Journal of Environmental Chemical Engineering 8 (2020) 103718

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Journal of Environmental Chemical Engineering

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Effect of silver doping on the photocatalytic activity of TiO2 nanopowders T

synthesized by the sol-gel route
S. Abbada, K. Guergouria,*, S. Gazaouta, S. Djebabraa, A. Zertalb, R. Barillec, M. Zaabata
a
Laboratory of Active Components and Materials, University Larbi Ben M'Hidi of Oum, El Bouaghi, 04000, Algeria
b
Laboratory of Innovative Techniques for Environmental Preservation, University of Frères, Mentouri Brothers - Constantine 1, Constantine, 25000, Algeria
c
MOLTECH-Anjou University of Angers, CNRS UMR 62002, Bd Lavoisier, 49045, Angers Cedex 01, France

A R T I C LE I N FO A B S T R A C T

Keywords: Nanopowders of TiO2 and Ag-TiO2 have been synthesized by the sol-gel route. The obtained gels were calcined at
Ag-TiO2 500 °C to obtain desired nanopowders. The characterization was done by X-Ray Diffraction (XRD), Transmission
Sol-gel Electron Microscopy (TEM), Ultraviolet-Visible Spectroscopy (UV–Vis) and Fourier Transform Infrared
Nanopowders Spectroscopy (FTIR). The photocatalytic activity of TiO2 and Ag-TiO2 was evaluated by measuring the de-
Photocatalysis
gradation of Methylene blue (MB) under UV irradiation. All obtained nanopowders exhibit peaks of anatase
Methylene-blue
structure with an average grain size varying between 18 nm and 16 nm, which is well supported by TEM mi-
crographs showing that the shape of nanopowders is spherical. The band-gap energy varies between 3.22 eV and
2.67 eV as a function of Ag concentration. FTIR spectra showed TiO2 peaks identified as: Ti-O-Ti metal bond in
all samples. The photocatalysis experiments demonstrated that the degradation of MB is higher for Ag-TiO2 and
increases when Ag concentration increases.

1. Introduction [11,13], optical characteristics [14], non-toxicity [15] and photo-

stability towards light [1].
The photocatalytic degradation studies have been extensively de- To improve the photocatalytic activity of most semiconductors or
veloped during the last two decades. For waste water treatment several oxides such TiO2 they are doped with non-metal or metal impurities
organic and inorganic pollutants have been degraded photocatalyticly [16–18]; the transition metal ion in TiO2 is that it provides a means of
using oxide semiconductors as a photocatalyst. A large number of trapping the charge carrier, improving thereby the efficiency of the
semiconductor oxides exhibit good photocatalytic activity [1], such as catalyst [19]. Recently, silver ions have attracted the interest of several
titanium dioxide (TiO2), one of the most widely studied for the de- researchers, because of their effect on the improvement of the photo-
gradation of organic contaminants from water and air [2]. activity of nanocrystalline semiconductors [20–22].
In nanocrystalline form, TiO2 is among well-known semiconductors By doping TiO2 with Ag we expect to have various effects on its
with photocatalytic activities, and a great potential for applications photocatalytic activity, based on the following mechanisms:
such as in environmental purification, decomposition of carbonic acid (i) It may enhance the electron-hole separation by acting as electron
gas, pigments, catalyst supports, fillers, coatings, photoconductors, di- traps, (ii) extend the light absorption into the visible range and enhance
electric materials, and generation of hydrogen gas [3]. The field of use surface electron excitation by plasmon resonances excited by visible
of TiO2 is very wide as it has been mentioned in many articles [4–9], light and (iii) modify the surface properties of photocatalysts [2].
where it is cited as: photoelectrolysis, dye sensitized solar cells, gas To elaborate TiO2 nanopowders, several synthesis methods have
sensor, optical fibers, electro chromic material for display devices been used, the most important are: the co-precipitation [23], the me-
biomedical fields, etc… chanochemical technique [24], the sol–gel route [25], the aerosol
Titanium dioxide has several advantages over other photocatalysts powder coating [26] and the hydrothermal crystallization [27].
because of its physical and chemical properties, such as its high stabi- Among the above mentioned methods, the sol-gel process is the
lity, catalytic activity and oxidative power, as well as its ease of pro- most simple and sophisticated method [28] offering several advantages,
duction [4,10–12] at lower cost. There are some other properties that such as the ability to go all the way from molecular precursor to the
make it very competitive such as its good transparency as thin film product [29], a control of the nanoparticles growth, a shorter

