –SiO2 formation (siloxane groups), or related groups
I41/amd, inorganic crystal structure database ICSD#92363 such as –Ti–OH and –Sb–OH [17–19].
[31]. No crystallization of antimony oxide at these treated Figures 4 and 5 show the scanning electron micrograph
temperatures was observed. For both heat treated SiTiSb-A (SEM) and the corresponding energy dispersive scanning
and SiTiSb-B samples at 1273 K, the anatase phase as well images (EDS) of Si, Ti, Sb and O for SiTiSb ternary oxides.
as a small content of the rutile phase of ­TiO2 was identified. The morphology of the particles does not present uniform

13
J Mater Sci: Mater Electron (2018) 29:2159–2169 2163

Fig. 3  Thermogravimetric anal-

150 100 100
ysis of SiTiSb-A and SiTiSb-B. 100
The graphs shows the DTA data 95 95

Weight Loss (%)

100

Weight Loss (%)

(dotted lines) and the relative 50

DTA (µV)
DTA (µV)
weight loss (dashed lines) 90
50 SiTiSb-A 90
DTA SiTiSb-B
Weight Loss 0 DTA
85 Weight Loss
0 85
80 -50
-50 80
75
0 200 400 600 800 1000 0 200 400 600 800 1000
Temperature (°C) Temperature (°C)

Fig. 4  Scanning electron micrograph of SiTiSb-A and EDS mapping of the Si, Ti, Sb and O elements, respectively. Magnification of ×150.
(Color figure online)

size and regular spherical shapes, being characterized by a the materials calculated through Fig. 6 of the EDS spec-
flat surface with a rough structure. The EDS shows that the tra reveals that SiTiSb-B sample have Sb ratios higher than
metal oxide particles are dispersed without phase segrega- SiTiSb-A sample, corroborating with the XRF analysis.
tion or formation of islands at the silica matrix. In addition, The XPS analyses were performed to investigate the
at the magnification level used (×150), the ternary oxides chemical states of the elements in the SiTiSb ternary
seem to be homogeneous, showing, therefore, high uniform- oxides synthesized. The SiTiSb-A and SiTiSb-B spectra,
ity for the distribution of the metal oxides on its surface. Figs. 7 and 8, respectively, show the presence of O, Ti,
This dispersion is very important because increases the num- Sb and Si elements, which confirm the mixture of ­SiO2,
ber of acidic sites on the surface or pores of SiTiSb ternary ­TiO2 and S ­ b2O5 oxides, also observed on XRF and EDS
oxides, and can be attributed to the strong interactions with analyses. Figures 7 and 8 show the high-resolution XPS
siloxane groups of the silica matrix forming strong covalent spectra of O 1s, Ti 2p and Si 2p regions obtained from the
bonds (e.g., of the –Si–O–Ti–OH, –Si–O–Sb–OH types, for SiTiSb-A and SiTiSb-B. The Sb 3d region shows a doublet
example). Table 3 shows the weight ratio at the surface of of Sb ­3d5/2 and Sb ­3d3/2 lines, with binding energy (BE)

13
2164 J Mater Sci: Mater Electron (2018) 29:2159–2169

Fig. 5  Scanning electron micrograph of SiTiSb-B and EDS mapping of the Si, Ti, Sb and O elements, respectively. Magnification of ×150.
(Color figure online)

are attributed to ­SiO2 (104.1 eV) and SiO (101.5 eV) [37,
Table 3  Weight ratios calculated through EDS analysis for SiTiSb-A
and SiTiSb-B 38].

