Journal of Thermal Analysis and Calorimetry (2020) 140:2131–2142

https://doi.org/10.1007/s10973-019-08896-0

Physicochemical and photocatalytic properties of tin dioxide

supported onto silica gel
S. Khalameida1 · V. Sydorchuk1 · S. Levytska1 · N. Shcherban2

Received: 27 March 2019 / Accepted: 6 October 2019 / Published online: 15 November 2019
© Akadémiai Kiadó, Budapest, Hungary 2019

Abstract
The samples containing 1–10% tin dioxide supported onto silica gel have been synthesized via precipitation or thermolysis
of tin tetrachloride. The prepared samples have been characterized using DTA–TG, XRD, Raman and UV–Vis spectroscopy,
TPD of ammonia, and low-temperature nitrogen adsorption–desorption. The supported samples have been tested as photo-
catalysts in the process of rhodamine B degradation under visible irradiation. It has been established that the deposited phase
is uniformly dispersed on the surface. Redshift of band gap is observed for the supported samples. Unlike a bulk ­SnO2, the
supported samples exhibit photocatalytic activity under visible irradiation.

Keywords  Tin dioxide · Silica gel · Photocatalysis · DTA–TG · UV–Vis spectroscopy

Introduction simultaneously optimizes the porosity, creating a meso-

Tin dioxide ­SnO2 is a versatile material since it has wide
numerous applications in a bulk and deposited state as cata-
lyst, ion-exchanger, and material for gas sensors [1–3]. Being
a semiconductor by its nature, it is a promising photocatalyst
for processes of organic pollutants degradation [4–6]. The
efficiency of these applications is determined by crystal and
porous structure, surface design, and electronic character-
istics of ­SnO2. The main disadvantages of tin dioxide as a
photocatalyst are (i) large band gap (3.4–4.0 eV [1, 4, 6]);
as a result, this material is active only under UV irradia-
tion; (ii) preferably, a microporous structure, whereby a large
portion of the surface is inaccessible for large molecules
of organic substrates and diffusion difficulties slow down
the photocatalytic transformations. There are several ways
to overcome these shortcomings. Among them, introduc-
tion of intrinsic (structural) and extrinsic (dopant) defects in
“white” oxides results in the band gap narrowing and mani-
festation of activity under visible irradiation [7]. The use of
mechano- and sonochemical processes for these purposes
* S. Khalameida
svkhal@ukr.net
1
Institute for Sorption and Problems of Endoecology, NAS
of Ukraine, Naumova Street 13, Kiev 03164, Ukraine
2
L.V. Pysarzhevsky Institute of Physical Chemistry, NAS
of Ukraine, Nauky Ave. 31, Kiev 03028, Ukraine
macroporous structure (the most suitable structure for most
adsorption and catalytic processes) as it was demonstrated
for different perovskites and ­SnO2 [4, 5]. Another approach
can be the deposition of an active phase onto the surface
of mesoporous supports as it was shown for ­TiO2 [8–10],
­BaTiO3 [11], and heteropolycompounds [12, 13]. However,
this method practically was not investigated for the prepara-
tion of supported photocatalysts based on tin dioxide. The
exceptions are the papers on photodegradation of rhodamine
B (RhB) under UV irradiation using tin dioxide supported
on porcine bone and SBA-15 [14, 15]. In the first case, it
has been showed that about 97.3% of RhB can be decom-
posed (based on bleaching of RhB solution degree) when the
composition ­SnO2/porcine bone as a photocatalyst was used,
while only 51.5% of RhB can be degraded using pure ­SnO2
nanoparticles. In the second case, the rate constant of RhB
photocatalytic degradation is 3.8 × 10−5 s−1; in the third case,
the rate constant achieves value of 1.5 × 10−4 s−1. Therefore,
the possibility of pollutants photodegradation under visible
irradiation using ­SnO2 embedded into structure of support,
as it was done for titania [8–10] and mixed oxides [11, 16],
was not studied.
At the same time, it is known that deposition of tin diox-
ide onto silica promotes to improvement of its catalytic per-
formance in acid-catalyzed and oxidation processes [17–21].
Several methods for deposition of S ­ nO2 on porous supports
are known from the literature: sol–gel [22], polymeric [20],

