inorganics

Article
Photocatalytic Reduction of Cr(VI) to Cr(III) and Photocatalytic
Degradation of Methylene Blue and Antifungal Activity of
Ag/TiO2 Composites Synthesized via the Template
Induced Route
Zunaira Zahid 1 , Abdul Rauf 1, * , Mohsin Javed 1 , Ahmad Alhujaily 2 , Shahid Iqbal 3, * , Adnan Amjad 1 ,
Muhammad Arif 1 , Sajjad Hussain 4 , Ali Bahadur 5 , Nasser S. Awwad 6 , Hala A. Ibrahium 7,8 ,
Foziah F. Al-Fawzan 9 and Eslam B. Elkaeed 10

1 Department of Chemistry, University of Management and Technology, Lahore 54770, Pakistan

2 Biology Department, College of Science, Taibah University, Al Madinah Al Munawarah 41477, Saudi Arabia
3 Department of Chemistry, School of Natural Sciences (SNS), National University of Science and
Technology (NUST), H-12, Islamabad 46000, Pakistan
4 School of Chemistry, Faculty of Basic Sciences and Mathematics, Minhaj University, Lahore 54000, Pakistan
5 Department of Chemistry, College of Science and Technology, Wenzhou-Kean University,
Wenzhou 325060, China
6 Chemistry Department, Faculty of Science, King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia
7 Biology Department, Faculty of Science, King Khalid University, P.O. Box 9004, Abha 61413, Saudi Arabia
8 Department of Semi Pilot Plant, Nuclear Materials Authority, P.O. Box 530, El-Maadi, Cairo 11381, Egypt
9 Department of Chemistry, College of Science, Princess Nourah bint Abdulrahman University, P.O. Box 84428,
Riyadh 11671, Saudi Arabia
10 Department of Pharmaceutical Sciences, College of Pharmacy, AlMaarefa University,
Riyadh 13713, Saudi Arabia
* Correspondence: abdulrauf@umt.edu.pk (A.R.); shahidgcs10@yahoo.com (S.I.)

Citation: Zahid, Z.; Rauf, A.; Javed,

M.; Alhujaily, A.; Iqbal, S.; Amjad, A.;
Arif, M.; Hussain, S.; Bahadur, A.;
Awwad, N.S.; et al. Photocatalytic
Reduction of Cr(VI) to Cr(III) and
Photocatalytic Degradation of
Methylene Blue and Antifungal
Activity of Ag/TiO2 Composites
Synthesized via the Template
Induced Route. Inorganics 2023, 11,
133. https://doi.org/10.3390/
inorganics11030133
Academic Editor: Antonino Gulino
Received: 11 February 2023
Revised: 11 March 2023
Accepted: 12 March 2023
Published: 21 March 2023
Abstract: Water treatment through photocatalysts has become an important topic regarding environ-
mental protection. In the present study, silver and TiO2 (Ag/TiO2 ) composites for photocatalysts
were effectively synthesized by adopting the template induced method. The prepared samples were
characterized using XRD, FTIR spectroscopy, SEM, and EDX. The constructed samples’ particle size
and shape were evaluated using a SEM, and the XRD patterns showed anatase crystalline phases.
Their morphologies were controllable with changing concentration of reactants and calcination tem-
perature. The synthesized composites act as catalyst in the degradation of methylene blue (MB) and
reduction of Cr(VI) to Cr(III) under solar irradiation. In both of these activities, the best result has
been shown by the 0.01 Ag/TiO2 composite. Methanol is used as the hole scavenger in the reduction
of Cr(VI) to Cr(III). While the pH factor is important in the photocatalytic reduction of Cr(VI) to
Cr(III). According to observations, S. macrospora and S. maydis were each subject to 0.01 Ag/TiO2
nanocomposites maximum antifungal activity, which was 38.4 mm and 34.3 mm, respectively. The
outcomes demonstrate that both photocatalytic and antifungal properties are effectively displayed by
the constructed material.
Keywords: Ag/TiO2 composites; template induced method; methylene blue; Cr(VI); photocatalytic
reduction; antifungal

Copyright: © 2023 by the authors.

Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
1. Introduction
The earth is immensely affected by wastewater management, environmental pollution,
and climate change crisis. The major portion of the earth is comprised of water that can be
regenerated, disseminated, distributed, and transported. These characteristics collectively
add to water’s great value to people [1–3]. The groundwater and surface water resources
are crucial for a variety of activities, including cattle development, energy generation,

Inorganics 2023, 11, 133. https://doi.org/10.3390/inorganics11030133 https://www.mdpi.com/journal/inorganics

Inorganics 2023, 11, 133 2 of 17

forestry, farming, aquaculture, seafaring, recreation, and so forth [4]. It is a remarkable gift
from the nature to humanity that must be preserved. However, environmental degradation,
particularly water contamination, is regarded as one of the fundamental issues facing the
entire planet, significantly affecting our everyday lives [5]. It comprises the introduction
of foreign chemicals into the environment, which harms and disturbs the biosphere [6].
These pollutants appear to be either native substances that have surpassed permitted limits
or foreign compounds [7–10]. Unfortunately, pollution is continually rising and is now a
severe issue that requires immediate attention [11]. The usage of dyes and their byproducts
significantly pollutes the environment. The nature of water is changed by its release of
chemicals from potable to non-potable [12]. Furthermore, microorganisms also change
the properties of water and cause different diseases. Many nanomaterials have significant
properties to control the growth of bacteria [13]. The aquatic center is unscrewed from the
dye waste, changing the soil’s composition and water content. In addition, it encourages
several illnesses, environmental degradation, and several infectious diseases.
Toxic metal and organic compound-related water contamination is still a significant
environmental and societal issue [14]. Additionally, water contamination has grown to
be a significant cause of worry and a top priority for most industrial sectors. Water
contamination is significantly influenced by dyes used in the paper, food, and textile
sectors. Due to their industrial use, dyes and associated hydrocarbons, which are among
the most significant and dangerous toxins in water, are linked to population expansion [15].
Because dyes have chromophore groups in their structure, they are utilized in coloring
fabrics. These colors may be distinguished from one another by how easily they dissolve
in water. Most dyes are categorized according to the fibers they will be imprinted on
and their chemical and physical makeup. MB (methylene blue) is used to tone down the
hues of silk in addition to dying paper and office supplies [16]. MB poses a significant
concern to human health and can have a negative impact on the environment because it
is poisonous, carcinogenic, and non-biodegradable [17–19]. The health of people can be
seriously harmed by color molecules at extremely low concentrations [20]. It can result in
eye burns, which may result in both human and animal eyes being permanently damaged.
When ingested through the mouth, it generates a burning feeling and may cause vomiting,
excessive perspiration [21], methemoglobinemia [22], and mental disorientation [23]. It can
also cause short periods of rapid or difficult breathing when inhaled.
Heavy metals also play a vital role in polluting and poisoning the water. In water,
the presence of heavy metals even in a very low concentration is considered to be poi-
sonous and the high specific density and atomic weight of the metalloids make them
dangerous [24]. Additionally, such contamination can result in several “neurological, car-
diovascular, hematological, respiratory and renal problems” that also impact the bladder,
lungs, liver, and kidneys [25]. Although there are naturally occurring heavy metals in the
ecosystem, man-made sources of heavy metals are the fourth major cause of pollution.
Chromium manganese, copper, arsenic, and lead are the examples of heavy metals that are
frequently found in water. Further, chromium is frequently employed in many industrial
processes, including the production of paint and metal plating [26]. The tanning business
utilized between 4.0 and 6.0 thousand tonnes of basic Cr annually, with 20.0 to 40.0% of that
amount being disposed of as waste [27]. Cr(VI) is on the list of priority pollutants in the
majority of nations due to its high water mobility and acute toxicity [28]. When compared
to Cr, Cr(VI) is 100 times more poisonous (III). Compounds made of Cr(VI) are exceedingly
toxic and cancer-causing.
The major reason why chromium(VI) is regarded as being particularly dangerous is
that it easily interacts with biological molecules [29]. Due to its low membrane permeability,
trivalent chromium Cr(III) is mostly safe in the environment. Chromium in hexavalent
form is more effective in piercing the cell membrane through openings for isostructural
and isoelectric anions such as HPO4 2− and SO4 2− channels, and these forms of chromium
are then raised through phagocytosis [30]. By the adsorption reduction method Cr(VI)
is converted into the less toxic form Cr(III) [31]. Hexavalent chromium (Cr(VI)) is the
Inorganics 2023, 11, 133 3 of 17