EDS point Si Ti Sb 3.2 Spectroscopic characterization of SiTiSb ternary

SiTiSb-A oxides
STS A 800 × 1_pt1 71.23 17.55 11.23
STS A 800 × 1_pt2 66.54 20.21 13.25 According to the Raman spectra of thermally treated samples
STS A 800 × 1_pt3 76.86 13.41 9.73 and the spectroscopic factor group analysis, the anatase pre-
SiTiSb-B sents six vibrational modes active in Raman ­(D4h19). Thus,
STS B 600 × 1_pt1 50.71 34.98 14.31 for ­TiO2 in anatase form, there are six active Raman modes
STS B 600 × 1_pt2 46.39 40.38 13.23 ­(3Eg + 2B1g + A1g), with these modes being centered at 144
STS B 600 × 1_pt3 51.79 32.67 15.54 ­(Eg), 197 (­ Eg), 399 (­ B1g), 513 (­ A1g), 519 (­ B1g) and 639 cm−1
­(Eg) [39]. These results were seen for all samples with differ-
ent proportions and treated at different temperatures. In the
Raman (Fig. 9) spectrum of the samples treated at 873 K,
of 530.6 and 540.1 eV, respectively, which is attributed the spectra lose definition. This result is corroborated with
to Sb in a ­Sb 2O5 oxide in all samples [33, 34]. The BE the DTA and DRX of the SiTiSb-B, which showed a slight
of Sb is characteristic of the Sb(V) state in ­Sb2O5 [35]. decrease in the degree of crystallinity caused, by the begin-
The high-resolution spectrum of Ti 2p presents the Ti ning of the 2nd endothermic event.
­2 p 3/2 and Ti 2­ p 1/2 lines in 458.7 and 464.4 eV, respec- The optical band-gap was obtained using the
tively, which can be attributed to Ti(V) state in T­ iO2 [36]. Kubelka–Munk function [F(R)] from the diffuse reflec-
The Si 2p region exhibits, for SiTiSb-A (Fig. 7), one peak tance data of the thermally treated SiTiSb-A and SiTiSb-
in 104.1 eV, which can be attributed to S ­ iO 2 [37]. The B (Fig. 10). The optical band-gap values for the SiTiSb-A
SiTiSb-B (Fig. 7) shows two peaks in this region, which and SiTiSb-B are shown in the Table 4. The values of the

13
J Mater Sci: Mater Electron (2018) 29:2159–2169 2165

Fig. 6  EDS mapping of SiTiSb-A (up) and SiTiSb-B (down)

Fig. 7  XPS analysis of SiTiSb-

O 1s Ti 2p
A. Figure shows the binging
Sb 3d Ti 2p3/2
energy graph (upper left), the fit
calculation of O and Sb (upper O 1s
Intensity (counts)

Intensity (counts)

left), Ti (upper right) and Si

(lower central). (Color figure
online)
Ti 2p1/2

Sb 3d5/2
Sb 3d3/2

544 542 540 538 536 534 532 530 528 526 470 465 460 455
Binding Energy (eV) Binding Energy (eV)

Si 2p
Intensity (counts)

108 106 104 102 100

Binding Energy (eV)

13
2166 J Mater Sci: Mater Electron (2018) 29:2159–2169

Fig. 8  XPS analysis of SiTiSb-

B. Figure shows the binging O1s Ti 2p
O 1s
Sb 3d
energy graph (upper left), the fit Ti 2p3/2

Intensity (counts)

Intensity (counts)
calculation of O and Sb (upper
left), Ti (upper right) and Si
(lower central). (Color figure
online)
Sb 3d5/2 Ti 2p1/2

Sb 3d3/2

544 542 540 538 536 534 532 530 528 470 465 460 455
Binding Energy (eV) Binding Energy (eV)

Si 2p

(counts)
Intensity

108 106 104 102 100 98

Binding Energy (eV)

Fig. 9  Raman spectra of SiTiSb-A SiTiSb-B

thermally treated samples at 473 K 473 K
different temperatures 673 K 673 K
873 K 873 K
Intensity (U.A)
Intensity (U.A)

1073 K 1073 K
1273 K 1273 K

1200 1000 800 600 400 200 1200 1000 800 600 400 200
Wavenumber(cm-1) Wavenumber(cm-1)

Fig. 10  DRS [Kubelka–Munk 2,5

SiTiSb-A
function, F (R)] and extrapola- 2,0 473 K
SiTiSb-B
473 K
tion of the tangent line to obtain 673 K 2,0 673 K
873 K
the optical band gap of the 1,5 1073 K
873 K
1073 K
SiTiSb-A and SiTiSb-B samples 1273 K 1,5 1273 K
treated at different temperatures
F(R)

F(R)

1,0
1,0

0,5
0,5
Optical Band gap
Optical band gap
0,0 0,0

2 3 4 5 6 7 2 3 4 5 6 7
Energy (eV) Energy (eV)