⁎
Corresponding author.
E-mail address: [email protected] (K. Guergouri).

https://doi.org/10.1016/j.jece.2020.103718
Received 20 October 2019; Received in revised form 21 January 2020; Accepted 23 January 2020
Available online 24 January 2020
2213-3437/ © 2020 Elsevier Ltd. All rights reserved.
S. Abbad, et al. Journal of Environmental Chemical Engineering 8 (2020) 103718

processing time, a lower processing temperature, a better homogeneity, 2.3. Characterization

a higher purity, an accurate control of composition and a lower cost
[30–33]. The obtained powders were characterized by several techniques: X-
In the present work, TiO2 and Ag-TiO2 powders were synthesized by ray diffraction, using the Cukα (λ = 0.1541838 nm) radiation of a
the sol–gel route. The physico-chemical properties of the prepared BRUKER-AXS, a D8 advance X-ray diffractometer, in order to identify
powders were characterized by several techniques: X-Ray Diffraction the structure and calculate the grain size. The morphology as well as the
(XRD), Transmission Electron Microscopy (TEM), Ultraviolet-Visible size of the particles were determined using transmission electron mi-
Spectroscopy (UV–Vis) and Fourier Transform Infrared Spectroscopy croscopy images obtained by a JEOL microscope, JEM-1400, operating
(FTIR). at 120 kV. UV–Vis absorption obtained on a (V-750, JASCO) spectro-
The influence of the irradiated photocatalyst TiO2 and Ag-TiO2 on photometer from 900−190 nm allowed the study of the optical prop-
the degradation of Methylene Blue (MB, C16H18N3S) was investigated erties and the calculation of the optical gap energy. Finally, the FTIR
using a fluorescent lamp TLD 15 W/05 (Philips) emitting within spectra measured by a Bruker Model Vertex 70 spectrometer with a
300−450 nm with a maximum emission at 365 nm. wavenumber ranging between 400 cm−1 and 4000 cm−1 allowed,
The study of all these properties and their relation with the photo- through their vibration frequencies, the identification of the different
catalytic activity, which represents the essential aim of this research, entities present in the powders.
has been clearly established.
2.4. Photocatalytic activity

2. Materials and methods The photocatalytic activity of all powders was evaluated by mea-
suring the degradation rates of methylene blue solution (0.03 mg/L)
2.1. Materials under ultraviolet (UV) light irradiation, where 0.05 g of catalyst powder
was added to 50 mL of methylene blue solution in a glass beaker. The
The titanium tetra n-butoxide Ti(C4H9O)4 (purity = 97 %, Sigma obtained suspension was then magnetically stirred. The irradiation was
Aldrich) has been used as titanium precursor and silver nitrate AgNO3 performed using a fluorescent lamp TLD 15 W/05 (Philips) emitting
(purity > 99 %, Fluka Chemika) as silver precursor. Acetic acid glacial: within 300−450 nm with a maximum emission at 365 nm. The ab-
CH3COOH (purity = 99.5 %, Biochem Chemopharma) was used as a sorption spectra were recorded using UV–Vis spectrophotometer (UV-
reagent and methylene blue C16H18N3S (E. Merck. Darmstadt) as a 1800, Shimadzu) andthe concentration of MB in the solution was de-
molecule model. All solutions were prepared in distilled water. termined as a function of irradiation time from absorbance change at
664.5 nm corresponding to the maximum absorption wavelength (λmax)
of MB.
2.2. Synthesis of the powders

