Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551

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Journal of Photochemistry & Photobiology, A: Chemistry

journal homepage: www.elsevier.com/locate/jphotochem

Electrostatic adsorption of ultra-small silver nanoclusters on titanium

dioxide modified mesoporous MCM-41as a high-performance photocatalyst
for wastewater treatment
Mostafa Farrag
Nanoclusters and Photocatalysis Laboratory, Chemistry Department, Faculty of Science, Assiut University, 71516 Assiut, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: For the first time, monodispersed bare silver nanoclusters with an average particle size of 1.2 nm were syn­
Strong electrostatic adsorption thesized without protecting ligand and deposited inside the pores of a titanium dioxide modified mesoporous
Point of zero charge MCM-41 utilizing the novel strong electrostatic adsorption (SEA) technique. The pH of the MCM-41 and TiO2/
Silver nanoclusters
MCM-41 surfaces was adjusted at 11 to optimize the electrostatic adsorption of the silver metal complexes and
MCM-41 mesoporous material
Wastewater treatment
MB dye. Where, the pH point of zero charges (pHPZC) of the MCM-41 and TiO2/MCM-41 are 4 and 4.9,
respectively. For comparison, microwave assisted sol–gel and hydrothermal methods were used to load silver
nanoparticles on a titanium dioxide modified mesoporous MCM-41, where, the average particle size of the silver
nanoparticles is 2–5 nm and 4–5.5 nm, respectively. The texture properties of the synthesized photocatalysts
were investigated using the liquid nitrogen sorption isotherms at _196 ◦ C. The crystallinity of the photocatalysts
was characterized by X-ray diffraction (XRD). The charge of the loaded silver nanoclusters and silver nano­
particles was investigated by X-ray photoelectron spectroscopy (XPS). The silver content was around 1.0 wt%
over the TiO2/MCM-41 and MCM-41 supports that was measured by the XPS. The performance of the synthesized
photocatalysts was tested by photocatalytic degradation of MB dye under visible light irradiation. Around 100 %
decolorization of 50 ppm MB solution was archived after two hours of irradiation over Ag/TiO2/MCM-41 (SEA)
photocatalyst. This catalyst shows stable efficiency for at least five cycles without significant leaching or loss of
catalytic activity. The surface morphology of the Ag/TiO2/MCM-41 (SEA) photocatalyst was investigated using
scanning electron microscopy (SEM). The excellent performance of the SEA catalyst is attributed to ultra-small
Ag nanoclusters that uniformly dispersed in the mesopores of MCM-41 so that more Ag surface sites are available
for the catalytic reaction. In conclusion, the SEA is an excellent synthetic strategy for the deposition of ultra-small
bare metal nanoclusters on porous materials.

1. Introduction photocatalytic applications under visible light irradiation [10]. There­

Great efforts have been made to enhance the efficiency of the solar
light-activated photocatalyst in recent years. Heterogeneous photo­
catalysis is the best technique for the removal of toxic and nontoxic dyes
contaminates from water. More than 100,000 dyes are being used for
industrial purposes, a considerable amount of which after processing is
released out to water resources [1,2].
TiO2 has been considered one of the most promising photocatalysts
due to its strong oxidizing power, high thermal and chemical stability,
low cost, and non-carcinogenic nature [3–9]. However, TiO2 limitation
due to its restricted activation in the near UV region as well as the fast
recombination of photogenerated electron-hole pair hinders its
fore many efforts have been considered to improve the photocatalytic
activity of TiO2 under solar irradiation [11,12].
Doping TiO2 with metal nanoparticles has been frequently used not
only to retard the charge pair recombination but also to enable visible
light absorption by providing defect states in the bandgap [13–15] or
usage of electron donors/acceptors and hole scavengers. The ability to
synthesize nanoparticles of controlled sizes and shapes is a big challenge
due to their unique properties. Recently, protected metal nanoclusters
have attracted attention to many researchers because of their size-
dependent optical and electronic properties, which differ significantly
from both the bulk and single atom properties. Various methods were
used to prepare protected monodispersed gold [16–18], silver [19–21],

E-mail address: mostafafarrag@aun.edu.eg.