13
Vol.:(0123456789)

2132
template [21], and impregnation [17]. We used the simplest
of them, namely impregnation of commercial silica gel and
subsequent precipitation or thermolysis of prepared precur-
sors. Silica being a dielectric was chosen as a support.
The aim of this work is the study of crystal and porous
structure, electronic characteristics of the supported ­SnO2/
SiO2 compositions of different ­SnO2 content and influence
of these physicochemical properties on their photocatalytic
activity under visible irradiation.
Experimental
Reagents and materials
Silica gel KSKG (China) was used as a support. In order to
increase the mesopore size, it was also subjected to hydro-
thermal treatment (HTT) in a vapor phase at 150 °C for 3 h
[23, 24]. Tin tetrachloride S
­ nCl4·5H2O was used as a source
of tin, aqueous ammonia solution—as a precipitant.
Preparation of supported ­SnO2/SiO2 compositions
Samples of ­SnO2/SiO2-supported compositions with differ-
ent tin dioxide content, designated as XSn, where X = 1, 3, 5,
7 and 10, (the number in the sample designation corresponds
to ­SnO2 content in mass%), were synthesized by deposition
of tin dioxide on silica gel granules using incipient wetness
impregnation. For this purpose, a fraction (0.5–2 mm) of
silica gel was impregnated with an appropriate amount of
­SnCl4·5H2O aqueous solution, held for 1 h, then treated
with 1 M N ­ H4OH solution to form an insoluble ­SnO2, then
dried at 110 °C and calcined in air at 450 and 550 °C (2 h).
This is precipitation method (designation of samples − XSn-
prec). In another procedure, the stage of precipitation using
­NH4OH was absent. This is thermolysis method (designation
of samples − XSn-therm). For the purpose of activation, a
precipitated sample containing 5% S ­ nO2 was also milled in
air for 0.5 h at 300 rpm (sample 5Sn-mill). For comparison,
the supported sample was also prepared by direct dry milling
of mixture of 5% ­SnO2 and silica gel under the same condi-
tions (sample 5Sn-mill-mix). Milling was carried out using
a planetary ball mill Pulverisette-7, premium line (Fritsch
Gmbh) with a vessel of silicon nitride. Twenty-five balls
from ­S3N4 with a 10 mm diameter (total ball mass − 40 g)
were used as working bodies.
Physicochemical measurements
The crystal structure of the supported samples was studied
by means of X-ray powder diffraction (XRD) using Philips
PW 1830 diffractometer with ­CuKα radiation. The curves
of DTA and TG were recorded using the Derivatograph-C
13
S. Khalameida et al.
apparatus (F. Paulik, J. Paulik, L. Erdey) in the temperature
range of 20–1000 °C at a heating rate of 10° min−1. The ini-
tial sample mass was about 200 mg, and the sensitivity was
50 mg. Raman spectra were recorded using spectrograph
of Renishaw system (Ar laser, 514 nm). Strength (H0) and
acid sites concentration in ­SnO2/SiO2 catalysts were deter-
mined using an indicator method and the back titration of
n-butylamine by hydrochloric acid in the presence of bro-
mothymol blue, respectively, as well as using temperature-
programmed desorption (TPD) of ammonia [19]. The porous
structure of the initial silica gel and supported samples was
studied using nitrogen adsorption–desorption technique. The
isotherms were obtained using an automatic gas adsorption
analyzer ASAP 2405 N (“Micromeritics Instrument Corp”)
after outgassing the catalysts at 150 °C for 2 h. The specific
surface area S, mesopore volume Vme, and micropore vol-
ume Vmi were calculated from these isotherms using BET,
BJH, and t-plot methods, respectively. The total pore volume
VΣ was determined by impregnation of the samples, which
were preliminarily dried at 150 °C, with liquid water (so-
called incipient wetness method [25]). Macropore volume
Vma was calculated as the difference between VΣ and sorp-
tion pore volume Vs. The latter one was determined from
the isotherms at nitrogen relative pressure close to 1.0.
The mesopore size dme was calculated from the curves of
pore size distribution (PSD) plotted using the desorption
branches of isotherms. Diffuse reflectance UV–Vis spec-
tra of the powders were registered on Lambda 35 UV–Vis
spectrometer (PerkinElmer Instruments). The band gap was
determined using Planks formula.
Photocatalytic testing
Photocatalytic degradation was performed in a glass reac-
tor under visible irradiation. LED Cool daylight lamp,
Philips (100 W) possessing emission spectra exclusively
in the visible range with a broad maximum in the region
of 500–700  nm and a local maximum around 440  nm,
was used as an irradiation source. The dye rhodamine
B (RhB) in the form of 1.5 × 10−5 mol ­L−1 solution was
used as a pollutant [16]. The main absorption bands λmax
in the spectra of substrate is 553 nm. The catalyst dose
was 1 g L−1 (80 mg of catalysts and 80 mL of solution).
Duration of dark adsorption to establish of equilibrium
was 60 min. The initial solution and solutions after dye
adsorption and degradation for 30–600 min were analyzed
spectrophotometrically at λmax (Lambda 35, Perkin Elmer
Instruments) after centrifugation of the reaction mixture
(10 min at 8000 rpm). The calculation of photodegrada-
tion rate Kd was based on the temporal changes of the dye