Pure and Ag-doped TiO2 nanopowders have been synthesized by the 3. Results and discussion
sol-gel technique: titanium tetra n-butoxide was dissolved in acetic
acid, distilled water was then added drop wise to this mixture, and all 3.1. XRD analysis
stirred at 80 °C to obtain a gel (Fig.1), which is then dried under air in a
furnace at 100 °C. The obtained matter was then ground in mortar and Fig. 2 shows the X-ray diffraction pattern of pure and Ag (1%, 5%
annealed at 500 °C for 5 h. and 10%) doped TiO2, annealed at 500 °C.
The heat treatment (drying at 100 °C and annealing at 500 °C) The recorded peaks indicate that the main phase of TiO2 and Ag-
performed after the elaboration of the TiO2 powder makes it possible to TiO2 nanopowders is the anatase, as indicated in the standard JCPDS
eliminate the residues of the precursor used, to densify the final ma- card (PDF # 21-1272). This may be due to the fact that doping with Ag
terial and crystallize it in the desired phase. does not alter the crystal structure of Ag-TiO2, or that the material is
To prepare Ag doped TiO2, the silver nitrate used with amounts stable even at 500 °C [15,35], and also indicates that doping with Ag
calculated so as to obtain Ag concentrations of: 1%, 5% and 10 % was leads to a solid solution, no phases linked to Ag such as AgNO3 ap-
added to water, and the procedure described above was repeated. peared.
Although the recorded peaks are those of the tetragonal structure
for all samples, but according to JCPDS 29-1360, the peak appearing at
(121) indicates the formation of the brookite phase. This observation

Fig. 1. Image of the gel. Fig. 2. XRD patterns of pure and Ag doped TiO2 nanopowders.

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S. Abbad, et al. Journal of Environmental Chemical Engineering 8 (2020) 103718

Table 1 different from the average crystallite size obtained from XRD pattern.
XRD data of pure and Ag doped TiO2. We notice a 15 nm for 1 % Ag-TiO2, 13 nm for 5 % Ag-TiO2 and 11 nm
%Ag θ (°) β (rad) D (nm) for 10 % Ag-TiO2. We notice a logical variation with Ag concentration.
In general, the size of the grains observed by TEM is greater than
0% 12.6664 0.00780 18 that measured by XRD, and this is due to the fact that the grains ob-
1% 12.6530 0.00904 16
served by TEM or SEM are composed of crystallites of TiO2 or other
5% 12.6627 0.00803 18
10 % 12.6644 0.00861 16
materials such as ZnO for example. What the XRD calculation gives is
the size of the crystallites and not the grain size observed by TEM or
SEM. In our case it was noted that the measured size was almost the
will contribute to explain the enhancement of the photocatalytic ac- same, which allowed us to conclude that the gains observed by TEM are
tivity as we will see later. none other than the crystallites whose size was calculated through the
The average grain sizes were calculated using X-ray line broadening XRD.
from Scherrer’s formula, given by the formula 1.
3.3. Color analysis
0.9λ
D=
β cos θ (1) The only parameter that can make a difference between the dif-
Where D is the grain size, λ the X-ray wave length ferent powders to the naked eye is the color of this powder.
(λCuKα = 1.541838 Å), β Δθ the full width at half-maximum (FWHM) Fig. 5 shows the color of the different powders, which changes ac-
and θ the Bragg angle. cording to the Ag concentration; it goes from white for pure TiO2 to the
The considered peak for this calculation is (101), which have the more or less dark gray for the doped TiO2. So there is a darkening as
highest intensity, thus the most appropriated. The results are shown in soon as the Ag concentration increases.
Table 1. This finding may be explained by the fact that pure silver is greyish
The Results (Fig. 3) show that the addition of silver did not sig- in color, so it influences the whitish color of pure TiO2, and thus the
nificantly affect the crystal size, which confirm the result obtained by higher the Ag concentration the more the color approaches black. This
M.A. Behnajady et al. [36]. However, one can say that average anatase result is very interesting since black TiO2 is very interesting because of
grain size decreases slightly with Ag concentration, indicating that the its tendency to absorb in the visible, which is well indicated by the
crystalline lattice remains almost constant [37]. absorbance spectra (Fig.6) where it is noticed that the absorbance in-
creases with the concentration of Ag in the visible range.