https://doi.org/10.1016/j.jphotochem.2021.113551
Received 10 July 2021; Received in revised form 8 September 2021; Accepted 13 September 2021
Available online 20 September 2021
1010-6030/© 2021 Elsevier B.V. All rights reserved.
M. Farrag
platinum [12,22] and palladium [19,23] nanoclusters.
Even though noble metals nanoparticles can improve the photo­
catalytic activity of TiO2, however, the loading of TiO2 with nano­
particles or protected nanoclusters causes a decrease in surface area and
block some pores of the TiO2 [18,22]. Therefore, mesopores materials
such as mesoporous silica (MCM-41) [24], activated carbon [25] and
zeolites were doped with TiO2 to enhance the surface area of the syn­
thesized catalysts. Recently, a thin film of TiO2 doped with mesoporous
silica (MCM-41) has been studied to improve the absorbability of TiO2
thin film [24].
MCM-41 (Mobil Composition of Matter No. 41) is one of the mem­
bers of the mesoporous molecular sieves of the M41S family. MCM-41
has a large surface area with a highly ordered hexagonal structure of
one-dimensional channels of mesopores with a pore diameter in the
range of 2–10 nm [26]. Moreover, the MCM-41 structure can generate
active hydroxyl radicals ( OH) from the functional groups of silanol
•
(Si–OH), which behave as a strong oxidizing agent in photocatalytic
reactions [26,27].
In this work, monodispersed bare silver nanoclusters with an average
particle size of 1.2 nm were deposited inside the pores of a mesoporous
MCM-41 and a titanium dioxide modified mesoporous MCM-41 using a
novel strong electrostatic adsorption (SEA) technique. The other two
methods were used to prepare Ag/TiO2/MCM-41 photocatalysts a mi­
crowave assisted sol–gel and hydrothermal techniques. There is a big
range between the average particle size of the silver nanoclusters syn­
thesized via the SEA method and the silver nanoparticles via the other
two methods. Where, the average particle size of the silver nanoparticles
was 2–5 nm and 4–5.5 nm, respectively. The synergistic effect between
the ultra-small Ag nanoclusters and the MCM-41 on TiO2 is beyond the
extremely catalytic activity of Ag/TiO2/MCM-41 (SEA) photocatalyst in
photocatalytic degradation of methylene blue dye under visible light
irradiation. The textural properties and crystallinity of the synthesized
photocatalysts were investigated with nitrogen adsorption–desorption
isotherms at − 196 ◦ C and XRD analysis, respectively. The charge of the
loaded silver was zero that was investigated by X-ray photoelectron
spectroscopy (XPS).
2. Experimental
2.1. Chemicals
The chemical agents for the synthesis of MCM-41 were cetyl­
trimethylammonium bromide (CTAB, Fluka, 96%), aqueous ammonia
solution (30 wt%), and tetraethyl orthosilicate (TEOS, 98%, Sigma­
–Aldrich). Titanium (IV) isopropoxide (Ti[OCH(CH3)2]4, 97%, Sigma­
–Aldrich), silver nitrate (AgNO3, 97%, Sigma–Aldrich), ethanol
(C2H5OH, Merck), acetylacetone (C5H8O2, Merck, 99%) and nitric acid
(HNO3, Merck, 65%) were used for the preparation of an Ag/TiO2 pre­
cursor solution. Methylene blue dye (MB) and hydrogen peroxide H2O2
(28%) were used to determine the photocatalytic activity of the pre­
pared photocatalysts. All chemicals were used as received. All glassware
was thoroughly cleaned with aqua regia (HCl:HNO3 = 3:1 v/v), rinsed
with double distilled water and ethanol, and then dried in an oven
before use.
2.2. Synthesis of the Ag/TiO2/MCM-41 photocatalysts.
Ag/TiO2/MCM-41 photocatalysts were prepared by using the novel
strong electrostatic adsorption (SEA) technique [28] and for compari­
son, the other two methods were tested a microwave assisted sol–gel and
hydrothermal techniques [29].
2
Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551