most toxic heavy metal to living things, and the most potent carcinogen [32]. Dermatitis
and recurrent ulcers have been connected to exposure to Cr (VI) [33]. Modern oxidation
techniques have proven effective at cleaning industrial effluent [34–36].
The use of solar light in photocatalysis, one of many methods for treating water, has
drawn a lot of interest because it is environmentally friendly, economical, and effective in
reducing pollutants and energy use [37]. Many commonly used techniques, including coag-
ulation, active carbon adsorption, and precipitation can be utilized to treat wastewater that
contains hexavalent chromium. The produced hole and OH• radical are quickly consumed
by sacrificial electron donors such as methanol, preventing the electrons and holes from
recombining and making the electrons accessible for the reduction of Cr(VI) [38]. AOPs
have a lot of potential for treating industrial waste water that contains dyes because they
can degrade soluble organic pollutants in liquid wastes [39]. To remove dye molecules,
researchers are now concentrating on heterogeneous catalysts. One of the best AOPs for
eliminating organic contaminants from both water and the atmosphere is heterogeneous
photocatalysis [40]. Essentially, heterogeneous photocatalysis consists of a catalyst that
contain a semiconductor which is activated by using the visible and ultraviolet electromag-
netic radiation. The elimination of industrial effluents via the photocatalytic degradation
method has attracted interest [41]. By breaking molecular bonds with the species around
them, extremely reactive free radicals produced by the photocatalysis process can trig-
ger oxidation–reduction processes, which can reduce or oxidize the pollutants [42]. By
inducing radiation, electron and hole pairs are produced on their outer most layers and
hydroxyl radical (OH. ) and superoxide radical (O. 2 ) are produced by the reaction of water
and oxygen with the charge carriers. Due to their potential properties, semiconductor
metal oxides (MO) such as SnO2 , CuO, ZnO, and TiO2 , are popular study materials [43–47]
such as nonlinear optics [48], photonic crystals [49], electro ceramics components [50], solar
cells [51], and gas sensors [52].
By the incorporation of the noble metal nanoparticles in semiconductive oxides, the
photocatalytic activity of semiconductors is highly increased [53]. All semiconductors’
mechanisms for electron excitation have the potential to lead to electron and hole recombi-
nation, which lowers photo-efficiency from the valence band to the conduction band [54].
Noble metals including Au, Ag, Pd, and Pt, can be used to dope TiO2 because these boost
photocatalytic activity by preventing electron–hole pair recombination, which increases
photocatalytic activity [55]. Band gap also plays a considerable role in the photocatalytic
process [56]. The band gap of the TiO2 is the 3.2 eV. However, when Titina is doped by the
noble metal, the band gap decreases. Reduction in the band gap results in an increased
photocatalytic degradation and reduction. One of the effective methods to raise TiO2 ’s
photocatalytic effectiveness is to load it with Ag. For water purification silver is doped on
the surface of the TiO2 which acts as the self-cleaning agent. In this way, Ag contributes
to the process of photocatalysis. The silver metal acts as electron sinks, making them
efficient co-catalysts for boosting TiO2 photo reactivity. To capture the electrons that are
transported from the TiO2 conduction band, Ag can operate as an electron trap. At the same
time, it produces a surface plasmon resonance (SPR) effect, extending the light absorption
to the visible spectrum which result in an increase in the photocatalytic performance of
TiO2 [57]. It was discovered that Ag could increase the rate of photocatalytic degradation,
facilitate charge separation, and increase the adsorption of organic pollutants on the TiO2
surface [58]. Ag/TiO2 also acts as the electron trapping center that prevents the recombi-
nation of electrons/holes pairs caused by the Schottky barrier resulting in an enhanced
photocatalytic activity [59]. The synergistic impact of Ag, TiO2 , and biochar allowed to
effectively manufacture a series of biochar-coupled Ag–TiO2 materials, and the findings
demonstrated that the degradation performance of Ag-modified TiO2 was better than the
pure TiO2 [60]. Jiang et al. showed that after two hours of exposure to light, doping TiO2
with silver demonstrated 100% photodegrade performance [61]. According to Arbiter et al.
after sixty minutes, silver titanium oxide shows 85% of dye degradation [62]. According to
Avciata et al. after 150 min of irritation, 75% dye degradation is shown by the TiO2 doped
Inorganics 2023, 11, 133 4 of 17

with Ag [63]. Further, the doping of the silver on the TiO2 also caused the photo reduction
of chromium (VI) to the chromium (III). Silver-TiO2 also acts as the photo catalyst which
enhances the reduction of Cr(VI) to Cr(III).
In our continued research work on water pollution, we focus to synthesize the Ag/TiO2
composites by using the template induce rout for photocatalytic degradation of methylene
blue and photocatalytic reduction of Cr (VI) to Cr (III).

2. Experimental Section
2.1. Material and Method
The reactants employed in this investigation included methylene blue (MB), analytical
grade sodium carbonate (Na2 CO3 ), magnesium chloride (MgCl2 ), silver nitrate (AgNO3 ),
and potassium dichromate (K2 Cr2 O7 ). TiO2 was used as the titania source. X-ray diffraction
(XRD) data were obtained employing a Rigaku D-Max 2400 diffractometer operating in
reflection mode (Cu-K radiation), and SEM was used to evaluate the produced Ag/TiO2
composites (FEI Nova Nano SEM 450).

2.2. Preparation of Ag/TiO2 Composites

The Ag/TiO2 composites are synthesized by following the template induced route.
This is the bottom-up approach for nanotechnology for synthesizing nanomaterials
(Figure 1). In this experiment 0.1 M solution of sodium carbonate (Na2 CO3 ) and 0.1 M
solution of Magnesium chloride (MgCl2 ) were combined uniformly in a beaker at 40 ◦ C.
The aforementioned combination was then mixed at a 400 rpm stirring rate for 7 min, after
which the suspension was kept at 80 ◦ C for 4 h. The obtained Mg5 (CO3 )4 (OH)2 .4H2 O
product (MCH) was then filtered off, three times washed with first ethanol and then water
after being dried at 60 ◦ C for 12 h. After dispersing 1 g of synthetic MCH template in
80 mL of pure ethyl alcohol, TiO2 was added. The solution of distilled water and ethanol
was continuously stirred for 4 h at 25 ◦ C temperature. Deionized water and ethanol were
used to wash the MCH/TiO2 intermediate in succession before it was dried. In 100 mL
of absolute ethyl alcohol, 0.8 g of MCH/TiO2 intermediate was dispersed. The aforesaid
combination was then given an adequate amount of AgNO3 solution in three different
contents (0.01 M, 0.1 M, and 0.5 M), and the mixture was agitated for two hours. The
resultant samples were labeled 0.01-Ag/TiO2 , 0.1-Ag/TiO2 , and 0.5-Ag/TiO2 with varying
concentrations of Ag+ . After bubbling CO2 gas into the mixture for 30 min to flush out
any remaining Mg2+ ions, the mixture was once again washed with the buffer solution of
CH3 COOH/CH3 COONH4. This buffer solution is prepared by dissolving 0.1 g ammonium
acetate in 10 mL acetic acid. Then the Ag/TiO2 composites were dried at 60 ◦ C for 12 h. To
create Ag/TiO2 composites, the Ag2 CO3 /TiO2 precursor was calcined at 550 ◦ C for 4 h.

2.3. Photocatalytic Degradation Experiment

In the photocatalytic degradation experiment, the 0.0006 g methylene blue dye was
taken and then added to the 500 mL of water. Afterward, this solution was sonicated for
fifteen minutes. Furthermore, three beakers were taken, and 100 mL solution was added to
each. About 0.2 g of composite was inserted to every beaker. The solutions were stirred in
the absence of light for thirty minutes to achieve adsorption equilibrium. Then, the stired
solutions were added to Petri dishes, and 5 mL of the solution was taken as the reference.
These Petri dishes were exposed to direct sunlight and 5 mL solution sample was taken
at 30, 60, 90, 120, and 150 min respectively. The color of MB faded. The photocatalytic
degradation rate can be estimated by using the following equation:

Photodegradation rate = Co − Ct/Co × 100

Inorganics 2023, 11, x FOR PEER REVIEW 5 of 20

was taken at 30, 60, 90,120, and 150 min respectively. The color of MB faded. The photo-
Inorganics 2023, 11, 133
catalytic degradation rate can be estimated by using the following equation: 5 of 17
Photodegradation rate = 𝐶𝑜 − 𝐶𝑡/ 𝐶𝑜 × 100

Figure 1.
Figure 1. Schematic diagram of the synthesis of Ag/TiO
Ag/TiO22composites
compositesby
bytemplate
templateinduced
inducedroute.
route.