concentration after reaching the adsorption equilibrium.
The total organic carbon (TOC), which is a measure of dye
Physicochemical and photocatalytic properties of tin dioxide supported onto silica gel 2133
mineralization [26], for selected solutions, was determined
using a Shimadzu TOC analyzer (model 5050A).
Results and discussion
Thermogravimetric measurements
In order to determine the temperature of thermodestruc-
tion of S
­ nCl 4·5H 2O resulting in tin dioxide formation,
the DTA–TG curves for bulk salt as well as for compo-
sitions precursors prepared on its basis were registered.
Obviously, ­SnCl4·5H2O is decomposed in air according
to Eq. (1):
SnCl4 ⋅ 5H2 O = SnO2 + 4HCl + 3H2 O
Theoretical mass loss for this process is 54.1% w/w.
Experimental value of mass loss calculated from DTA–TG
curves of bulk S ­ nCl 4·5H 2O is 55.5% w/w. At the same
time, this process takes place in a wide temperature
range—from 100 to 450 °C (Fig. 1a). It can be divided into
two stages: (i) sharp stage at 100–200 °C with an intensive
endoeffect at about 150 °C when mass loss is 47.9% w/w
(crystallization water) and (ii) slow stage at 200–450 °C
when mass loss is 7.6% w/w. It should be noted that simi-
lar curves were obtained for hydrous copper, cobalt, and
manganese chlorides [27].
On the other hand, there is an endoeffect at 20–200 °C
with a maximum at 115  °C, which is accompanied by
release of water from the pores, for the initial porous silica
and supported samples, namely their precursors (Fig. 1b, c,
respectively). These endoeffects are characteristic for porous
materials including supported compositions based on porous
carriers [11–13, 16, 28, 29]. Therefore, the first stage of
­SnCl4·5H2O decomposition for supported precursors is over-
lapped with removal of this physically bound water from
the pores of silica gel. At the same time, removal of surface
OH groups additionally occurs on the second stage which
is the characteristic for silica [23]. This value is 0.72% w/w
(Table 1).
Therefore, mass loss in the range of 200–450 °C for
precursors is determined by the tin chloride decomposi-
tion process and the removal of hydroxyl groups. The first
component depends on the precursor composition, i.e.,
content of S­ nCl 4, and the second one is approximately
constant—about 0.72% w/w:
Δm200−450_therm = X ⋅ 7.6∕100 + (1 − X) ⋅ 0.72∕100 (%w/w),
(2)
where X—SnO2 content in composition.
It can be seen that Δm200–450_therm values, determined
from the experimental data (Table  1, column 6), are
well-consistent with those ones calculated by the formula
(2).
Precursors, prepared with a precipitation stage, contain
tin dioxide and ammonium chloride which are formed in the
pores of silica gel according to the equation:
SnCl4 + 4NH3 + 2H2 O = SnO2 + 4NH4 Cl (3)
In line with it, mass loss in the range of 200–450 °C for
these precursors is determined by the ammonium chloride
sublimation [30] and the removal of hydroxyl groups both
for silica gel and precipitated tin dioxide [1, 4, 5]. The
­NH4Cl content in the products of the reaction (3) is about
58.6% w/w and mass loss in the range of 200–450 °C for
precipitated ­SnO2 is 4.86% [4]. Therefore, total mass loss
in the range of 200–450 °C for the precursors prepared via
precipitation can be calculated as follows:
(1)
Δm200−450_prec = X ⋅ 58.6∕100 + X ⋅ 4.86∕100 + (1 − X) ⋅ 0.72∕100
(4)
The experimental data presented in column 7 of Table 1
are in a good agreement with those ones calculated by
the formulas (2) and (4).
Based on the results of thermogravimetric measure-
ments, the first calcination temperature of precursors was
determined as 450 °C. The second calcination temperature
of 550 °C was chosen since content of surface OH groups
was reduced by 11% compared with the samples calcined at
450 °C for silica gel as shown in [21] and by 8% for tin diox-
ide xerogel [4] according to the data of DTA–TG. Therefore,
use of the samples calcined at these temperatures makes
it possible to establish the influence of the content of OH
groups on the photocatalytic activity. It should also be noted
that the indicated values of temperature (450 and 550 °C)
correspond to optimal conditions for regeneration of oxide
catalysts using oxygen and air, respectively [31].
Crystal structure
Crystal structure of tin dioxide in composition is formed
during calcinations of precursors. XRD patterns for some
supported samples as well as for pure S ­ nO2 calcined at
550 °C are depicted in Fig. 2. As can be seen, positions
of the diffraction peaks corresponding to the planes (110),
(101), (200), and (211) are attributed to tetragonal modifica-
tion of cassiterite/rutile (JCPDS N 41-1445). The intensity
of all the peaks is predictably increased with an increase in
the content of tin dioxide. The reflexes also differ in width,
which is a measure of crystallinity (crystallite size Dhkl),
and I110/I101 ratio. Since reflex with maximal intensity (110)
is overlapped with halo characteristic for amorphous silica,
calculation of crystallites size was performed using reflex
attributed to the plane (101) (D101). These parameters are
determined by ­SnO2 content in composition and calcinations
13