2.2.1. Synthesis of Ag/TiO2/MCM-41(SEA) photocatalyst via strong
electrostatic adsorption (SEA) technique.
2.2.1.1. Preparation of MCM-41 material.. 2.5 g of cetyl­
trimethylammonium bromide (CTAB) was dissolved in 50 mL of
doubled distilled water, 15.1 g ammonia solution was added dropwise
with constant stirring at 500 rpm till the complete dissolution of the
CTAB. And then 60 mL of ethanol was added under constant stirring for
2.5 h. 4.7 g tetraethyl orthosilicate (TEOS) was then added, a white gel
was formed. The obtained gel was stirred for 2 h and aged for another 2
h. The obtained white material was filtered and washed with distilled
water and methanol and dried in an oven at 100 ◦ C overnight [30,31].
The obtained product was named ‘as-synthesized MCM-41′ .
2.2.1.2. Preparation of TiO2/MCM-41 material.. The as-synthesized
MCM-41 has suspended in ethanol and titanium (IV) isopropoxide as
titanium source was dropped wise under vigorous stirring for 1 h after
that 10 mL of doubled distilled water was added until complete pre­
cipitation of TiO2 with stirring for 2 h at room temperature. The molar
ratio of the Ti:Si was 1:2 [29]. The product was filtered and dried in an
oven at 100 ◦ C overnight. Finally, the dried powder was calcined at
550 ◦ C for 5 h. The obtained product was donated as TiO2/MCM-41.
2.2.1.3. Loading of Ag nanoclusters on MCM-41 and TiO2/MCM-41 via
SEA technique.. Silver nitrate was used for silver metal loading. A stock
solution of the silver salt was prepared using 5 N NH3 (aq) to prepare a
stable silver complex [Ag(NH3)2]+ [28]. The total volume of the solution
was calculated to yield a surface loading of 1000 m2 L− 1 according to Eq.
(1) [28]. The calculated weight of the silver metal stock solution was
added over the suspended supports (MCM-41 and TiO2/MCM-41) and
stirred for 30 min to allow the adsorption of the cationic silver metal
(Ag+) precursor on the supports. The loaded catalysts were centrifuged
and washed with water and ethanol to replenish the basic solution. The
catalysts were dried overnight under ambient conditions and then dried
in an oven for four hours at 120 ◦ C. The silver cations over the different
supports were reduced by H2 gas at 350 ◦ C for four hours, donated as
Ag/MCM-41 (SEA) and Ag/TiO2/MCM-41 (SEA).
SL = SA × mass of support in g/volume in L (1)
2 − 1 2 − 1
Since SL is surface loading in m L and SA is surface area in m g .
2.2.2. Synthesis of Ag/TiO2/MCM-41(MWI) photocatalyst via the
microwave assisted sol–gel method.
The as-synthesized MCM-41 was loaded with titanium salt by the
same molar ratio (1Ti:2Si) as was described in Section 2.2.1. The
required mol % of silver ions was loaded by using the impregnation
method. The slurry was stirred one day at room temperature, and then
the silver ions were reduced using microwave irradiation at 100 W and
75 ◦ C for 5 min [29]. The obtained photocatalyst was collected by
centrifuge at 6000 rpm, 10 min, and dried in an oven at 100 ◦ C over­
night. Finally, the dried powder was calcined at 550 ◦ C for 5 h. The
obtained product was donated as Ag/TiO2/MCM-41 (MWI).
2.2.3. Synthesis of Ag/TiO2/MCM-41(HT) photocatalyst via the
hydrothermal method.
The as-synthesized MCM-41 was loaded with titanium salt by the
same molar ratio (1Ti:2Si) as was described in Section 2.2.1. The
required mol % of silver ions was loaded by using the impregnation
method. The slurry was reflexed at 80 ◦ C for 48 h [29]. The obtained
nanocomposite was cooled, collected by centrifuge at 6000 rpm, 10 min,
and dried in an oven at 100 ◦ C overnight. Finally, the dried powder was
calcined at 550 ◦ C for 5 h. The obtained product was donated as Ag/
TiO2/MCM-41 (HT).
M. Farrag Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551