3.2. TEM analysis 3.4. UV-Vis spectroscopy

TEM images (Fig. 4) obtained for pure TiO2 and doped with Ag The spectra of Fig. 6, which plot the absorbance of the powders -
nanopowders indicate clearly that the morphology of the powders is annealed at 500 °C - versus the wavelength, indicate that the absor-
influenced by Ag doping. bance increases with increasing concentration of Ag with an absorption
In Fig. 4a, the micrograph for the pure TiO2 shows a cuboidshaped edge located between 380 and 500 nm for all samples.
TiO2 particles well crystallized and uniformly dispersed with a mean It is well demonstrated that the absorbance increases with the
size of ∼18 nm. concentration of Ag in the visible range, indicating that the black TiO2
In Ag doped TiO2 (Fig.4b–d), the images revealed the presence of is well indicated for visible absorption.
spherical Ag and TiO2 particles. The black spots that can be assigned to The optical band gap energy (Eg) has been determined by using
silver metallic particles [38] are quite small but with good crystallinity. Tauc equation (formula 2) by plotting (αhν)2 versus photon energy (hν)
It is well known that Ag doping inhibits grain growth of TiO2 sample (Fig.7) and extrapolating the linear portion to (αhν)2 = 0 [35].
[38], but we recorded a small difference in the particles size between
pure TiO2 and doped with Ag. (hυ − Eg )2
α=K
The micrograph (Fig.4d) representing the TEM image of TiO2 doped hυ (2)
with 10 % Ag is quite different from the other powders; the particles Where, K is constant, hν is the photon energy and Eg is the band gap
still exist with spherical shape, but the number of small spots became energy for indirect transitions.
more important. The variation of Eg as a function of Ag concentration is shown in
The particles size calculated from TEM micrographs are slightly Fig. 8, which indicate that the optical band-gap energy decreases with
the dopant concentration, varying from 3.22 eV for pure TiO2 to
2.67 eV for TiO2 doped with 10 % Ag, leading to a delay in the re-
combination of electron-hole and then contributes [14], as we can see
later, to improve the photocatalytic activity.

3.5. FTIR analysis

The FTIR spectra (Fig. 9) of nanopowders calcined at 500 °C show

the appearance of bands at 3455 cm−1 linked to the bending vibration
of O-H molecules due to the presence of some traces of water. There are
also traces of CO2 (2340 and 2360 cm−1). This last band is due to the
fact that the elaboration of the powder was carried out in ambient air
[39]. The carbonyl (C = O) peak appeared at 1216 cm−1; 1366 cm−1;
1438 cm−1 and 1738 cm-1 according to reference [40]. The peak at
1092 cm−1 is related to the stretching vibrations of TieOH molecule.
The absorption peak around 512 cm−1 is linked to the bending vibra-
tions of Ti-O-Ti.
Fig. 3. Effect of Ag concentration on grain sizes. The peaks related to Ti atoms appear under two forms: the first is

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S. Abbad, et al. Journal of Environmental Chemical Engineering 8 (2020) 103718

Fig. 4. TEM images of pure and Ag doped TiO2 nanopowders.

(a): pure, (b): 1 % Ag, (c): 5 % Ag and (d): 10 % Ag

Fig. 5. Images of different colors of powders: (a): pure, (b): 1 % Ag, (c): 5 % Ag.
and (d): 10 % Ag

the molecule Ti−OH and the second is Ti-O-Ti molecule. In both cases molecule structure in the powders. However this does not mean at all,
there is no change according to the Ag concentration and we have re- that Ag has no effect on catalytic, photocurent or other proprieties of
corded no peaks linked to Ag. This confirms the results previously ob- TiO2.
tained by DRX.
Furthermore this also means that Ag does not influence the

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S. Abbad, et al. Journal of Environmental Chemical Engineering 8 (2020) 103718

Fig. 6. UV–Vis absorption spectra of annealed TiO2 and Ag-doped TiO2 nanopowders.

Fig. 7. Band gap obtained by extrapolating the linear portion of the (αhν)2
Fig. 8. Variation of Eg as a function of Ag concentration.
versus photon energy (eV) curve of TiO2 and Ag-doped TiO2 nanoparticles.