2134 S. Khalameida et al.

Fig. 1  a DTA, TG, DTG curves DTG/mg min–1

for ­SnCl4·5H2O. b DTA, TG,
(a) Mass loss/% DTA/µV mg–1
DTG curves for the initial silica
0.6 0.2
gel. c DTA, TG, DTG curves TG
for a precursor containing 10% 0
­SnCl4 DTG 0.5 0.0

12 0.4
– 0.2

0.3
24 – 0.4
DTA
0.2
36 – 0.6

0.1
– 0.8
48
0.0
– 1.0
60 – 0.1
– 1.2
200 400 600 800
Temperature/°C

DTG/mg min–1
(b) Mass loss/%
DTA/µV mg–1 0.45
0
TG 0.40
0.0
1
DTG 0.35

2 0.30

DTA 0.25
3
– 0.1

4 0.20

0.15
5

0.10
6 – 0.2
0.05
200 400 600 800
Temperature/°C

DTG/mg min–1
(c) Mass loss/% DTA/µV mg–1
0.50
TG
0
0.45
1
0.40
DTA
0.0
2 0.35

3 DTG 0.30

4 0.25

0.20 – 0.1
5

0.15
6
0.10
7
0.05 – 0.2
200 400 600 800
Temperature/°C

13
Physicochemical and photocatalytic properties of tin dioxide supported onto silica gel 2135

Table 1  Results of N Synthesis conditions Temperature of effect Δm20–200/% w/w Δm200–450/% Δm450–550/%

thermogravimetric from DTG curve/°C w/w w/w
measurements for some ­SnO2/
SiO2 samples 1 Initial silica gel 113 3.71 0.72 0.19
2 3Sn without precipitation 110 3.88 0.93 0.20
3 5Sn without precipitation 115 3.60 1.13 0.21
4 5Sn with precipitation 118 4.11 3.94 0.26
5 7Sn without precipitation 113 3.69 1.31 0.22
6 10Sn without precipitation 118 3.53 1.48 0.24
7 10Sn with precipitation 121 4.55 6.88 0.29
8 Precipitated ­SnO2 128 13.01 4.86 0.48

1200 Table 2  Some parameters of crystal structure

900 Sample Method of prepara- Temperature/°C D101/nm I110/I101
a
600 tion
300 3Sn Precipitation 450 5.0 1.69
0 550 5.8 1.55
3300 5Sn Precipitation 450 6.0 1.88
b 550 7.1 1.70
2200
Thermolysis 450 7.3 1.58
1100
550 10.0 1.50
0
7Sn Precipitation 450 7.5 1.55
3300 550 8.8 1.45
Intensity/a.u.

c 10Sn Precipitation 450 10.4 1.52

2200

1100
550 11.0 1.40
Thermolysis 550 11.2 1.34
0
100Sn Precipitation 450 12.0 1.05
3300
d 550 15.6 1.11
2200

1100

0
110 101
A feature of the supported samples also is an increase
17700
in I110/I101 value (Table 2, column 5) compared to that for
11800 e pure ­SnO2 prepared under the same conditions as well as
5900 described in the literature [1, 6, 33]. It can also be seen that
0 this value is larger for the samples prepared via precipitation
10 15 20 25 30 35 40 45 50 55 60 and decreases when calcinations temperature is elevated.
2θ /° This parameter characterizes the surface orientation of
defined planes which can be very important for catalytic
Fig. 2  XRD patterns for the supported samples after calcinations at processes [34, 35] including photocatalytic transformation
450 °C: 3Sn_prec (a), 5Sn_therm (b), 5Sn_prec (c), 10 Sn_prec (d), [36]. Particularly, the  ratio of different crystallographic
bulk precipitated ­SnO2 (e) planes (surface content) and, as a result, catalytic proper-
ties, could be changed by various types of treatment for
temperature which is also quite expected (Table 2). Thereby, vanadium–molybdenum oxides [35, 37]. These are so-called
­D101 value is increased as a result of enrichment of the com- structural-sensitive reactions [1, 36].
position with tin dioxide and an elevation in the calcinations Raman spectra confirm low crystallinity for deposited
temperature. On the other hand, calculated crystallite size ­SnO2 phase which can be seen from the comparison of the
for the supported samples is 2–3 times smaller than for bulk spectra registered for bulk and supported tin dioxide (Fig. 3)
­SnO2 calcined at 450–550 °C. It indicates well-dispersion As can be seen (Fig. 3, spectra b, c), there are low-inten-
of the deposited phase on the support surface as it was pre- sity bands centered at 795 and 590 cm−1 which attributed
viously observed for supported titania [8–10] as well as for to ­SnO2 nanoparticles with a size less than 10 nm [17, 38,
mixed oxide compositions [11, 32]. 39]. Besides, broad bands at 300–550 cm−1, which can be a