2.3. Determination of the point of zero charge (PZC) values. was shielded from the surface charge due to the high ionic strength
which is known as the double-layer screening effect [38,42].
The PZC values of MCM-41 and TiO2/MCM-41 were determined Deposition of palladium or silver metal over silica (SiO2 or MCM-41)
using a salt titration technique [32,33]. 1 g of each sample was placed in is hard because of the low surface free energy of SiO2 relative to Pd or Ag
a 50 mL glass tube. 20 mL of doubled distilled water was added and the [43,44]. To facilitate the nucleation of the silver atoms on the MCM-
pH values of the resulting suspensions were adjusted using either 0.1 41support, the SEA technique was used and deposition of TiO2 firstly
mol/L HC1 or 0.1 mol/L NaOH. The final volume was 30 mL. The over MCM-41 surface by ratio 1:2 (Ti:Si). Where the MB decolorization
resulting solutions were allowed to equilibrate for four days with efficiency over TiO2/MCM-41 nanocomposites are arranged, in the
discontinuous stirring, after that the equilibrium pH was recorded and following: Ti:Si (1:2) > (1:1) > (1:0.5) > (1:0) [29].
donated as pH1. 0.5 mL of a 1 mol/L NaC1 solution was added and the
tube was agitated for 3 h, and then the pH2 value was recorded. ΔpH =
(pH2–pH1) was calculated and the ΔpH values were plotted versus pH1 3.1. Characterization of the synthesized photocatalysts.
to determine the point at which ΔpH = 0. The corresponding pH equaled
the PZC value for the sample. The nitrogen adsorption–desorption isotherms at − 196 ◦ C of the
550 ◦ C calcined MCM-41 material, titanium dioxide modified meso­
porous MCM-41 (TiO2/MCM-41), and the doped silver nanoclusters over
2.4. Photocatalytic studies of the synthesized photocatalysts.
the two supports (MCM-41 and TiO2/MCM-41) are shown in Fig. 1(a–d),
respectively. All of them showed isotherms belong to Type IV with H1
The photocatalytic degradation of methylene blue (MB) solution was
hysteresis loops, corresponding to mesoporous materials according to
carried out to evaluate the photocatalytic activity of the synthesized
the IUPAC classification of hysteresis loops [45].
silver nanoclusters and nanoparticles over TiO2/MCM-41 nano­
The sorption isotherm of MCM-41 contains several stages. At very
composite. For comparison, the bare supports (MCM-41 and TiO2/MCM-
low pressure (P/P0 < 0.01) the steep sorption isotherm slope is related to
41) were tested also. The photocatalytic experiments were carried out
the filling of micropores or small mesopores. Mono- to multi-layer
with a 450 W medium-pressure mercury lamp with a <420 nm UV cut-
adsorption of liquid N2 occurs at a relative pressure (0.05 < P/P0 <
off filter (visible light) was employed as a light source and fixed at 10 cm
0.3), where the BET specific surface area is calculated [46]. A steep step
away from the reaction system [34–36].
and the hysteresis loop can be observed in the pressure range 0.3 < P/P0
50 mg of the used photocatalysts were suspended in 50 mL of freshly
< 0.4 that corresponds to capillary condensation in the mesopores [47].
prepared aqueous solution MB with a concentration of 50 ppm under
The flat sorption curve reflects multi-layer adsorption or desorption of
magnetic stirring. The reaction system was firstly kept in the dark for 60
liquid N2 molecules on the external surface at higher relative pressures
min to establish an adsorption–desorption equilibrium and then exposed
of more than 0.4 [48]. After loading of MCM-41 with TiO2 these steps
to the visible light for two hours. At the desired time intervals, 5 mL
moved towards a lower relative pressure and smaller hysteresis loops are
aliquots from each sample were taken, followed by centrifugation and
observed, indicating a partial filling of the mesopores (Fig. 1b).
filtration to remove the photocatalyst. The decolorization of MB was
In the case of silver nanoparticles over titanium dioxide modified
evaluated by measuring the change in its characteristic optical absor­
mesoporous MCM-41 that was reduced via microwave assisted sol–gel
bance using an Evolution 300 UV–vis spectrophotometer [12].
method (Ag/TiO2/MCM-41(MWI)) and hydrothermal method (Ag/
To check the advantages of the prepared photocatalysts and their
TiO2/MCM-41(HT)), both of them exhibited H3 hysteresis loops ac­
applicability to reuse [12,18,22], the photodegradation reaction of the
cording to the IUPAC classification of hysteresis loops (Fig. 1). The
MB solution was achieved with Ag/TiO2/MCM-41 (SEA) photocatalyst.
specific surface areas and pore volume of the prepared photocatalysts
Then the photocatalyst was collected at the end of the reaction and
are summarized in Table 1.
reused for a second cycle and the process repeated so on till five cycles
keeping all other parameters constant. Ag/TiO2/MCM-41 (SEA) photo­
catalyst shows a very good activity for five catalytic runs with a very
small loss in the photodegradation of MB. This means, this photocatalyst
possesses high stability and may be reusable for at least 5 runs, showing
a good potential for industrial applications.