2.4.
2.4. Photocatalytic
Photocatalytic Reduction
Reduction Experiment
Experiment
In
In the photocatalytic reduction experiment,
the photocatalytic reduction experiment, 10 10 ppm
ppmsolution
solutionof ofanhydrous
anhydrousKK2 Cr 2Cr22O
O77
was prepared and 0.2 g of 0.01, 0.1, and 0.5 Ag/TiO was added to it as
was prepared and 0.2 g of 0.01, 0.1, and 0.5 Ag/TiO22 was added to it as a catalyst. Further, a catalyst. Further,
22 ml
ml ofof methanol
methanol waswas added
added into
into the
the solution
solution which
which acted
acted as as aa hole
hole scavenger.
scavenger. TheThe pHpH ofof
the solution was altered to 1.5 by utilizing NaOH
the solution was altered to 1.5 by utilizing NaOH and H2SO and H SO .
2 4. The
4 The solution was stirred
solution was stirred for
for thirty
thirty minutes
minutes to achieve
to achieve chemical
chemical equilibrium.
equilibrium. Taking
Taking 0-min
0-min reading
reading as the
as the reference
reference af-
afterward,
terward, the solutions were poured into a Petri dish and exposed to the sunlight. A
the solutions were poured into a Petri dish and exposed to the sunlight. A total
total
of
of 55 mL solutionwas
ml solution wastaken
takeninina aburette
buretteafter
after5,5,10,
10,15,15,20,20,
15,15,
20,20,25,25,
30,30,
35,35,
40,40,
45,45,
andand50
50 min respectively. This experiment
min respectively. This experiment was
was performed
performed in
in thethe last
last days
days of
of May.
May. The
The intensity
intensity
of the sun was 2100 Wm22. The removal rate of the chromium can be determined by using
of the sun was 2100 Wm . The removal rate of the chromium can be determined by using
the following equation:
the following equation:
Photoreduction rate==Co𝐶𝑜−−Ct/Co
Photoreductionrate 𝐶𝑡/ 𝐶𝑜× ×
100
100

3. Result and Discussion

3. Result and Discussion
The FTIR results as shown in Figure 2 revealed that the 3420 cm−1 peak relates to the
The FTIR results −1 peak −
stretching vibration of as
theshown in Figure
hydroxyl group 2[64].
revealed that the
However, the peak
3420 at
cm1621 cm relates to the
1 originated
stretching vibration of the hydroxyl group [64]. However, the peak at 1621 cm
due to the bending vibration of the water molecule. The O-Ti-O lattice and Ti-O stretching −1 originated

due to theare
vibration bending vibration
responsible forofthe
theTiO
water molecule. Thebands
2 characteristic O-Ti-O in lattice and Ti-O
the range cm−1 .
stretching
500–900
vibration
[Journal of are responsible
Materials Science:forMaterials
the TiO2incharacteristic bands29:18111–18119].
Electronics (2018) in the range 500–900 cm .[ Jour-
−1

nal ofTo
Materials
analyzeScience: Materials in
the crystallinity of Electronics (2018) 29:18111–18119].
Ag/TiO2 composites, XRD was used in the fractional
angle range of 10◦ to 80◦ as shown in Figure 3. The XRD results show that the peak
at 0.01 represents peak a, while the other two peaks represent the peaks of 0.1 and 0.5
given the names b and c respectively. The XRD results of 0.5 Ag/TiO2 , 0.1 Ag/TiO2 , and
0.01 Ag/TiO2 composites are categorized into two sets. In these two sets, one category
shows the peaks of the silver, while all the other peaks are matched with the structure
of TiO2 which is present in the rutile phase. The face-centered cube structure of silver is
Inorganics 2023, 11, 133 6 of 17

presented by showing 111, 200, 220, and 311 peaks at definite positions [65]. These peaks
are present at the 38.11◦ , 44.20◦ , 64.44◦ , and 77.39◦ positions [PDF: JCPDS 03–065-2871].
While the other peaks 110,101,210,211,220, 301, and 112 represent the rutile structure of
TiO2 . Strong diffraction peaks in XRD patterns at 27◦ , 36◦ , and 55◦ indicated that TiO2 was
Inorganics 2023, 11,
inxthe
FORrutile phase [66]. θ values are 27.3◦ , 36.0◦ , 41.0◦ 54.2◦ , 56.5◦ , 68.8◦ , and 70◦ , which
PEER REVIEW 6 of
correspond to tetragonal phase and can be indexed to the [PDF JCPDS 88-1175].

0.01Ag/TiO2
1.4 0.1Ag/TiO2
0.5Ag/TiO2

1.2
Transmittance(%)

(a)

1.0
(b)

(c)
0.8
1621 990
3420

0.6
570

Inorganics 2023, 11, x 4000 3500

FOR PEER REVIEW 3000 2500 2000 1500 1000 500 7 of
-1
Wavelength(cm )

Figure 2. (a) FTIRFigure

spectrum
2. (a)ofFTIR
0.01spectrum
Ag/TiO2 ofcomposite. (b)2 composite.
0.01 Ag/TiO FTIR spectrum of 0.1
(b) FTIR Ag/TiOof
spectrum 2 composite.
0.1 Ag/TiO2 compos
(c) FTIR spectrum(c)ofFTIR spectrum
0.5 Ag/TiO 2 . of 0.5 Ag/TiO2.

To analyze the crystallinity of Ag/TiO2 composites, XRD was used in the fraction
angle range of 10° to 80°as shown in Figure 3. The XRD results show that the peak at 0
represents peak a, while the other two peaks represent the peaks of 0.1 and 0.5 given t
names b and c respectively. The XRD results of 0.5 Ag/TiO2, 0.1 Ag/TiO2, and 0.01 Ag/Ti
composites are categorized into two sets. In these two sets, one category shows the pea
of the silver, while all the other peaks are matched with the structure of TiO2 which
present in the rutile phase. The face-centered cube structure of silver is presented by sho
ing 111, 200, 220, and 311 peaks at definite positions [65]. These peaks are present at t
38.11°, 44.20°, 64.44°, and 77.39° positions [PDF: JCPDS 03–065-2871]. While the oth
peaks 110,101,210,211,220, 301, and 112 represent the rutile structure of TiO2. Strong d
fraction peaks in XRD patterns at 27°, 36°, and 55° indicated that TiO2 was in the rut
phase [66]. θ values are 27.3°, 36.0°, 41.0° 54.2°, 56.5°, 68.8°, and 70°, which correspond
tetragonal phase and can be indexed to the [PDF JCPDS 88-1175].

Figure 3. (a) XRD of 0.01 Ag/TiO2 composite. (b) XRD of 0.1 Ag/TiO2 composite. (c) XRD of
Figure 3. (a) XRD of 0.01 Ag/TiO2 composite. (b) XRD of 0.1 Ag/TiO2 composite. (c) XRD of
0.5 Ag/TiO2 composite.
Ag/TiO2 composite.

Figure 4 depicts the scanning and flask-like electron microscope that was used
analyze the Ag/TiO2 composites’ morphology. The shapes of the given images are sph
ical. Due to spherical shapes, these composites enhance their surface area which increa
the capabilities of these composites toward different activities. On the other hand, E
Inorganics 2023, 11, 133 7 of 17
Figure 3. (a) XRD of 0.01 Ag/TiO2 composite. (b) XRD of 0.1 Ag/TiO2 composite. (c) XRD of 0.5
Ag/TiO2 composite.

Figure
Figure 44 depicts
depicts the
the scanning
scanning and
and flask-like
flask-like electron
electron microscope
microscope that
that was
was used
used to
to
analyze the Ag/TiO composites’ morphology. The shapes of the given images
analyze the Ag/TiO2 composites’ morphology. The shapes of the given images are spher-
2 are spherical.
Due to spherical
ical. Due shapes,
to spherical thesethese
shapes, composites enhance
composites theirtheir
enhance surface areaarea
surface which increases
which the
increases
capabilities of these composites toward different activities. On the other hand, EDS
the capabilities of these composites toward different activities. On the other hand, EDS (Figure 5
and Table 1) showed the Ag element peaks, which demonstrated that
(Figure 5 and Table 1) showed the Ag element peaks, which demonstrated that Ag wasAg was combined
within
combinedTiOwithin
2. TiO2.