13
J Mater Sci: Mater Electron (2018) 29:2159–2169 2167

Table 4  Optical band gap of SiTiSb-A and SiTiSb-B from the func- 8
tion of Kubelka–Munk SiTiSb-A
a
Sample Optical band Sample Optical 6 b
gap (eV) band gap c
d

% Transmitance
(eV)
4
SiTiSb-A 3.37 SiTiSb-B 3.20
SiTiSb-A-473 3.36 SiTiSb-B-473 3.20
2
SiTiSb-A-673 3.24 SiTiSb-B-673 3.25
SiTiSb-A-873 3.40 SiTiSb-B-873 3.36 1576
0 8b
SiTiSb-A-1073 3.30 SiTiSb-B-1073 3.35 1544
1598 19b
SiTiSb-A-1273 3.26 SiTiSb-B-1273 3.15 8a 1490 1446
19a 19b
-2
1650 1600 1550 1500 1450 1400
band gap (Eg) were obtained by extrapolating the linear Wavenumber (cm-1)
part of the graphics to the axis of the abscissa. The ­TiO2
8
is activated with photons of energy of a longitude close to SiTiSb-B
400 nm, which involves a band gap of 3.2 eV, the literature a
b
reports a 3.23 eV value for anatase phase [40]. This transi- 6 c
d
tion occurring in anatase can be described as an absorption

% Transmitance
of the valence band (essentially 2p filled O ­ 2−) to the con- 4
duction band (essentially 3d voids of the Ti). Optical band 1575
gap values are close to those reported and that such values 2
8b 1545
19b
are dependent on the content of the other oxides ­(SiO2 and
1598
­Sb2O5). It is also observed that for the SiTiSb-A treated at a 8a 1490 1446
0 19a 19b
temperature of 873 K, the band gap value increases consid-
erably, probably associated to the increase in the number of
defects of the anatase phase due to the second endothermic -2
1650 1600 1550 1500 1450 1400
event, as observed by the Raman spectroscopy data.
Wavenumber (cm-1)
The acidic properties of the SiTiSb ternary oxides were
studied at various temperatures using pyridine adsorbed as
probe molecule (Fig. 11), and the FT-IR spectra are com- Fig. 11  Infrared spectra of pyridine adsorbed on SiTiSb-A and
SiTiSb-B at different temperatures under vacuum: (a) pure SiTiSb,
pared to the spectrum of the surface adsorbed pyridine-free (b) room temperature, (c) 373 K, (d) 423 K
materials. Spectra are limited in the range of the wavenum-
ber from 1650 to 1400 cm−1, where, typically, the vibra-
tional modes of pyridine are observed. Brønsted acidic sites 1575 cm−1 is due to the vibrational mode 8a of the liquid
are a result of –TiOH or –SbOH groups presents on the silica pyridine physically adsorbed by van der Waals forces and
matrix surface [7, 41]. On the other hand, the titanium or because it shows low interaction with the ternary oxide,
antimony ions coordinatively unsaturated are responsible which disappears with the temperature increase [46–51].
for the presence of Lewis acidic sites [42–45]. As it was A broad band at 1545 or 1544 cm−1 was attributed to the
observed by XRF and EDS analyses, the SiTiSb-B has a vibrational mode 19b of the pyridinium ion, related to the
larger percentage by mass of ­TiO2 and ­Sb2O5, explaining, pyridine molecule bound to the Brønsted acid sites [48, 49].
therefore, the FT-IR spectra with more intense bands in the The different characteristics observed for the SiTiSb ter-
presence of immobilized pyridine for this oxide, corrobo- nary oxides as the presence of the Lewis and Brønsted acid
rating with the XRF and EDS data. These results could be sites on its surface makes these materials interesting for vari-
explained by the more presence of acid sites in SiTiSb-B ous applications. In addition, band-gap values obtained for
surface, leading to a more pyridine adsorption. The bands the SiTiSb-A and SiTiSb-B, show that the materials can be
at 1598 and 1446 cm−1 are due to the 8a and 19b modes use as p-type semiconductors.
of pyridine bonded to the free silanol groups, –SiOH, by
hydrogen bonds, being observed for the pure SiTiSb ternary
oxide treated at room temperature, which disappear with 4 Conclusions
the temperature increase [46]. The band at 1490 cm−1 cor-
responds to the vibrational mode 19a and is always present The synthesis method provided SiTiSb ternary oxides with
for all sorts of adsorbed pyridine. The shoulder at 1576 or high dispersion of the metals at silica matrix, with antimony