3. Results and discussion

The pH point of zero charge (pHPZC) of the synthesized MCM-41 is 4

that was measured via the salt titration technique [32,33], the value is in
line with other silica supports reported previously [37–39]. Also, the
TiO2/MCM-41 support has pHPZC of 4.9 that was measured by the same
technique, where TiO2 has pHPZC of 6.2 [40,41]. The charge of the
surface of the photocatalyst will be negative or positive at pH values
higher or smaller than the pHpzc, respectively. Hence, at pH values
higher than pHpzc, the negatively charged surface of the MCM-41 and
TiO2/MCM-41 attracts the MB molecules throw their positively charged
groups, thus increases the adsorption efficiency. Therefore we adjusted
the pH at 11 to reach maximum adsorption of MB dye.
The strong electrostatic adsorption (SEA) technique was used to load
ultra-small silver nanoclusters over the MCM-41 and TiO2/MCM-41
Fig. 1. The nitrogen adsorption–desorption isotherms of (a) MCM-41, (b) TiO2/
supports since this technique prevents the silver particles from growing.
MCM-41 (1:2), (c) Ag/MCM-41(SEA), and (d) Ag/TiO2/MCM-41(SEA), all of
The supports were dispersed in double-distilled water and then 5 N them exhibited type IV adsorption isotherms with H1 hysteresis loops according
aqueous ammonium solution was used to adjust the pH of 11 to optimize to the IUPAC classification of hysteresis loops. The nitrogen adsorp­
electrostatic adsorption of the metal complexes [37]. Higher than pH 11 tion–desorption isotherms of (e) Ag/TiO2/MCM-41(MWI) and (f) Ag/TiO2/
the native hydroxyl groups of the supports become deprotonated, and MCM-41(HT), both of them exhibited H3 hysteresis loops according to the
the adsorption of the silver metal will lower since the metal precursor IUPAC classification of hysteresis loops.