Inorganics 2023, 11, x FOR PEER REVIEW 8 of 20

The morphology of the Ag/TiO2 composites was examined by using the scanning and
flask-like
Figure 4. electronimage
4. (a) microscope. The shapes of the given images are spherical. Due to spher-
Figure (a) SEM
SEM image of
of 0.5
0.5 Ag/TiO
Ag/TiO 2 composite. (b) SEM image of 0.01 Ag/TiO2 composite. (c)
2 composite. (b) SEM image of 0.01 Ag/TiO2 composite.
ical shapes, these composites enhance
SEM image of 0.1 Ag/TiO2 composite. their surface area which increases the capabilities
(c) SEM image of 0.1 Ag/TiO2 composite.
of these composites toward different activities.

Figure 5.
5. (a)
(a) EDS
EDS of
of 0.5
0.5 Ag/TiO
Ag/TiO2 2composite.
composite.(b)(b)
EDS ofof
EDS 0.01
0.01Ag/TiO
Ag/TiO2 composite. (c) EDS of 0.1
Figure 2 composite. (c) EDS of
Ag/TiO2 composite.
0.1 Ag/TiO2 composite.
TableThe
1. The elemental composition
morphology of (a)
of the Ag/TiO 0.5 Ag/TiO2 composite; (b) 0.01 Ag/TiO2 composite; (c)
2 composites was examined by using the scanning and
0.1Ag/TiO2 composite.
flask-like electron microscope. The shapes of the given images are spherical. Due to spheri-
cal shapes, these composites enhance their surface area which increases the capabilities of
these composites toward different activities.
The smallest amount of energy needed by an electron to break out from its bound
state is known as the band gap in Figure 6. Talc plots were created using absorbance
data from UV–VIS spectrophotometry at room temperature to calculate the band gap for
Inorganics 2023, 11, 133 8 of 17

manufactured nanoparticles. To do this, relations were used to compute the photon energy
“E” and the absorption co-efficient “α” of synthesized samples:

E = hv = 1240/λ

α = 4π ( absorbance)/λ

Table 1. The elemental composition of (a) 0.5 Ag/TiO2 composite; (b) 0.01 Ag/TiO2 composite;
(c) 0.1 Ag/TiO2 composite.

Apparent
Composite Element Line Type k Ratio Wt% Wt% Sigma Standard Lable Factory Standard
Concentration
O K series 10.63 0.0357 25.65 0.52 O2 Yes
Ti K series 14.32 0.1432 21.19 0.32 Ti Yes
(a)
Ag L series 25.29 0.2529 37.96 0.53 Ag Yes
Au M series 2.42 0.0242 4.03 0.24 Au Yes
O K series 10.69 0.0359 26.53 0.55 O2 Yes
Ti K series 17.00 0.1700 25.58 0.33 Ti Yes
(b)
Ag L series 22.69 0.2268 34.87 0.46 Ag Yes
Au M series 2.75 0.0275 4.69 0.28 Au Yes
O K series 11.58 0.0389 27.23 0.46 O2 Yes
Ti x FOR PEER
Inorganics 2023, 11, K series
REVIEW 14.57 0.1456 21.34 0.28 Ti Yes 10 of 20
(c)
Ag L series 24.79 0.2479 36.89 0.46 Ag Yes
Au M series 2.43 0.0242 4.01 0.21 Au Yes

Figure 6. (a)
Figure Band
6. (a) gapgap
Band of 0.5 Ag/TiO
of 0.5 2 composite.
Ag/TiO (b) Band gap of 0.1 Ag/TiO2 composite.
2 composite. (b) Band gap of 0.1 Ag/TiO
(c) Band
2 composite. (c) Band
gap of 0.01 Ag/TiO
gap of 0.01 Ag/TiO composite.
2 2 composite.

After exposure to methylene blue under sunlight, degradation of methylene blue

started. The readings taken at different time intervals are shown in the Figure 7. After
taking the readings at these intervals, the collected solutions were run in a UV-visible
spectrophotometer, and the degradation percentage was recorded. After analysis, it was
Inorganics 2023, 11, 133 9 of 17

The absorption coefficient “α” and the energy band gap have the following relation:

(αhv) = B (hv–Hg)1/2

The band gap calculated for the 0.5 Ag/TiO2 composite is 3.6 eV, while for the 0.1 the
band gap is 3.4 eV, and for 0.01 Ag/TiO2 composite 2.7 eV.
After exposure to methylene blue under sunlight, degradation of methylene blue
started. The readings taken at different time intervals are shown in the Figure 7. After
taking the readings at these intervals, the collected solutions were run in a UV-visible
spectrophotometer, and the degradation percentage was recorded. After analysis, it was
observed that the 0.5 Ag/TiO2 , 0.1 Ag/TiO2 , and 0.01 Ag/TiO2 composites degraded at
54%, 68%, and 90% respectively. So, the result shows the composite 0.01 Ag/TiO2 shows
Inorganics 2023, 11, x FOR PEER REVIEW 11 of 20
the highest degradation of methylene blue as compared to the others. Because as the Ag
loading exceeds 0.06 wt %, the photocatalytic effectiveness steadily declines, which is
mostly caused by the shielding effect of the high Ag coverage.

Figure 7. (a)
Figure TheThe
7. (a) UVUV visible spectrum
visible spectrum ofof
methylene
methyleneblue
blueininthe
thepresence
presence of
of 0.5
0.5 Ag/TiO composite.
Ag/TiO2 2composite.
(b) In
(b)the presence
In the presenceof 0.1 Ag/TiO
of 0.1 Ag/TiO2 composite,
2 composite,methylene
methylene blue’s
blue's UV spectrum.
spectrum. (c)(c)The
TheUVUVvisible
visible
spectrum
spectrum of MBof MB in the
in the presence
presence of 0.01
of 0.01 Ag/TiO
Ag/TiO 2
2 composite.(d)
composite. (d) The
The comparison
comparison graph
graph of
of 0.5
0.5 Ag/TiO
Ag/TiO 2, ,
2
0.1 Ag/TiO
0.1 Ag/TiO 2, and 0.01 Ag/TiO2 composites.
, and 0.01 Ag/TiO composites.
2 2

To To study
study thethekinetics
kineticsofofthe
the degradation
degradation ofofmethylene
methylene blue,
blue,a graph waswas
a graph plotted be-
plotted
tween the instantaneous concentration (at radiation time) and the starting
between the instantaneous concentration (at radiation time) and the starting concentration concentration
of the
of the sample
sample introduced
introduced at at zero
zero minutes,resulting
minutes, resultingininaastraight
straight line
line with
with an
an R
R2>>0.95
2
0.95asas
shown Figure 8 and Table 2. It shows that a first-order reaction was used to quantifythe
shown Figure 8 and Table 2. It shows that a first-order reaction was used to quantify the
photocatalytic degradation rates for synthesized photocatalysts:
photocatalytic degradation rates for synthesized photocatalysts:
co
−ln co= kt
− lnct = kt
c t
where ce is the instantaneous concentration and co is the starting concentration of the ma-
terial being injected at zero minutes (at irradiation of time). While the value of ct was de-
termined by comparing the Beer–Lamberts Law at zero minutes and at various irradiation
times, the value of co is known for each photocatalyst.
A 𝜀
Inorganics 2023, 11, 133 10 of 17

where ce is the instantaneous concentration and co is the starting concentration of the

material being injected at zero minutes (at irradiation of time). While the value of ct
was determined by comparing the Beer–Lamberts Law at zero minutes and at various
irradiation times, the value of co is known for each photocatalyst.