13
2168 J Mater Sci: Mater Electron (2018) 29:2159–2169

at its higher oxidation charge as it can be seen by XPS analy- 7. C.R.T. Tarley, G.F. Lima, D.R. Nascimento, A.R.S. Assis, E.S.
sis, contributing, therefore, for higher acidity of the materi- Ribeiro, K.M. Diniz, M.A. Bezerra, M.G. Segatelli, Novel on-line
sequential preconcentration system of Cr(III) and Cr(VI) hyphen-
als. It is extremely difficult to obtain ternary oxides in the ated with flame atomic absorption spectrometry exploiting sorb-
desired proportions because of the differences between the ents based on chemically modified silica. Talanta 100, 71 (2012)
hydrolysis processes of the precursors in the same reaction 8. A. Aronne, E. Marenna, V. Califano, E. Fanelli, P. Pernice, M.
media. However, the sol–gel process is a method extremely Trifuoggi, A. Vergara, Sol–gel synthesis and structural charac-
terization of niobium–silicon mixed-oxide nanocomposites. J Sol
useful and reproductive for the synthesis of the ternary Gel Sci. Technol. 43, 193 (2007)
oxides. It was shown in this work that the SiTiSb ternary 9. R.J. Davis, Z. Liu, Titania–silica: a model binary oxide catalyst
oxide was obtained successfully. The different characteristics system. Chem. Mater. 9, 2311 (1997)
observed for the SiTiSb ternary oxides as the presence of the 10. B. Stuyven, J. Emmerich, P. Eloy, J.V. Humbeeck, C.E.A.
Kirschhock, P.A. Jacobs, J.A. Martens, E. Breynaert, Molybde-
Lewis and Brønsted acid sites on its surface, good thermal num–vanadium–antimony mixed oxide catalyst forisobutane par-
stability, uniform dispersion of the metals on the surface and tial oxidation synthesized using magneto hydrodynamic forces.
high surface area make these materials interesting for vari- App. Catal. A 474, 18 (2014)
ous applications, as electrochemical sensors, solid matrices 11. N. Letaïef, A. Lucas-Girot, H. Oudadesse, R. Dorbez-Sridi, P.
Boullay, Investigation of the surfactant type effect on character-
for solid phase extraction, heterogeneous catalysts, photoca- istics and bioactivity of new mesoporous bioactive glass in the
talysis, among others. Also, SiTiSb ternary oxides can also ternary system S­ iO2–CaO–P2O5: structural, textural and reactivity
be applied as p-type semiconductors. studies. Microporous Mesoporous Mater. 195, 102 (2014)
12. T. Graham, On the properties of silicic acid and other analogous
Acknowledgements The authors thanks to Fundação de Amparo colloidal substances. J. Chem. Soc. 17, 318 (1864)
à Pesquisa do Estado do Rio de Janeiro (FAPERJ), Coordenação de 13. L.L. Hench, J.K. West, The sol–gel process. Chem. Rev. 90, 33
Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Conselho (1990)
Nacional de Desenvolvimento Científico e Tecnológico (CNPq) for 14. C.J. Brinker, G.W. Schere, Sol–Gel Science: The Physics and
financial support. The authors wish to acknowledge Fernando Celso Chemistry of Sol–Gel Processing. (Academic Press, San Diego,
Ribeiro Soares Junior for checking the English and Priscila Pio of 1990)
LACCO-INT for the XRF analysis. 15. M.S. Ribeiro, F.J.V. Júnior, B.T. Fonseca, F.C. Souza, F.D.R.
Soares, E.C. Lima, M.F. Cabral, E.S. Ribeiro, E. D’Elia, On the
Compliance with ethical standards applicability of ­SiO2/Al2O3/Nb2O5 and ­SiO2/Al2O3/TiO2 as a bio-
compatible platform for chloroperoxidase. Anal. Methods 6, 521
(2014)