3
M. Farrag Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551

Table 1 mesoporous MCM-41 (Fig. 3-II). The average particle size of the silver
Surface area data for the synthesized photocatalysts and bare supports and Ag nanoclusters was 1.2 nm (Fig. 3-I and 3-II). However, the used other two
loading percentage. techniques a microwave assisted sol–gel and hydrothermal produce
Photocatalysts SBET St Pore Ag Loading* silver nanoparticles with average particle size 2–5 nm and 4–5.5 nm
(m2 g¡1) (m2 g¡1) volume (wt%) over the titanium dioxide modified mesoporous MCM-41 (Fig. 3-III and
(cm3/g) 3-VI), respectively. The octahedral titanium (IV) oxide (TiO2) crystal­
MCM-41 906 906 0.5 – lites particles that corresponding to anatase (1 0 1) with an average
TiO2/MCM-41(1:2) 794 794 0.45 – particle size of 10–20 nm appeared in the TEM images (Fig. 3). Since the
Ag/MCM-41(SEA) 788 787 0.42 0.99
growth of TiO2 crystallite is suppressed when MCM-41 is incorporated
Ag/TiO2/MCM-41(SEA) 585 585 0.38 1.01
Ag/TiO2/MCM-41 323 323 0.34 0.97 into the TiO2 structure [49]. The bare silver nanoclusters were achieved
(MWI) over MCM-41 and TiO2/MCM-41 because the SEA technique limits the
Ag/TiO2/MCM-41(HT) 313 313 0.32 0.98 coverage of the support surface, only a monolayer of metal ions was
*
As were measured by XPS. loaded therefore hinder the agglomeration of the silver nanoparticles
[37–40].
The morphological surface of the Ag/TiO2/MCM-41(SEA) photo­
In the low-angle X-ray diffraction range of the synthesized MCM-41,
catalyst was investigated using SEM analysis. Fig. 4 presents the orderly
a strong peak at 2θ = 3◦ with (1 0 0) diffraction plane appeared. This
crystallization of the Ag/TiO2/MCM-41(SEA) photocatalyst with ho­
peak is diagnostic for the highly ordered hexagonal pore structure of the
mogeneous dispersion of TiO2 over MCM-41. The crystal size of the TiO2
MCM-41 material (Fig. 2a) [31]. Moreover, a hump can be observed in
was 10–20 nm (Fig. 4). Also, the silver nanoclusters appeared over TiO2/
the 2θ range 15–30◦ within the wide-angle XRD region [31]. XRD dif­
MCM-41 nanocomposite with a very narrow size distribution of 1–1.3
fractogram of Ag/MCM-41 (SEA) photocatalyst is similar to the pure
nm (Fig. 4), which is in good agreement with the TEM analysis (Fig. 3-
MCM-41, as shown in Fig. 2c, where the Ag nanoclusters percentage is
II).
around 1% which is less than the detection limit of the XRD and the
X-ray photoelectron spectroscopy (XPS) is used to obtain information
particle size of the silver nanoclusters is very low [12,18,23]. XRD dif­
concerning the elemental composition of the Ag/TiO2/MCM-41(SEA)
fractograms of the synthesized TiO2/MCM-41 support and the doped
photocatalyst. Fig. 5-I displays a typical survey spectrum of Ti 2p, Si 2p,
TiO2/MCM-41 with silver nanoclusters (SEA) or silver nanoparticles
O 1s, C 1s, and Ag 3d. Ti and O elements show the strongest peaks in the
(MWI and HT) are shown in Fig. 2b, d, e, f, respectively. All of them
survey spectrum indicated the crystal lattice of TiO2. To estimate the
show strong XRD peaks of TiO2 anatase, indexed at 2θ of 25.3◦ (1 0 1),
chemical state of Ag/TiO2/MCM-41(SEA) photocatalyst, the high-
37.8◦ (0 0 4), 48.0◦ (2 0 0), 53.9◦ (1 0 5), 62.7◦ (2 0 4), and 62.72◦ (1 1 6),
resolution XPS spectra of Si, Ti, O, C and Ag are analyzed separately,
corresponding to anatase card (JCPDS No. 21–1272) [22,49]. Also, the
as shown in Figs. 5 and 6, respectively. The XPS spectrum of Si 2p
characteristic peak of MCM-41 at 2θ = 3◦ still appears with these pho­
showed one broad peak at binding energy (BE) values of 103.6 eV that
tocatalysts (Fig. 2). However, there is no peak for Ag nanoparticles was
attributed to the existence of Si4+ in the framework of the synthesized
found.
MCM-41, i.e. Si–O–Si linkage [31], and another small peak at 101.5 eV
The morphological characteristic of the synthesized MCM-41 mate­
that contributes to Ti–O–Si linkage, which confirms that Si4+ can replace
rial and TiO2/MCM-41 nanocomposite and the particle size of the syn­
Ti4+ in a titania octahedral lattice (Fig. 5-II) [29]. Fig. 5-III showed the
thesized bare silver nanoclusters and silver nanoparticles were
XPS spectrum of Ti 2p that can be deconvoluted into two peaks located
identified by a transmission electron microscope (TEM) [25,50,51].
at a binding energy of 458.6 eV and 464.3 eV, which correspond to Ti
Fig. 3-I shows some homogenous special black dots of the silver nano­
2p3/2 and Ti 2p1/2, respectively. Since the strongest peat at 458.6 eV is
clusters inside the MCM-41 mesopores that were loaded via the SEA
corresponding to tetravalent Ti4+ in a titania octahedral lattice [29,52].
technique. The strong electrostatic adsorption (SEA) technique was used
The XPS spectrum of O 1s consists of several peaks, in the regions from
also to load the silver nanoclusters over the titanium dioxide modified
528 to 537 eV (Fig. 5-IV). At 533.2 eV and 530 eV appear the strong two
peaks of O 1s that are attributed to OH groups in Ti-OH and Si-OH
bonding and oxygen in the Ti–O–Ti linkage of TiO2, respectively.
There are another two peaks in the XPS spectrum of O 1s appear at
530.6 eV that is contributed to Ti–O–Si bonds, due to the coordination of
Si and Ti atoms in the matrix surface [29,52], and at 534 eV, which
refers to the oxygen bonding of Si–O–Si linkages [53]. Fig. 4-V shows the
deconvoluted C1s peak, which can be fitted into three peaks at binding
energy values of 288.22, 285.8, and 284.8 eV. These contributions could
be assigned to O–C– – O, C–O, and C–C linkages, respectively [31].
The XPS analysis was used to determine the charge of the Ag nano­
clusters and nanoparticles over the titanium dioxide modified meso­
porous MCM-41. The XPS spectra of Ag 3d show two peaks at binding
energy around 368 eV and 374 eV, corresponding to Ag 3d5/2 and Ag
3d3/2, respectively (Fig. 6). This is a characteristic of metallic silver
(Ag0) [29]. This means the used three reduction methods (hydrogen
reduction, microwave assisted sol–gel and hydrothermal) succeeded in
the reduction of Ag+ to Ag0 (Fig. 6).

3.2. Photocatalytic activity of the synthesized photocatalysts under visible

light irradiation.

The photocatalytic degradation of methylene blue (MB) dye was

Fig. 2. X-ray diffractograms of the synthesized photocatalysts, (a) MCM-41, (b) used to evaluate the photocatalytic performance of the synthesized
TiO2/MCM-41 (1:2), (c) Ag/MCM-41(SEA), (d) Ag/TiO2/MCM-41(SEA), (e) photocatalysts (Ag/MCM-41(SEA), Ag/TiO2/MCM-41(MWI), Ag/TiO2/
Ag/TiO2/MCM-41(MWI) and (f) Ag/TiO2/MCM-41(HT). MCM-41(HT), and Ag/TiO2/MCM-41(SEA)) under visible light