A ε
=
c 1
The UV data, as shown in Figure 9, indicate that 50 min of exposure to the sunlight
using the 0.5 Ag/TiO2 catalyst results in a 50% reduction of Cr (VI) to Cr (III), while using
the 0.1 Ag/TiO2 catalyst shows a 54% reduction of Cr (VI) to Cr (III), and 0.01 Ag/TiO2
composite as the catalyst shows 75% reduction of the Cr (VI) to Cr (III). The pH affects the
photoreduction of the Cr (VI) to Cr (III) as shown in Figure 10. The best result is shown by
the Ag/TiO2 composites at 1.5 pH as compared to the 5 and 3. So all the experiments of
photoreduction of the Cr (VI) to Cr (III) were carried out at pH 1.5.

r = −dC/dt = K0 C;

In the above equation, K’, with a unit of time-1, is the fictitious first-order rate constant.
r represents the reaction rate where the illumination (reaction) time is represented by t. The
amount of aqueous Cr (VI) concentration is denoted by C; where Ce represents the level of
Cr (VI) at time t and Co represents the starting level of Cr (VI). The relationship between the
Cr (VI) concentration and absorbance is linear as shown in Figure 11 and Table 3 as well.
Inorganics 2023, 11, x FOR PEER REVIEW 12 of 20
ln (Ct /Co ) = −K0

Figure 8.8. (a) The first-order kinetic

Figure kinetic of
of 0.01
0.01 Ag/TiO
Ag/TiO 2 composite.
2 composite.(b)(b)
The first-order
The kinetic
first-order of of
kinetic 0.1
Ag/TiO
0.1 2 composite.
Ag/TiO 2
(c)
composite. The
(c) first-order
The kinetic
first-order of
kinetic0.5
of Ag/TiO
0.5 2 composite.
Ag/TiO 2 composite.

Table 2. kinetics study of photocatalytic degradation of methylene blue.

Ag/TiO2 Composites R2 Kapp Degradation

0.01Ag/TiO2 0.0090 0.0135 90%
0.1Ag/TiO2 0.981 0.007 68%
0.5Ag/TiO2 0.9682 0.0051 54%

The UV data, as shown in Figure 9, indicate that 50 min of exposure to the sunlight
using the 0.5 Ag/TiO2 catalyst results in a 50% reduction of Cr (VI) to Cr (III), while using
Inorganics 2023, 11, 133 11 of 17

Table 2. Kinetics study of photocatalytic degradation of methylene blue.

Ag/TiO2 Composites R2 Kapp Degradation

0.01 Ag/TiO2 0.0090 0.0135 90%
Inorganics 2023, 11, x FOR PEER REVIEW 13 of 20
0.1 Ag/TiO2 0.981 0.007 68%
0.5 Ag/TiO2 0.9682 0.0051 54%

Figure 9. (a) The UV visible spectra of 0.5 Ag/TiO2 composite of photocatalytic reduction of Cr (VI)
Figure 9. (a) The UV visible spectra of 0.5Ag/TiO2 composite of photocatalytic reduction of Cr (VI)
to to
Cr(III). (b)(b)
Cr(III). The UVUV
The visible spectra
visible of 0.1
spectra Ag/TiO2 composite
of 0.1Ag/TiO of photocatalytic reduction of Cr(VI)
2 composite of photocatalytic reduction of Cr(VI)
to to
Cr(III). (c) (c)
Cr(III). Photocatalytic reduction
Photocatalytic of Cr(vi)
reduction to Cr(III).
of Cr(vi) (d) (d)
to Cr(III). Comparison graph
Comparison of 0.5
graph of Ag/TiO 2 , 2,
0.5Ag/TiO
0.10.1Ag/TiO
Ag/TiO2 ,2,and and0.01 Ag/TiO 2 composites.
0.01Ag/TiO composites.

Table 3. Kinetics study of photocatalytic reduction of Cr(VI) to Cr(III).

Ag/TiO2 Composites R2 Kapp Reduction

0.01 Ag/TiO2 0.8965 0.0259 75%
0.1 Ag/TiO2 0.8708 0.014 54%
0.5 Ag/TiO2 0.9243 0.0166 50%
 Inorganics 2023, 11, x FOR PEER REVIEW 14 of 20

Inorganics 2023, 11, 133 12 of 17

Inorganics 2023, 11, x FOR PEER REVIEW 15 of 20

Figure 10. Comparison graph of photocatalytic reduction of Cr (VI) to Cr (III) at different pH values.
Figure 10. Comparison graph of photocatalytic reduction of Cr (VI) to Cr (III) at different pH val-
ues.

𝑟 = − 𝑑𝐶/ 𝑑𝑡 = 𝐾 ′𝐶
In the above equation, K’, with a unit of time-1, is the fictitious first-order rate con-
stant. r represents the reaction rate where the illumination (reaction) time is represented
by t. The amount of aqueous Cr (VI) concentration is denoted by C; where Ce represents
the level of Cr (VI) at time t and Co represents the starting level of Cr (VI). The relationship
between the Cr (VI) concentration and absorbance is linear as shown in Figure 11 and
Table 3 as well.
ln (𝐶t /𝐶o) = −𝐾 ′
The kinetics study indicates the photocatalytic reduction of Cr(VI) to Cr(III) follows
the pseudo first-order reaction.

11. (a) The

Figure 11. The pseudo
pseudo first
first order
orderkinetics
kineticsof
of0.01Ag/TiO
0.01Ag/TiO22 composite. (b) The pseudo first-order
Ag/TiO22 composite.
kinetics of 0.1 Ag/TiO composite.(c)
(c)The
Thepseudo
pseudofirst-order
first-orderkinetics
kinetics of
of 0.5
0.5 Ag/TiO
Ag/TiO2 2composite.
composite.

Table 3. Kinetics study of photocatalytic reduction of Cr(VI) to Cr(III).