Conflict of interest The authors of this work declare that they have 16. M. Wiśniewska, P. Nowicki, V.M. Bogatyrov, A. Nosal-
no conflict of interest. Wiercińska, R. Pietrzak, Comparison of adsorption properties
of ­MgxOy–SiO2 and Z ­ nxOy–SiO2 in the mixed oxide-poly(vinyl
alcohol) system. Colloids Surf. A 492, 12 (2016)
17. N.B. Wutke, K.M. Diniz, M.Z. Corazza, F.M. Oliveira, E.S.
References Ribeiro, B.T. Fonseca, M.G. Segatelli, C.R.T. Tarley, Preconcen-
tration of nickel(II) by a mini-flow system with a novel ternary
1. J.E. Gonçalves, Y. Gushikem, S.C. Castro, Preparation and proper- oxide solid phase and flame atomic absorption spectrometry. Anal.
ties of antimony(V) oxide adsorbed on silica–titania mixed oxide. Lett. 49, 723 (2016)
J. Non-Cryst. Solids 260, 125 (1999) 18. E.G. Vieira, I.V. Soares, N.L.D. Filho, N.C. Silva, E.F. Garcia,
2. T.C. Canevari, R.C.G. Vinhas, R. Landers, Y. Gushikem, S ­ iO2/ A.C. Bastos, S.D. Perujo, T.T. Ferreira, A.H. Rosa, L.F. Fraceto,
SnO2/Sb2O5 microporous ceramic material for immobilization Preconcentration and determination of metal ions from fuel etha-
of Meldola’s blue: application as an electrochemical sensor for nol with a new 2,2′-dipyridylamine bonded silica. J Colloid Inter-
NADH. Biosens. Bioelectron. 26, 2402 (2011) face Sci. 391, 116 (2013)
3. E.S. Ribeiro, S.L.P. Dias, S.T. Fujiwara, Y. Gushikem, R.E. Bruns, 19. M.E. Mahmoud, I.M.M. Kenawy, M.M.A.H. Hafez, R.R. Lashein,
Electrochemical study and complete factorial design of toluidine Removal, preconcentration and determination of trace heavy metal
blue immobilized on the binary oxide ­SiO2/Sb2O3. J App. Elec- ions in water samples by AAS via chemically modified silica gel
trochem. 33, 1069 (2003) N-(1-carboxy-6-hydroxy) benzylidenepropylamine ion exchanger.
4. A. Jacqueline, H.A. Masosso, R.R. Ramos, T.C. Canevari, R. Desalination 250, 62 (2010)
Landers, V.L. Pimentel, Y. Gushikem, Structural and electro- 20. S.S.P. Sultana, D.H.V. Kishore, M. Kuniyil, M. Khan, M.R.H.
chemical characterization of a cobalt phthalocyanine bulk-modi- Siddiqui, A. Alwarthan, K.R.S. Prasad, N. Ahmad, S.F. Adil, Pro-
fied ­SiO2/SnO2 carbon ceramic electrode. Electrochim. Acta 54, moting effects of thoria on the nickel–manganese mixed oxide
1948 (2009). catalysts for the aerobic oxidation of benzyl alcohol. Arab. J.
5. C.S. Umpierres, L.D.T Prola, M.A. Adebayo, E.C. Lima, G.S. Chem. 10, 448 (2017)
Reis, D.D.F. Kunzler, G.L. Dotto, L.T. Arenas, E.V. Benvenutti, 21. H. Zhang, K. Sun, Z. Feng, P. Ying, C. Li, Studies on the S ­ bOx
Mesoporous ­Nb2O5/SiO2 material obtained by sol–gel method and species of ­SbOx/SiO2 catalysts for methane-selective oxidation to
applied as adsorbent of crystal violet dye. Environ. Technol. 38, formaldehyde. Appl. Catal. A 305, 110 (2006)
566 (2017) 22. M. Wawrzkiewicz, M. Wiśniewska, V.M. Gun’ko, V.I. Zarko,
6. M.T. Laranjo, N.C. Ricardi, L.T. Arenas, E.V. Benvenutti, M.C. Adsorptive removal of acid, reactive and direct dyes from aque-
Oliveira, S. Buchner, M.J.L. Santos, T.M.H. Costa, Influence of ous solutions and wastewater using mixed silica–alumina oxide.
ball milling on textural and morphological properties of ­TiO2 and Powder Technol. 278, 306 (2015)
­TiO2/SiO2 xerogel powders applied in photoanodes for solar cells. 23. F.M.S. Garrido, R.F. Medeiros, N.O.B. Nogueira, R.C.D. Peres,
J Solid State Electrochem. 20, 1731 (2016) E.S. Ribeiro, M.E. Medeiros, Síntese de óxidos mistos ­SiO2/