4
M. Farrag
Fig. 3. Transmission electron microscopy images of the bare silver nanoclusters over MCM-41 (a) and TiO2/MCM-41 (b), where the average particle size of the silver
clusters was 1.2 nm. Silver nanoparticles were loaded over the titanium dioxide modified mesoporous MCM-41 via microwave assisted sol–gel and hydrothermal
methods with average particle sizes 2–5 nm and 4–5.5 nm, respectively.
Fig. 4. Scanning electron microscopy (SEM) image of the Ag/TiO2/MCM-41
(SEA) photocatalyst that shows a homogeneous dispersion of TiO2 over MCM-
41 with a very narrow size distribution of silver nanoclusters 1–1.3 nm.
irradiation. The bare supports (MCM-41 and TiO2/MCM-41) were tested
also as reference catalysts for comparison (Fig. 7).
The photo experiments were carried out in a 100 mL Pyrex glass
beaker under a magnetic stirrer. The 50 ppm MB dye solution was stirred
an hour in dark over the synthesized photocatalysts to establish an
adsorption–desorption equilibrium and then was irradiated with a 450
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Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551
W medium-pressure mercury lamp with a <420 nm UV cut-off filter for
two hours [34–36]. The photodegradation reaction was followed up by a
UV–vis spectrophotometer (Evolution 300). To measure the light ab­
sorption from a clear solution at λmax for MB (664 nm) at a set time, the
suspended photocatalyst was removed by centrifugation.
Despite MCM-41 has a high surface area (906 m2 g− 1) but the
adsorption of the dye is very low, also the photodegradation of the dye
over the MCM-41 is low due to the absence of photosensitization effect
(Fig. 6a). Modification of MCM-41 with TiO2 plays an important role in
the photocatalytic degradation of MB dye (Fig. 6b). Since the MCM-41
reduces the recombination rate of electrons-holes in TiO2 and the
MCM-41 pores can transfer electrons from the conduction band of TiO2
to O2 molecules [26].
There are two challenges to improve the photocatalytic efficiency of
photocatalysts, firstly shifting the optical absorption of photocatalysts
from the UV region to the visible light region and delaying the recom­
bination of the electron-hole pairs [12,25,26]. Loading of the meso­
porous materials with silver nanoparticles is a suitable photocatalyst for
efficient photodegradation of dyes from an aqueous solution. Sohrab­
nezhad et al. [26] loaded MCM-41 with silver nanoparticles (~7 nm)
and used it as photocatalyst in photodegradation of methyl orange (MO)
dye under visible light irradiation [26]. The degradation percentage of
MO over AgMCM-41 was 7 and 8 % within an hour and two hours
irradiation under visible light, respectively [26]. In our work, the novel
strong electrostatic adsorption technique was used to load ultra-small
silver nanoclusters over MCM-41, which achieved around 40% photo­
degradation of MB within two hours of visible light irradiation (Fig. 7c).
M. Farrag Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551

Fig. 5. High-resolution X-ray photoelectron spectroscopy (HR-XPS) spectra of the Ag/TiO2/MCM-41(SEA) photocatalyst. (I) Survey spectrum. (II) The XPS spectrum
of Si 2p with two peaks at 103.6 eV and 101.5 eV. (III) The XPS spectrum of Ti 2p can be deconvoluted into two peaks located at 458.6 eV and 464.3 eV. (IV) The XPS
spectrum of O 1s consists of several peaks, in the regions from 528537 eV. (V) The XPS spectrum of C1s can be deconvoluted into three peaks at 288.22, 285.8, and
284.8 eV.

Fig. 6. High-resolution X-ray photoelectron spectroscopy (HR-XPS) spectra of the silver nanoclusters (I) and silver nanoparticles (II and III) over TiO2/MCM-41. The
XPS spectra of Ag 3d show two peaks at 368 eV and 374 eV, corresponding to Ag 3d5/2 and Ag 3d3/2, respectively, that is characteristic of metallic silver (Ag0).

By the same technique, the TiO2/MCM-41 support was loaded with TiO2 conduction band will react with the adsorbed molecular oxygen on
silver nanoclusters that show extremely photocatalytic activity in the the TiO2 surface producing superoxide anion radicals (O2 –) [56].
•

degradation of the MB solution (Fig. 7f). The results indicated that the Adsorbed water on the TiO2 surface or water molecules from the dye
photocatalytic degradation of the 50 ppm MB solution over Ag/TiO2/ solution will lose electrons at the positive valence band of TiO2 to pro­
MCM-41(SEA) was ~100% within two hours of illumination with the duce hydroxyl radical ( OH). O2 − and OH radicals are powerful
• • •