Ag/TiO2 Composites R2 Kapp Reduction

0.01 Ag/TiO2 0.8965 0.0259 75%
0.1 Ag/TiO2 0.8708 0.014 54%
0.5 Ag/TiO2 0.9243 0.0166 50%
- +
 Figure 11. (a) The pseudo first order kinetics of 0.01Ag/TiO2 composite. (b) The pseudo first-order
kinetics of 0.1 Ag/TiO2 composite. (c) The pseudo first-order kinetics of 0.5 Ag/TiO2 composite.
Figure 11. (a) The pseudo first order kinetics of 0.01Ag/TiO2 composite. (b) The pseudo first-order
kinetics
Table 3. of 0.1 Ag/TiO
Kinetics study 2 composite. (c) Thereduction
of photocatalytic pseudo first-order kinetics
of Cr(VI) to Cr(III).of 0.5 Ag/TiO2 composite.
Inorganics 2023, 11, 133 Figure 11. (a) The pseudo first order kinetics of 0.01Ag/TiO2 composite. (b) The pseudo first-order 13 of 17
kinetics
Ag/TiO of 20.1 Ag/TiO2 composite. (c)R
Composites The
2 pseudo first-order kinetics
K app of 0.5 Ag/TiOReduction
2 composite.
Table
Figure3.11.Kinetics
(a) Thestudypseudo of photocatalytic
first order kineticsreduction of Cr(VI) 2tocomposite.
of 0.01Ag/TiO Cr(III). (b) The pseudo first-order
kinetics of 0.1 Ag/TiO2 composite. (c)2The pseudo first-order kinetics of 0.5 Ag/TiO2 75%
0.01 Ag/TiO 2 0.8965 0.0259 composite.
Table 3. Kinetics
Ag/TiO
Figure 211. (a) study
Composites
The of photocatalytic
pseudo reduction
R kinetics
first order of of Cr(VI) to
0.01Ag/TiO Kapp2Cr(III).
composite. (b) The Reduction
0.1
The Ag/TiO
kinetics 2 study indicates 0.8708 the photocatalytic 0.014
reduction of Cr(VI) topseudo
54% first-order
Cr(III) follows
kinetics
0.01 of 0.1 Ag/TiO
Ag/TiO 2 2 composite. (c) The pseudo first-order
0.8965 0.0259 kinetics of 0.5 Ag/TiO75% 2 composite.
Table
Ag/TiO
Figure 3.2 Composites
the pseudo
0.5
11. Kinetics
Ag/TiO
(a) The 2study of
first-order
pseudo photocatalytic
reaction.
first Rkinetics
0.9243
order 2 reduction of Cr(VI)
of 0.01Ag/TiO K
0.0166to Cr(III). (b) The Reduction
2 composite.
app pseudo50% first-order
kinetics0.1
0.01 Ag/TiO
ofAg/TiO
0.1 Ag/TiO2
2
2 composite.0.8965
0.8708
(c) The pseudo first-order 0.014
kinetics of 0.5 Ag/TiO2 composite.
0.0259 54%
75%
Table
Ag/TiO
Figure 3.2 Kinetics
11. Composites
(a) The study Ag/TiO
pseudo offirst
photocatalytic
order+ Rhv2 reduction
kinetics of of Cr(VI)
0.01Ag/TiO K −to
e -cbCr(III).
+ h
composite. ++vb (b) The Reduction
pseudo (1)
0.5Ag/TiO
0.1 Ag/TiO 2
2 Ag/TiO 2
0.87082 + hv
0.9243 0.0166
2
0.014
app
e cb + h vb 50% first-order
54%
(1)
kinetics
0.01 ofAg/TiO
0.1 Ag/TiO 2 2 composite.0.8965(c) The pseudo first-order kinetics
0.0259 of 0.5 Ag/TiO 2 composite.
75%
Table 3. Kinetics
Ag/TiO study of photocatalytic
2 Composites h vb + H2O
+ R 2reduction of Cr(VI) toK Cr(III).
HO + H
app + Reduction (2)
0.50.1
Ag/TiO
Ag/TiO 2
2 h+0.9243
Ag/TiO vb2 ++hv
0.8708 H2 O 0.0166
HO
0.014e-cb++H h++vb 50%
54% (1)
(2)
Ag/TiO 0.01 Ag/TiO
Table 3.2 Composites 2
Kinetics study of photocatalytic R0.8965
2 reduction of Cr(VI)
K 0.0259
to Cr(III).
app
75%
Reduction
0.5 Ag/TiO
0.1
HO+
Ag/TiO 2
HO+2
targeth+pollutant
Ag/TiO
target vb2 +0.9243
hv
H2O
pollutant
0.8708 e-degradation
0.0166cb + h
HO
degradation
0.014 ++vb
H+ productproduct
50%
54%
(3)
(1)
(2)
(3)
0.01
Ag/TiO Ag/TiO 2
2 Composites
0.8965 R 2 0.0259
K 75%
Reduction
+ app
0.1 0.5
Ag/TiOhHO+
Ag/TiO vb +
2 h vb
2+ target
h+vb
target pollutant
+Ag/TiO
target 2 0.9243
+0.8708
H
pollutant+2O hv
pollutant 0.014 Oxidation
0.0166
HO e-cb++H
degradation
Oxidation Product
h++vb Product
product
54%50% (4)
(1)
(2)
(3)
(4)
0.01 Ag/TiO 2 0.8965 0.0259 75%
0.50.1Ag/TiO - 0.9243 0.0166 . 50%
h+vb2 +target
HO+
Ag/TiO 2 eAg/TiO
target h
cb+ +O
vb
pollutant
pollutant − +cb2hv
+e0.8708
22H O+ O2 O OHO2e2 cb + H
. -
degradation
Oxidation
0.014 h vb Product
++
product54% (5)(1)
(2)
(3)
(4)
(5)
0.5 Ag/TiO
Oh.2+vbHO+
+O +target 2 +0.9243
pollutant
Ag/TiO 0.0166
degradation product 50%
2.
+target
e-cb
2target O+hv
hpollutant
+vb
pollutant
target + 2 H2O
pollutant e-cb.degradation
Oxidation
degradation
O + h+vb +Product
2HO + Hproduct product (1)
(6)(2)
(3)
(4)(6)
(5)
-+ −
O.e2hcb+HO+++target
vbe
target +eAg/TiO
hcb+vb
target
-target
cbtarget
2 +2O
pollutant hv
+pollutant
H
pollutant
+pollutant
pollutantO 2 HOe-degradation
cb++H
.reductionh++vbproduct
2Oxidation
Oreduction
degradation product
product
Product
product (2)(1)
(7)
(4)
(5)
(6) (3)
(7)
+ target
The O . HO+
Theproposed
2 e+h
proposed + mechanism
- target
cb vb e-hpollutant
+mechanism
target +vb + H2O
pollutant
target Oofof
2 removal
removalof
pollutant
+
pollutant
cb HO
ofphotocatalytic
photocatalytic
O
degradation + H+product
degradation
2 pollutants
.Oxidation
pollutants
reduction product
by
byAg/TiO
Product
product Ag/TiO (3)
2 2com-(2)
com-
(5)
(6)
(7) (4)
posite
positeisisshown
shown + in
in Figure 12. 12. The
The Ag/TiO
Ag/TiO 22 in an aqueous
aqueous matrix
matrix isis exposed
exposed toto light
light with
with an
Oeh-.cb
The proposed HO+
2vb+++targettarget
target
target
- pollutant
epollutant
cb + of
pollutant
mechanismpollutant degradation
O .
Oxidation
O2removal of photocatalytic
degradation
reduction product
Product
product
product
2 pollutants by Ag/TiO2 com- (7)(3)
(4)(6)
(5)
an energy
energy level
level over over itsitsbandband gapgap (Eg (Eg = 2.7
= 2.7 eV), eV), andand electrons
electrons are are produced
produced in inthethe conduc-
conduction
posite
tion is shown
band and h .-+vb
holesin +Figure
target
in - 12.
the The
pollutant
valance Ag/TiO
band 2 in an
(Equation aqueous
(1)). matrix
. Oxidation
Hydroxyl is exposed
Product
radicals to light with
band and
The proposedholes in the
Oe 2cb++mechanism
target
target valance
e + O band
cbpollutant
pollutant
of (Equation
2 removal of photocatalytic (1)). Hydroxyl
O degradation
2reductionradicals
pollutants by Ag/TiO2created
can
product
product becan be
created when
com- (4)
(5)(7)(6)
anthe
when energy
adsorbed
the levelwater
adsorbed overreacts
its band
water with gap
reacts the (Eg = the
2.7 eV),
photogenerated
with andvalance
photogenerated electrons bandare gaps
valance produced(Equation
band in the
gaps conduc-
(2)).
(Equation Target
posite is shown . in- Figure e12. - The Ag/TiO2 in an aqueous matrix
+to Oaof2photocatalytic .
Oreduction is exposed to light with(6)(5)
tion The O
band
pollutants and 2 +holes
proposed
can etarget
cb +
be in pollutant
target
mechanism
the cb
subjected pollutant
valance removal
bandto(Equation degradation
of photocatalytic
(1)). 2 pollutants
Hydroxyl product
product
radicals bycan Ag/TiO 2 com-
behydroxyl
created (7)
an(2)). Target
energy pollutants
level over its canbandbegap subjected
(Eg = 2.7 eV), andinteraction
a photocatalytic with
electronsinteraction
are the
produced generated
with inthe thegenerated
conduc-
posite
when is shown
the
radicals . theinvalance
adsorbed
and Figure
water 12.
reacts
band The Ag/TiO
with
holes the in (Equations
an aqueous
2photogenerated
(Equations (3) matrix
valance isthe
exposed
band gaps to lightthe
(Equation with
hydroxyl
tion bandThe radicals
and Oe-holes
2+
proposed
cb and
+ target
target thepollutant
inmechanism
the valance
pollutant
valance of band
removal
band holes
(Equation (1)).and (4)).
(3)
degradation
reduction
of photocatalytic
Hydroxyl andOnradicals
(4)).
product
pollutants other
On
product by hand,
the
can other
Ag/TiO
be created hand,
2 (7)
ad-
(6)
com-
an
(2)). energy
Target
sorbed
the level
pollutants
molecular
adsorbed over
molecular its
oxygen can band
be
on
oxygen gap
subjected
Ag/TiO
on (Eg =
Ag/TiO2.7
to
can a eV), and
2combine
can electrons
photocatalyticwith
combine are produced
interaction
the
with with
photogenerated
the in
the
photogenerated the conduc-
generated
conduction con-
posite is
when the adsorbed shown - in Figure 12. The Ag/TiO
2 in an aqueous
water reacts with the photogenerated valance band gaps (Equation(7)
2 matrix is exposed to light with
tion The
hydroxyl
band band andeelectrons
proposed
radicals
electrons cbto+
holes and target
mechanism
makeinthe pollutant
valanceofsuperoxide
thesuperoxide
valance removal
bandholes
band of radical
photocatalytic
(Equation (1)).
(Equations reduction
Hydroxylpollutants
(3)(Equation
and(5)). product
by the
radicals
(4)). On Ag/TiO
can be
other com-
2created
hand,
duction
(2)).an energy
Target band level
pollutants over canitstobemake
band gap (Egradical
subjected to= 2.7 anions
eV),
a photocatalytic (Equation
andanions
electrons are produced
interaction Moreover,
(5)).
with Moreover,
the the
ingenerated
the target
conduc-the
Inorganics 2023, 11, x FOR PEER posite
REVIEW
when
the
Inorganics 2023, 11, x FOR PEER REVIEW
target is shown
the
adsorbed
pollutants adsorbed
pollutantscan in
molecular
causeFigure
can water
cause 12. The
reacts
oxygen
degradation
degradationAg/TiO
on with
and Ag/TiOthe
reduction
and2 in an
2 can aqueous
photogenerated
reduction combine
products matrix
by
products with is
valance
the exposed
interacting
by band to
gaps
photogenerated
with
interacting light
newly
with
16with
(Equation of
of 20
16 con-
formed
newly 20
tionThe
hydroxyl band proposed
and holes
radicals andmechanism
in the
the valance
valance ofbandremoval
bandholes of(Equations
photocatalytic
(Equation (1)).(3)Hydroxyl
andpollutants
(4)).radicals by Ag/TiO
On the can behand,
other com-
2created
an energy
(2)).
duction Target
superoxide
formed level
band over its
pollutants
electrons
radical
superoxide anionsband
radicalcan
to begap
make
and
anions (Eg
subjected = 2.7
superoxide
conduction
and toeV), aband
conduction andelectrons
radical electrons
photocatalytic
anions
band are produced
interaction
(Equation
(Equations
electrons with
(5)).
(6)
(Equations inMoreover,
and the
the (7))
(6)conduc-
generated
[67].
and the
(7)
Inorganics 2023, 11, x FOR PEER REVIEW the posite
when isthe
adsorbed shown
adsorbed
molecular in Figure water 12.
oxygen The
reactson Ag/TiO
with the 22 in ancombine
aqueouswith
photogenerated
can matrix theisphotogenerated
valance exposed
band gaps 16to oflight
(Equation
20 con- with
tion
target
[67]. band
hydroxyl and
pollutants holes
radicals can incause
and the
thevalance
valanceband
degradation bandand (Equation
holes (1)).products
(Equations
reduction Hydroxyl
(3) and byradicals
(4)). Oncan
interacting the be
other
with created
hand,
newly
an energy
(2)). Target level over
pollutants its band
can be gap (Eg
subjected = 2.7to eV),
duction band electrons to make superoxide radical anions (Equation (5)). Moreover, thea and electrons
photocatalytic are produced
interaction with in the
the conduc-
generated
when
formed thesuperoxide
the adsorbed adsorbed molecular water
radical reacts
oxygen
anions with
onand the
Ag/TiO photogenerated
conduction 2 can combine
band valance
with the
electrons band gaps (Equation
photogenerated
(Equations (6) and con-
(7)
tion
target band and
hydroxyl
pollutants radicals holes and
can cause in the the valance
valanceband
degradation and(Equation
band holes
reduction (1)).
(Equations Hydroxyl
products (3) by
and radicals
(4)). On the
interacting canwith benewly
other created
hand,
(2)). Targetband
duction
[67]. pollutantselectrons cantobemake subjected to a photocatalytic
superoxide radical anions interaction
(Equationwith (5)).the generated
Moreover, the
when
formed the adsorbed
the adsorbed
superoxide molecular wateranions
radical reacts and
oxygen with the photogenerated
on Ag/TiO
conduction 2 canbandcombineelectronsvalance theband
with (Equations gaps (6)(Equation
photogenerated and (7) con-
hydroxyl radicals and
target pollutants the valance
can cause degradation band holes (Equations
and reduction (3) and by
products (4)). On the other
interacting withhand, newly
(2)).
[67]. Target
duction bandpollutants
electrons cantobe subjected
make superoxideto a photocatalytic
radical anions interaction
(Equationwith (5)). the generated
Moreover, the
the adsorbed
formed molecular
superoxide radicaloxygen anionson Ag/TiO
and conduction 2 can combine band with electronsthe photogenerated
(Equations (6) and con-(7)
hydroxyl radicals can
target pollutants andcause the valance
degradation band holes (Equations
and reduction (3) andby
products (4)). On the other
interacting withhand, newly
duction
[67]. band electrons to make superoxide radical anions (Equation (5)). Moreover, the
the adsorbed
formed superoxide molecular radical oxygenanions on andAg/TiO 2 can combine
conduction with the (Equations
band electrons photogenerated (6) and con- (7)
target pollutants can cause degradation and reduction products by interacting with newly
duction
[67]. band electrons to make superoxide radical anions (Equation (5)). Moreover, the
formed superoxide radical anions and conduction band electrons (Equations (6) and (7)
target pollutants can cause degradation and reduction products by interacting with newly
[67].
formed superoxide radical anions and conduction band electrons (Equations (6) and (7)
[67].