13
J Mater Sci: Mater Electron (2018) 29:2159–2169 2169

MnxOy para aplicação na reação de redução de ­O2. Matéria 35. L. Zhang, J. Wei, X. Zhao, F. Li, F. Jiang, M. Zhang, X. Cheng,
(UFRJ) 18, 1294 (2013) Competitive adsorption of strontium and cobalt onto tin antimo-
24. A.A.H. Rocha, E.B. Pires, A.S. Nectoux, S.L.P. Dias, E.C. Lima, nite. Chem. Eng. J. 285, 679 (2016)
C. Radtke, L.T. Kubota, Preparation and electrochemical behavior 36. L. Zhang, Y. Qin, B. Chen, Y. Peng, H. He, Y. Yuan, Catalytic
of the CA/TiO2/Sb2O5 composite electrode modified with p-ben- reduction of S ­ O2 by CO over C ­ eO2–TiO2 mixed oxides. Trans.
zoquinone. J. Electroanal. Chem. 690, 74 (2013) Nonferrous Met. Soc. China 26, 2960 (2016)
25. J.F. Giarola, K.B. Borges, C.R.T. Tarley, F.M. Oliveira, E.S. 37. R. Alfonsetti, L. Lozzi, M. Passacantando, P. Picozzi, S. Santucci,
Ribeiro, A.R. Pereira, Development and application of graphite- XPS studies on ­SiOx thin films. App. Surf. Sci. 70/71, 222 (1993)
SiO2/Al2O3/Nb2O5-methylene blue (GRP–SiAlNb–MB) compos- 38. L. Wang, J. Zhu, H. Yang, F. Wang, Y. Qin, T. Zhao, P. Zhang,
ite for electrochemical determination of dopamine. Arab. J. Chem. Fabrication of hierarchical graphene@Fe3O4@SiO2@polyaniline
10, 430 (2017) quaternary composite and its improved electrochemical perfor-
26. J.P. Marco, K.B. Borges, C.R.T. Tarley, E.S. Ribeiro, A.C. mance. J. Alloys Compd. 634, 232 (2015)
Pereira, Estudo eletroquímico do processo de eletrooxidação da 39. H.C. Choi, Y.M. Jung, S.B. Kim, Size effects in the Raman spectra
prometazina empregando sensor a base de pasta de nanotubos of ­TiO2 Nanoparticles. Vib. Spectrosc. 37, 33 (2005)
de carbono contendo DNA imobilizado em matriz in orgânica. 40. M.I. Litter, Heterogeneous photocatalysis transition metal ions in
Semin. Ciênc. Exatas Tecnol. (Impresso) 35, 215 (2014) photocatalytic systems. Appl. Catal. B 23, 89 (1999)
27. J.P. Marco, K.B. Borges, C.R.T Tarley, E.S. Ribeiro, A.C. Pereira, 41. R. Camposeco, S. Castillo, I. Mejía-Centeno, J. Navarrete, N.
Development of a simple, rapid and validated square wave volta- Nava, Boosted surface acidity in ­TiO2 and ­Al2O3–TiO2 nanotubes
metric method for determination of promethazine in raw material as catalytic supports. Appl. Surf. Sci. 356, 115 (2015)
and pharmaceutical formulation using DNA modified multiwall 42. S. Imamura, T. Nakai, H. Kanai, T. Ito, Effect of tetrahedral Ti
carbon nanotube paste electrode. Sens. Actuator B 177, 251 in titania–silica mixed oxides on epoxidation activity and Lewis
(2013) acidity. J. Chem. Soc. Faraday Trans. 91, 1261 (1995)
28. K.M. Diniz, F.A. Gorla, E.S. Ribeiro, M.B.O Nascimento, R.J. 43. S. Imamura, T. Nakai, H. Kanai, T. Ito, Titanium sites of titania
Corrêa, C.R.T. Tarley, M.G. Segatelli, Preparation of S ­ iO2/ silica mixed oxides for epoxidation activity and Lewis acidity.