13

2136 S. Khalameida et al.

superposition of several bands characteristic for tin dioxide

4000 a [39], are presented in Fig. 3 (spectra b and c). Similar spectra
3000 were also obtained for samples containing 5–10% of ­SnO2
incorporated into structure of dealuminated zeolite ß [18]. It
2000 should be noted that there are no bands for amorphous silica
in this range [40].
1000

0
Porous structure
750
b
Parameters of porous structure for initial silica gel and
Intensity/a.u.

500 supported samples were calculated from nitrogen adsorp-

tion–desorption isotherms, examples of which are shown in
250 Fig. 4. All of them belong to type IV according to IUPAC
classification which is characteristic for mesoporous materi-
0
als. The curves of pore size distribution PSD (inset of Fig. 4)
1000 also indicate it.
c Thus, initial silica gel contains mesopores with a size
750 in the range of 2–14  nm and maximum on PSD curve
about 7.8 nm but does not contain micro- and macropores
500 (Table 3). Deposition of tin dioxide on siliceous surface
predictably leads to some decrease in the specific surface
250 area, total pore volume and mesopore volume but their size
remains almost the same (inset of Fig. 4, Table 3, columns
0 7). Silica gel subjected to HTT has a smaller specific sur-
0 500 1000 1500 2000
face area but larger mesopores, namely 9.8 nm. Therefore,
Raman shift/cm–1
the supported sample based on the hydrothermally treated
silica gel also has a smaller specific surface area and larger
Fig. 3  Raman spectra for bulk tin dioxide (a) and supported samples
containing 5 (b) and 10% (c) of S
­ nO2 mesopores. Maximum reduction in the specific surface area

Fig. 4  Nitrogen adsorption–
0.035
desorption isotherms and PSD Initial silica gel
curves for the initial silica gel
700 0.030
and some supported samples 1Sn-prec
0.025 5Sn-prec
600
0.020 5Sn-mill
dv/dr

0.015
500

0.010

400
a/cc g–1

0.005

0.000
300
0 5 10 15 20
r /nm

200

100

0
0.0 0.2 0.4 0.6 0.8 1.0
P/P0

13
Physicochemical and photocatalytic properties of tin dioxide supported onto silica gel 2137

Table 3  Parameters of porous Sample Method of preparation Temperature/°C S/m2 g−1 VΣ/cm3 g−1 Vme/cm3 g−1 dme/nm
structure of supported samples
SiO2 – – 371 0.97 0.98 7.8
1Sn Precipitation 450 365 0.92 0.92 7.8
Thermolysis 450 367 0.93 0.92 7.8
3Sn Thermolysis 450 362 0.90 0.90 7.8
550 359 0.91 0.90 7.8
5Sn Thermolysis 450 357 0.93 0.92 7.9
550 355 0.94 0.93 7.9
Precipitation 450 360 0.91 0.91 7.8
Precipitation 550 354 0.90 0.89 7.8
5Sn-HTT Precipitation 450 320 0.90 0.89 9.5
5Sn-mill Precipitation – 198 0.50 0.48 7.9
5Sn-mill-mix Precipitation – 301 0.74 0.73 7.8
7Sn Thermolysis 450 350 0.90 0.89 8.1
550 345 0.89 0.89 8.0
10Sn Thermolysis 450 344 0.88 0.87 8.1
550 340 0.87 0.87 8.1

and pore volume is observed for the milled sample 5Sn-
mill (Fig. 4, Table 3, column 4) which is consistent with the
results obtained for a milled silica gel of different porous
structure [23, 41].
UV–Vis spectra
Diffuse reflectance UV–Vis spectra for some supported
samples with different ­SnO2 content are presented in Fig. 5.
One can see that they differ in the position of the absorp-
tion edge λ and the magnitude of absorption in the visible
region. It is important that significant redshift of absorption

Fig. 5  UV–Vis spectra for some

supported samples 1.0 1Sn-prec
10Sn-prec
0.9 5Sn-prec
5Sn-therm
0.8

0.7
0.5
K – M index

0.6

0.5 0.4
K – M index

0.4
0.3

0.3

0.2
0.2
350 400 450
Wavenumber/nm
0.1
200 300 400 500

Wavenumber/nm

13

2138 S. Khalameida et al.

Table 4  Electronic and photocatalytic properties of the supported samples

N SnO2 content/% Preparation conditions λ/nm Eg/eV a/% Kd 105/s−1 Bleaching
degree/%