Figure
Figure12.
12.The
Thesimultaneous
The simultaneousremoval
simultaneous removalof
ofphotocatalytic
photocatalyticpollutants
pollutantsby
byAg/TiO
Ag/TiO222composite.
Ag/TiO composite.
composite.

3.1.The
Figure 3.1.
12.
3.1. Effect ofMethanol
Methanol
simultaneous
Effect
Effect ofof removal of photocatalytic pollutants by Ag/TiO2 composite.
Methanol
Methanol was
Methanol
Methanol waschosen
chosentoto
chosen toserve
serve
serve asas
a hole
as aa holescavenger.
hole scavenger.
scavenger. Methanol
Methanol
Methanol radicals are created
radicals
radicals are when
are created
created
3.1. Effect
theofCH
Methanol
OH scavenges the h + in the++invalence band (CH OH . ). The hole scavenger produces
when
when the CH3OH scavenges the h in the valence band (CH2OH ). The hole scavengerpro-
the
3 CH 3OH scavenges the h the valence band 2(CH 2 OH .).
. The hole scavenger pro-
Methanol
a radical
duces was chosen
by removing
aa radical by tothe
serve as hydrogen
hydrogen a holefromscavenger.
the hydroxylMethanol radicals
groupgroup [68,69]. are
Thecreated
valence band
duces radical by removing
removing the
the hydrogen from
from the
the hydroxyl
hydroxyl group [68,69].
[68,69]. The
The valence
valence
when the CH
receives
band 3OH scavenges
e- from
receives e- the the formaldehyde
h+ in the valence
formaldehyde radicals band
created (CH by2OH
theby ). The
.oxidation holeofscavenger
the methanolpro- radical.
band receives e-from
from the
the formaldehyde radicals
radicals created
created bythe theoxidation
oxidation of
ofthe
themethanol
methanol
duces radical.
aThe
radical by removing
formaldehyde the
undergoeshydrogen from
additional the hydroxyl
oxidation to group
generate [68,69].
formic The valence
acid before being
radical. The formaldehyde undergoes additional oxidation to generate formic acidbefore
The formaldehyde undergoes additional oxidation to generate formic acid before
band receives
broken
being e- from
down the
into formaldehyde
CO and H O. radicals created by the oxidation of the methanol
beingbroken
brokendown downinto 2 CO
into CO22and2
and HH22O.
O.
radical. The formaldehyde undergoes additional oxidation to generate formic acid before
++
being broken down into CO2 and H2CH O. 333OH
CH
CH OH+++hhh+ CH CH
CH 22OH
2 OH OH
·· •+ ++ + −− −
CH
CH 2OH
CH3CHOH
2OH +h
2 OH
CH22O
CHCHO2++
CH O2H
+ H++
H
OH e+e e
The
Theconducting − 2O), H+, and e- as donations or fill
CHband
conducting OH·can
2band canaccept
acceptCHformaldehyde+
formaldehyde (CH
2O + H + e(CH2O), H+, and e- as donations or fill
the
the positively
positively charged
charged vacancies,
vacancies, which
which slows
slows the
the rate
rate+ofof ee/h
- - ++ recombination. The pro-
/h recombination. The pro-
The conducting
duced band can accept formaldehydewhich(CH2O), H , oxidized
and e- as donations or fillspecies
ducedholes
holesare
arescavenged
scavengedby bythe
themethanol,
methanol, whichisisthen
then oxidized to
toproduce
producethe
the species
the positively
that charged vacancies, which slows the rate of e -/h+ recombination. The pro-
that donate
donate electrons.
electrons. CHCH22OH.
OH. EEo == 0.95
0.95 VV (CH
(CH22OH/CH
OH/CH22O) O) [70].
[70]. When
When aa methanol
methanol hole
o
hole
ducedscavenger
holes are scavenged by the photogenerated
methanol, which is then oxidized to produce the species
scavengerisisemployed,
employed,the theophotogeneratedholesholesare
arenot
notimmediately
immediatelyconsumed.
consumed.Instead,
Instead,
that donate
the electrons. CH2OH. E = 0.95 VCH (CH2OH/CH 2O) [70]. in Whenformation
a methanol ehole
thehydroxyl
hydroxylradicals
radicalsradicalize
radicalizethe
the CH33OH,
OH,which
whichresults
results inthe the formationofof e-[71].
-
[71].
Inorganics 2023, 11, 133 14 of 17
Figure 12. The simultaneous removal of photocatalytic pollutants by Ag/TiO2 composite.