Nb2O5/ZnO mixed oxide by sol–gel method and its application Catal. Lett. 28, 277 (1994)
for adsorption studies and on-line preconcentration of cobalt ions 44. J.C. McAteer, Acidic and basic properties of mixed tin–antimony
from aqueous medium. Chem. Eng. J. 239, 233 (2014) oxides. J. Chem. Soc. Faraday Trans. 75, 2762 (1979)
29. G.F. Lima, O.M. Ohara, D.N. Clausen, D.R. Nascimento, E.S. 45. A. Corma, H. García, Lewis acids as catalysts in oxidation reac-
Ribeiro, M.G. Segatelli, M.A. Bezerra, C.R.T. Tarley, Flow injec- tions: from homogeneous to heterogeneous systems. Chem. Rev.
tion on-line minicolumn preconcentration and determination of 102, 3837 (2002)
trace copper ions using an alumina/titanium oxide grafted silica 46. S. Denofre, Y. Gushikem, S.C. Castro, Y. Kawano, Stability and
matrix and FAAS. Microchim. Acta 178, 61 (2012) surface acidity of niobium(V) oxide grafted on a silica gel surface.
30. L.M. Costa, E.S. Ribeiro, M.G. Segatelli, D.R. Nascimento, F.M. J. Chem. Soc. Faraday Trans. 89, 1057 (1993)
Oliveira, C.R.T. Tarley, Adsorption studies of Cd(II) onto A ­ l2O 3/ 47. M.S.P. Francisco, R. Landers, Y. Gushikem, Local order struc-
Nb2O5 mixed oxide dispersed on silica matrix and its on-line ture and surface acidity properties of a N­ b2O5/SiO2 mixed oxide
preconcentration and determination by flame atomic absorption prepared by the sol–gel processing method. J. Solid State Chem.
spectrometry. Spectrochim. Acta. B 66, 329 (2011) 177, 2432 (2004)
31. T.E. Weirich, M. Winterer, S. Seifried, H. Hahn, H. Fuess, Riet- 48. E.A. Campos, Y. Gushikem, M.C. Gonçalves, S.C. Castro, Prep-
veld analysis of electron powder diffraction data from nanocrystal- aration and characterization of niobium oxide coated cellulose
line anatase, ­TiO2. Ultramicroscopy 81, 263 (2000) fiber. J. Colloid Interface Sci. 180, 453 (1996)
32. D.M. Tobaldi, A. Tucci, A.S. Škapin, L. Esposito, Effects of ­SiO2 49. M. Lefrancois, G. Malbois, The nature of the acidic sites on mor-
addition on T ­ iO2 crystal structure and photocatalytic activity. J. denite: characterization of adsorbed pyridine and water by infrared
Eur. Ceram. Soc. 30, 2481 (2010) study. J. Catal. 20, 350 (1971)
33. T.L. Barr, S. Seal, Nature of the use of adventitious carbon as a 50. C. Morterra, G. Cerrato, On the use of pyridine adsorption as an
binding energy standard. J. Vac. Sci. Technol. A 13, 1239 (1995) analytical tool in surface chemistry. Langmuir 6, 1810 (1990)
34. F.A. Rodríguez, E.P. Rivero, L. Lartundo-Rojas, I. González, 51. G. Busca, G. Centi, L. Marchetti, F. Trifiro, Chemical and spec-
Preparation and characterization of ­Sb2O5-doped Ti/RuO2–ZrO2 troscopic study of the nature of a vanadium oxide monolayer
for dye decolorization by means of active chlorine. J. Solid State supported on a high-surface-area ­TiO2 anatase. Langmuir 2, 568
Electrochem. 18, 3153 (2014) (1986)

13