visible light source since the bandgap of Ag/TiO2/MCM-41(SEA) pho­
tocatalyst is 1.91 eV. The extremely photocatalytic activity of the bare
silver nanoclusters over TiO2/MCM-41 was attributed to their ultra-
small size distribution as shown in HRTEM analysis (Fig. 3-II). When
the silver nanoclusters come in contact with TiO2/MCM-41 a Schottky
junction is formed between the silver nanoclusters and TiO2, because the
Fermi level of TiO2 is higher than the silver nanoclusters. The electron
injection from the Ag clusters to TiO2 has been proven in Au/TiO2 and
Ag/TiO2 systems [54,55]. Once these electrons are transferred to the
oxidizing agents for the degradation of MB solution [34–36]. The
mechanism of photocatalytic degradation of MB over Ag/TiO2/MCM-41
(SEA) photocatalyst was exhibited in the supplementary information
(Fig. S1).
In contrast, the traditional techniques such as microwave assisted
sol–gel and hydrothermal produce large silver nanoparticles with big
size distribution that show less photocatalytic activity in comparison to
the strong electrostatic adsorption technique (Fig. 7). Where 2–5 nm and
4–5.5 nm silver nanoparticles over TiO2/MCM-41 exhibited only 69 %

6
M. Farrag
Fig. 7. The photocatalytic decomposition of 50 mL (50 ppm) methylene blue
(MB) dye over 50 mg of the synthesized photocatalysts.
and 56% photodegradation of the MB solution within two hours irra­
diation (Fig. 7e and d), respectively.
It is well known that hydrogen peroxide produces hydroxyl radical
( OH) under irradiation, which is a strong oxidizing agent [35]. In this
•
work, 2.5 mL of H2O2 (28%) was added to the reaction mixture over the
Ag/TiO2/MCM-41(SEA) photocatalyst. These few amounts of H2O2
enhanced the photocatalytic activity of the photocatalyst, where the MB
solution was completely degraded within<90 min irradiation (Fig. 7g).
The best photocatalyst in the industry should have good photo­
catalytic activity and high stability. To test the photocatalytic stability or
the recyclability properties of the synthesized photocatalysts, Ag/TiO2/
MCM-41(SEA) was chosen as a model photocatalyst. The photocatalyst
was recycled up to five times (Fig. 8). Once the adsorption and photo­
catalytic degradation of the MB solution was completed, the photo­
catalyst was collected, washed several times with pure water,
ultrasonicated, filtered, dried, and reused for a second cycle. This pro­
cess was repeated so on till five cycles. Fig. 8 shows that the synthesized
photocatalyst (Ag/TiO2/MCM-41(SEA)) has high stability and recycla­
bility in the degradation of MB dye. Therefore, we can say the synthe­
sized photocatalyst is highly suitable for industrial applications, such as
wastewater treatment.
4. Conclusion
In this work, the novel strong electrostatic adsorption (SEA) tech­
nique was used to synthesize bare silver nanoclusters with an average
particle size of 1.2 nm inside the pores of the titanium dioxide modified
mesoporous MCM-41 material. The traditional methods such as micro­
wave assisted sol–gel and hydrothermal methods were tested for com­
parison. The synthesized photocatalysts have high crystallinity
properties as confirmed by XRD analysis. Their textural properties were
investigated with nitrogen adsorption–desorption isotherms at − 196 ◦ C.
The three used reduction methods succeeded in the conversion of Ag ion
to silver zero as was confirmed by the X-ray photoelectron spectroscopic
(XPS) analysis. Ag/TiO2/MCM-41 (SEA) showed the highest photo­
catalytic activity in photodegradation of MB dye due to the synergistic
effect between the ultra-small Ag nanoclusters and mesoporous MCM-41
on TiO2. Moreover, the addition of a small amount of H2O2 to the mother
solution enhanced the catalytic activity of Ag/TiO2/MCM-41 (SEA)
photocatalyst since the strong oxidizing agent hydroxyl radical (⋅OH)
was produced. The synthesized photocatalyst (Ag/TiO2/MCM-41(SEA))
showed high recyclability properties in the photodegradation of MB dye
7
Journal of Photochemistry & Photobiology, A: Chemistry 422 (2022) 113551
Fig. 8. Recyclability effect of Ag/TiO2/MCM-41(SEA) photocatalyst was stud­
ied for visible light degradation of MB solution.
at least five times.
CRediT authorship contribution statement
Mostafa Farrag: Conceptualization, Methodology, Validation,
Investigation, Formal analysis, Resources, Data curation, Writing –
original draft, Writing - review & editing, Visualization, Project
administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgment
This work was financially supported by Assiut University, Egypt.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.jphotochem.2021.113551.
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