1 1Sn Precipitation, 450 °C 392 3.16 40 5.6 84

2 3Sn Precipitation, 450 °C 399 3.11 45 7.2 88
3 5Sn Precipitation, 450 °C 407 3.05 56 9.1 92
4 5Sn Precipitation, 550 °C 388 3.20 40 7.0 84
5 5Sn Thermolysis, 450 °C 375 3.31 44 6.1 80
6 5Sn Thermolysis, 550 °C 365 3.40 37 5.1 76
7 5Sn Precipitation, 450 °C, ­SiO2 treated via HTT *n.d – 33 3.9 63
8 5Sn Precipitation, 450 °C MChT *n.d – 32 3.1 68
9 5Sn Precipitation, 450 °C + SiO2 MChT *n.d – 37 0.1 11
10 7Sn Precipitation, 450 °C 367 3.38 41 5.8 82
11 10Sn Precipitation, 450 °C 364 3.41 25 3.1 59
12 10Sn Thermolysis, 450 °C 356 3.48 36 2.0 44
13 100Sn Precipitation, 450 °C 341 3.64 30 – –

*n.d not done

edge is observed for the supported samples compared with
bulk ­SnO2.
Thus, λ is 364–341 nm for bulk tin dioxide [4, 5], while
its value is shifted toward 407–356 nm for the precipi-
tated samples containing 1–10% ­SnO2 (Table 4). It cor-
responds to narrowing the band gap Eg from 3.64 eV for
bulk ­SnO2 [4, 5] to 3.05–3.48 eV for the supported sam-
ples (Table 4, columns 4, 5). Such an effect was earlier
described for silica supported T ­ iO2 photocatalysts [8, 9]
and for ­SnO2–TiO2 solid solution embedded into SBA-15
structure [42]. But it was not observed for deposited S ­ nO2,
as a rule [15, 21, 42]. Similar spectrum is given only in the
paper [18] for sample containing 10% S ­ nO2 incorporated
into the structure of dealuminated ß zeolite. However, the
authors do not discuss it. Moreover, co-precipitated (but
not supported) ­SnO2–SiO2 samples prepared by a sol–gel
method and additionally calcined at 800 °C showed red-
shift in UV–Vis spectra with an increase in ­SnO2 content
from 1 to 10% [43].
A feature of the spectrum for 5Sn-prec-450 is the pres-
ence of another absorption edge in the long-wavelength
region—about 540 nm (selected fragment in Fig. 5). As a
result, the occurrence of an additional level in the forbidden
zone of ­SnO2 is possible. Similarly, a new metastable surface
phase exhibits with much reduced band gap from that one of
bulk ­TiO2 (about 2 eV) on the rutile ­TiO2 (011) surface [36].
Photocatalytic tests
It is well-known that the photocatalytic properties of semi-
conductors depend on their electronic characteristics, crystal
and porous structure, specific surface area and degree of
hydroxylation, and therefore, adsorption capacity toward
the substrate [7, 26]. It is also natural that the first stage of
1.0
0.30

It is noteworthy that observed redshift of absorption 0.8

0.25
edge for the precipitated samples is significantly larger
than for the samples prepared via thermolysis (Fig. 5,
TCD signal/a.u.

0.20
0.6
Table 4). An observed redshift effect can be associated
dVHCl/dT

with different surface orientations of deposited crystallites 0.15

compared to crystallites in bulk S ­ nO2 (Table 2, increase in 0.10

0.4

I110/I101 ratio from 1.05–1.10 to 1.34–1.88). It is in a good

agreement with the results described for ­TiO 2 in [30]; 0.05 0.2
UV–Vis spectroscopy measurements of anatase crystals
0.00
with different surface orientations have revealed differ-
0.0
ences in the band gap indicating the upward shift in the 0 100 200 300 400 500 600 700
conduction band minimum for anatase (101) and (100) Temperature/°C
compared to (001) surfaces.
Fig. 6  NH3-TPD profile for the sample 5Sn_prec-450

13
Physicochemical and photocatalytic properties of tin dioxide supported onto silica gel 2139

catalysis is the adsorption of reagents on the catalyst surface. (a) 0.3 0

Based on the fact that the tested dye has a basic nature, it was 1800 s
important to evaluate the acidic properties of the photocata- 3600 s
7200 s
lyst surface. Using the indicator method, it was established 10,800 s
0.2
that the supported samples have concentration of acid sites 18,000 s
within 1.58–1.68 mmol g−1 or 4.3–4.6 μmol m−2. The value 27,000 s
36,000 s