4. Photocatalytic activity that we propose to this phenomenon will be based on the enlargement
of the active surface. Indeed, as shown on the TEM images, there is
It is observed from Fig. 10, that the degradation rate of MB increases appearance of Ag particles, which increase when the concentration of
with UV irradiation time and the photocatalytic activity is improved Ag increases which widens the pollutant's absorption surface.
when TiO2 is doped with Ag atoms. Pure TiO2 shows 96 % degradation The results given above for the degradation of MB, which is the most
of MB after ≈ 2 h of UV exposure, whereas, 10 % Ag-TiO2 sample important for TiO2 with 10 % Ag is confirmed with the calculation of
shows 97 % degradation after only 35 min, it is the highest degradation the reaction rate constant k, which is the biggest for this sample.
efficiency recorded until now. The results thus achieved are unexpected and amazing, since in the
According to Ohtani et al. the degradation phenomenon is explained literature we find products that degrade the BM for more than five
as follows: the high activity of TiO2 photocatalyst should satisfy two hours, whereas we reach with our products a total degradation in only
requirements: large surface area for absorbing dye and high crystal- 35 min using TiO2 doped with 10 % Ag.
linity to reduce photo-excited electron-hole recombination rate [41]. Fig. 11 show the plot of –ln(C/C0) of MB versus irradiation time for
The crystallinity being unchanged for all our powders, the explanation photocatalytic reactions. As it is clear from the figure, the dye removal
is obtained with good precision. This means that the pseudo-first order

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S. Abbad, et al. Journal of Environmental Chemical Engineering 8 (2020) 103718

Were k and R2 are the reaction rate constant (min−1) and the square
correlation coefficient, respectively.

5. Conclusion

Nanopowders of pure TiO2 and doped with Ag have been success-

fully synthesized by sol-gel. The main phase of all nanopowders is
anatase, in the form of grains ranging in size from 18 to 16 nm de-
pending on Ag concentration.
TEM micrographs confirm that the main phase constituting the
nanopowders of TiO2 and Ag-TiO2 is the anatase, consisting of gains
whose average size decreases with the increase in Ag concentration. In
addition spherical Ag particles appeared on the surface of TiO2 nano-
particles, where the number increases with increasing concentration of
Ag.
Fig. 9. FTIR spectra of pure and Ag doped TiO2 nanopowders. The synthesis of the powders and the appearance of the brookite
phase for TiO2 doped with 10 % Ag have an almost certain influence on
the improvement of the photocatalytic activity obtained in this study,
which can be explained by a decrease in the recombination rate of
photo generated charge carriers related to the decrease in the band gap
from 3.22 eV to 2.67 eV.
The total degradation of Ag-TiO2 with 10 % Ag for 35 min is
probably the most important result to highlight in this study.

Author contributions

S. Abbad : Synthesis of materials, charactrization, analysis of re-

sults. K. Guergouri1 : Supervisor of the study, charactrization, analysis
of results. S. Gazaout1 : Synthesis of materials, charactrization, ana-
lysis of results. S. Djebabra : Synthesis of materials, charactrization,
analysis of results. A. Zertal : Contribution in photocatalysis : scientific
material and analysis. R. Barille : Contribution in Electronic
Microscopy. M. Zaabat : Supply of different synthesis products.
Fig. 10. Photodegradation of MB. Effect of Ag doping.
Special considerations

The article that is in the process of submitting represents part of a

doctoral study specializing
in semiconductors.

Information to support the submission

This work is original and it isn’t submitted elsewhere. The interest in

this work can be
summarized in:

• The well-defined optimal conditions for the synthesized powders

have been found.
• High-resolution TEM images of Ag doped TiO particles indicate
2
that the morphology of TiO2 powders is clearly influenced by Ag
doping.
• The 10 % Ag-TiO2 sample shows 97 % degradation after only
Fig. 11. Pseudo-first order kinetics for MB photocatalytic degradation.
35 min.

Declaration of Competing Interest

Table 2
Summary of the kinetic parameters.
The information below are provided as a Declaration of Interest
%Ag 0 1 5 10 Statement and motivation for the editor and reviewers.

k (min−1) 0.0264 0.0322 0.0521 0.0965

R2 0.9801 0.986 0.9883 0.9878
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