D
of Gammet function H0 is about − 3, i.e., acid sites are weak. RhB initial
At the same time, ammonia TPD profile obtained for the 0.1

sample 5Sn_prec-450 (Fig. 6) shows the value of acid sites

concentration equal to 1.51 mmol g−1 which is close to the
above indicated range. Temperature of the maximum is at 0.0
172 °C which also corresponds to weak acid sites. It should
be noted that similar results were obtained for ­SnO2–SiO2 400 500 600

xerogels containing 3–9% w/w of tin dioxide [44], while Wavenumber/nm

content of acid sites for bulk ­SiO2 and ­SnO2 is 1.10 and
(b) 0.30
0.38 mmol g−1 or 3.0 and 6.5 μmol m−2, respectively. As 0
can be seen, the supported samples have close acidity val- 0.25 1800 s
ues, but higher than the values based on the additivity rule. 3600 s
7200 s
Therefore, the difference in RhB adsorption during dark 0.20
10,800 s
stage a (%), determined as the ratio of optical density of 18,000 s
0.15
RhB solution before and after dark stage, depends primarily 27,000 s
D 36,000 s
on the value of the specific surface area and, possibly, on the 0.10
surface content of (110) plane (I110/I101 ratio).
At the same time, band gap (namely < 3.26  eV) and 0.05
absorption value in the region with wavelength > 380 nm for
the photocatalyst determine its activity under visible irradia- 0.00

tion [7]. As shown in Table 4, some of the prepared samples

(namely NN 1-4) meet these conditions. Consequently, the
appearance of an electron–hole pair on the catalyst surface
due to the action of photons of visible light is possible in this
case. It results in initiation of a conventional photocatalytic
process. As a result, these samples showed high activity in
the process of RhB degradation. The latter is evidenced by
the character of the changes in the RhB spectrum during
its degradation in the presence of the samples of different
activity (Fig. 7a, b). The similar spectra were also obtained
for other photocatalysts. It should be noted that bulk pre-
cipitated ­SnO2 prepared under the same conditions does not
show noticeable activity when it is exposed to visible light
[4] which is associated with a high band gap value (3.41 eV)
and minimal absorption in visible region for this sample.
It is well-known that RhB photodegradation in the pres-
ence of tin dioxide can occur by two pathways [4–6]: as de-
ethylation process in a stepwise manner (with the formation
of three intermediates from RhB to Rh110) or as a direct
cleavage of the chromophore rings. A gradual blueshift of
the band at 553 nm on the spectrum of the RhB solution is
observed in the first case and the reduction in its intensity
without shift takes place in the second case. As shown in
Fig. 7a, b, mixed mechanism is realized in this case as it
was described earlier for doped and milled ­SnO2 [4, 5]: (i)
decrease of the intensity band at 553 nm occurs for 60 min
which corresponds to direct degradation of RhB [16]; (ii)
200 300 400 500 600 700
Wavenumber/nm
Fig. 7  a Spectra of RhB depending on degradation time in the pres-
ence of 5Sn_prec_450. b Spectra of RhB depending on degradation
time in the presence of 3Sn_prec_450
shift of this band toward 498–500 nm for 180 min which is
accompanied by complete de-ethylation of RhB to Rh110;
(iii) decrease in intensity of the band at 498–500 nm which
is associated with degradation of Rh110 with cleavage of the
chromophore rings (for duration > 180 min).
The photocatalytic tests showed that the degradation
of RhB under visible irradiation (as dye bleaching) using
the supported samples proceeds according to first-order
kinetic equation (Fig.  8) with a correlation coefficient
R2 = 0.93–0.99, which is agreed with literature data [4–6,
16]. The photodegradation rate constants Kd were calculated
from the slopes of the plots ln(D/D0) − τ (where D and D0
are values of optical density of RhB solution after time τ
and dark adsorption, respectively). One can see (Table 4)
that photocatalytic activity, the measure of which is the Kd
magnitude, for the precipitated samples is increased with
an increase in S­ nO2 content up to 5% and decreased with a
further increase in its content up to 10%. In general, it corre-
lates with the electronic characteristics of the photocatalysts:

13

2140
0.5
0.0
– 0.5
– 1.0
In/D/D0
– 1.5
– 2.0
SnO2 bulk
– 2.5 1Sn/SiO2
5Sn/SiO2
– 3.0
10Sn/SiO2
– 3.5
– 4.0
0 5000 10000 15,000 20,000 25,000 30,000 35,000 40,000
τ /s
Fig. 8  Kinetic curves of RhB degradation for some tested samples
the samples containing 1–5% ­SnO2 have Eg = 3.05–3.20 eV,
i.e., less than 3.26 eV and absorption in visible region for
them is 25–40%, while these parameters are 3.35–3.41 eV
and 15–20%, respectively, for samples containing 7–10%
­SnO2 (Table 4). Therefore, generation of an electron–hole
pair is possible in the first case. Moreover, the number of
active sites should be increased with an increase in ­SnO2
content. In the second case, the samples also exhibit suffi-
cient photocatalytic activity. The latter can be explained as
follows. The spectrum of RhB absorption is overlapped in a
wide region with the emission spectrum of a lamp—illumi-
nation source; the maxima are located at 553 and 565 nm,
respectively. Therefore, the absorption of visible light and
the direct excitation of RhB molecules are very likely. Sub-
sequent injection of an electron from the excited RhB mol-
ecules into the conduction band of a photocatalyst occurs. It
is so-called photosensitization contributing the initiation of
photocatalytic process [26, 45]. Obviously, this mechanism
determines the photocatalytic activity of the samples pos-
sessing Eg > 3.26 eV, although it can also contribute to the
activity of the samples with Eg < 3.26 eV.
For the most active sample, namely containing 5% S ­ nO2,
the influence of preparation conditions on the photocatalytic
activity was studied. One can see that the samples prepared
via thermolysis have lower activity, and it is directly related
to the larger Eg value and lower absorption for visible irra-
diation (Table 4). An increase in calcinations temperature
for the samples prepared via precipitation and thermolysis
from 450 to 550 °C results in a slight decrease in activity. It
can be explained by a decrease in concentration of the sur-
face OH groups which influence on photocatalytic processes.
As mentioned above, their content according to TG data is
reduced by approximately 10% in this temperature range.
It is also important to evaluate the effect of other phys-
icochemical characteristics on photocatalytic properties.
13
S. Khalameida et al.
Particularly, it is difficult to associate an increase in crys-
tallite size D101, which is observed with increasing S ­ nO2
content (Tables 2, 4), with activity. Here, it is important to
have an actual increase in the content of the active phase,
as established for 5.8–17.7% of S ­ nO2 embedded into SBA-
15 under UV irradiation [15]. At the same time, surface
exposition of certain crystallographic planes can affect the
dye adsorption and through it on photocatalytic activity. On
the contrary, the dependence of the activity on the specific
surface area was precisely established earlier [1, 7]. At the
same time, the tested samples have close S values (Table 3).
In order to reduce the specific surface area of the support,
and therefore the supported sample, silica gel was subjected
to HTT. Photocatalyst prepared on the basis of a hydrother-
mally treated support showed significantly lower activity
(Table 4, sample 7).
Finally, an attempt to activate the most effective cata-
lyst (sample 3) by milling, as was done for bulk S ­ nO2 [5],
was made. As shown in Table 4 (sample 8), positive effect
was not achieved. Furthermore, the samples prepared via
milling of tin dioxide and silica gel mixture (without pre-
liminary deposition of ­SnO2 on silica gel) was practically
inactive, although the adsorption of RhB was quite large
(sample 9). It can be explained as follows. Under milling,
­SnO2 (semiconductor) is partially (sample 8) or completely
(sample 9) coated by a silica layer (dielectric). As a result,
the active sites of S
­ nO2 are blocked. Taking into account a
large excess of silica in relation to S­ nO2, as well as the dif-
ference in the hardness of the components (Mohs hardness
of amorphous silica and S ­ nO2 is 5 and 6.5, respectively)
[46, 47], “smearing” of amorphous silica on S ­ nO2 nano-
crystallites is possible. Similar results were described when
“core–shell” particles were formed during dry milling of
cerium and molybdenum oxides mixtures [48].
As shown in Table 4 (column 8) bleaching degree of RhB
under visible irradiation for the most active sample reaches
88–92% which is comparable with ones obtained in [14]
for the same dye using the ­SnO2/porcine bone photocatalyst
but under UV irradiation. At the same time, the mineraliza-
tion degree of a dye is even more important indicator for
evaluating of the photocatalyst efficiency [26]. This param-
eter, calculated as the degree of total organic carbon (TOC)
reduction, is 40 and 75% for sample containing 5% S ­ nO2
calcined at 450 °C and prepared via thermolysis and pre-
cipitation, respectively.
Conclusions
Using thermogravimetric analysis, it has been established
that hydrous tin tetrachloride is transformed into tin dioxide
in silica gel pores at 450 °C. The choice of the temperature
of the precursor transformation into the oxide composition
Physicochemical and photocatalytic properties of tin dioxide supported onto silica gel 2141
is based on these results. Also, it has been estimated the
degree of surface dehydroxylation within the range of
450–550 °C. Deposition of 1–10% tin dioxide onto silica
gel contributes to its dispersion on the surface; crystallite
size of ­SnO2 is decreased from 12 nm for a bulk sample to
5–10 nm (depending on ­SnO2 content) for the supported
samples. Besides, surface re-orientation of the crystallites
occurs: content of (110) plane, expressed as I110/I101 ratio,
is increased by 45–80%. Moreover, narrowing the band gap
from 3.64 eV for bulk ­SnO2 to 3.05–3.48 eV for the samples
containing 1–10% ­SnO2 is observed. As a result, the sup-
ported samples, in contrast to the bulk S­ nO2, exhibit photo-
catalytic activity under visible irradiation. The precipitated
samples are more effective compared with the samples pre-
pared by thermolysis. An increase in calcinations tempera-
ture decreases the photocatalytic activity due to a reduction
in the specific surface area and surface dehydroxylation.
The precipitated sample with 5% of tin dioxide calcined at
450 °C, which has I110/I101 = 1.88 and band gap 3.05 eV,
possesses maximal activity.
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