3.1. Effect of Methanol

The conducting band + and e− as donations or
Methanol was chosen to can
serve accept
as a formaldehyde
hole scavenger. (CH 2 O), H ,radicals
Methanol are created
fillthe
theCH
positively −
charged vacancies, which slows the rate of e /h+ recombination. The
when 3OH scavenges the h+ in the valence band (CH2OH.). The hole scavenger pro-
produced
duces a radicalholes are scavenged
by removing by the methanol,
the hydrogen which is group
from the hydroxyl then oxidized to produce
[68,69]. The valence the
species that donate electrons. CH OH. E o = 0.95 V (CH OH/CH O) [70]. When a methanol
band receives e- from the formaldehyde 2 radicals created by 2 the oxidation
2 of the methanol
holeThe
radical. scavenger is employed,
formaldehyde undergoesthe photogenerated holestoare
additional oxidation not immediately
generate formic acidconsumed.
before
Instead, the hydroxyl radicals
being−broken down into CO2 and H2O. radicalize the CH 3 OH, which results in the formation of
e [71].
OH CH•
+3OH
CH3+OH h+ CH CH •
2OH+ H2 O
2 OH

CH2OH
3.2. Antifungal Performance
·
CH2O + H+ + e−
The0.01 Ag/TiOband
conducting 2 , 0.1 Ag/TiO
can accept2 , and 0.5 Ag/TiO(CH
formaldehyde 2 nanocomposites
2O), H+, and e- were further tested
as donations or fill for
their antifungal activity against S. macrospora and S. maydis using the
the positively charged vacancies, which slows the rate of e /h recombination. The pro-
- + agar well-diffusion
method
duced holes and amphotericin
are scavenged B methanol,
by the as a reference.
whichAn overview
is then oxidizedof to
theproduce
findingstheisspecies
shown in
thatTable 4. When
donate compared
electrons. CH2OH. to 0.1
E =Ag/TiO
o and2OH/CH
0.95 V2 (CH 0.5 Ag/TiO nanocomposites,
2O) 2[70]. When a methanol0.01 Ag/TiO
hole 2
nanocomposites
scavenger display
is employed, stronger toxicity,holes
the photogenerated withare
zonenotinhibition
immediately values of 38.4 and
consumed. 34.3 mm,
Instead,
the as shownradicals
hydroxyl by the radicalize
antifungalthe activity
CH3OH,data (Table
which 4). Reduced
results size andofthe
in the formation synergistic
e- [71].
interaction of 0.01 Ag/TiO2 nanocomposites resulted in an increased antifungal effect.
OH·+ CH3OH CH2OH·+ H2O
Table 4. Zones of inhibition for the antifungal activity of 0.01 Ag/TiO2 , 0.1 Ag/TiO2 , and 0.5 Ag/TiO2
nanocomposites were determined using the Agar Well cut diffusion method.
3.2. Antifungal Performance
0.01 Ag/TiO2, 0.1 Ag/TiO2, and 0.5 Ag/TiO2Performance
Antifungal nanocomposites were further tested for
their antifungal activity against Samples
Bacterial Strains S. macrospora and S.Blank
maydis using theZone
agarof well-diffusion
Inhibition (mm)
method and amphotericin B as0.01
S. macrospora a reference.
Ag/TiO2 An overview 0 of the findings is shown
38.4 in Table
4. When compared to 0.1 Ag/TiO 2 and 0.5
0.1 Ag/TiO2 Ag/TiO 2 nanocomposites,
0 0.01 Ag/TiO
30.6 2 nano-
composites display stronger toxicity, with
0.5 Ag/TiO2
zone inhibition
0
values of 38.4 and 34.3 mm, as
27.8
shown by the antifungal activity data (Table 4). Reduced size and the synergistic interac-
S. maydis 0.01 Ag/TiO2 0 34.3
tion of 0.01 Ag/TiO2 nanocomposites resulted in an increased antifungal effect.
0.1 Ag/TiO2 0 29.4
0.5antifungal
Table 4. Zones of inhibition for the Ag/TiO2 activity of 0.01Ag/TiO
0 27.20.5Ag/TiO2
2, 0.1Ag/TiO2, and

nanocomposites were determined using the Agar Well cut diffusion method.
4. Conclusions
Antifungal Performance
The Ag/TiO composites are synthesized by using the template induced method. For
Bacterial Strains 2 Samples Blank Zone of Inhibition (mm)
the crystallinity of the Ag/TiO2 composites, the XRD technique is used. In contrast, the
S. macrospora 0.01 Ag/TiO2 0 38.4
Ag/TiO2 composites’ morphology is determined using the SEM technique. EDS is used
for element detection. Moreover, the photocatalytic removal of MB and30.6
0.1 Ag/TiO 2 0 the photocatalytic
0.5 Ag/TiO 2 0 27.8
reduction of the Cr (VI) to Cr (III) are performed by using the Ag/TiO2 composites as
theS.catalysis.
maydis After performing
0.01 Ag/TiO
these
2 activities, it0 is concluded that 54%,
34.3 68%, and 90%
methylene blue is degraded by using the 0.5 Ag/TiO2 , 0.1 Ag/TiO2 ,and 0.01 Ag/TiO2
composites respectively. While 50%, 54%, and 75% Cr(III) is reduced to Cr(III) by using the
0.5 Ag/TiO2 , 0.1 Ag/TiO2 , and 0.01 Ag/TiO2 composites. The kinetics study shows that
degradation of methylene blue follows the first-order kinetics and reduction of Cr(VI) to
Cr(III) follows the pseudo first-order reaction. In both of these activities (photocatalytic
degradation of methylene blue and photocatalytic reduction of Cr(VI) to Cr(III)) the best
result is shown by 0.01 Ag/TiO2 composite after 150 and 50 min respectively of exposure
to sunlight.

Author Contributions: Methodology, M.A.; Software, A.R., S.H., H.A.I., F.F.A.-F. and E.B.E.; Val-
idation, M.J.; Formal analysis, Z.Z., A.A. (Adnan Amjad) and A.B.; Investigation, A.A. (Ahmad
Alhujaily) and S.H.; Resources, E.B.E.; Data curation, M.J.; Writing—original draft, A.R. and S.I.;
Writing—review & editing, N.S.A., H.A.I. and F.F.A.-F.; Visualization, M.A.; Supervision, S.I.; Project
administration, A.A. (Ahmad Alhujaily). The manuscript was written with the contributions of all
authors. All authors have read and agreed to the published version of the manuscript.
Funding: The authors extend their appreciation to the Deanship of Scientific Research at King
Khalid University for supporting this work through research groups program under grant number
Inorganics 2023, 11, 133 15 of 17

RGP.2/334/44. We are thankful to Higher Education Commission of Pakistan for funding my research
work under HEC funded project (No: 20-15745/NRPU/R&D/HEC/2021 2021). This research was
funded by Princess Nourah bint Abdulrahman University Researchers Supporting Project number
(PNURSP2023R156), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.
Data Availability Statement: The datasets generated during and/or analyzed during the current
study are available from the corresponding author upon reasonable request.
Acknowledgments: The authors extend their appreciation to the Deanship of Scientific Research
at King Khalid University for supporting this work through research groups program under grant
number RGP.2/334/44. We are thankful to Higher Education Commission of Pakistan for funding
my research work under HEC funded project (No: 20-15745/NRPU/R&D/HEC/2021 2021). This re-
search was funded by Princess Nourah bint Abdulrahman University Researchers Supporting Project
number (PNURSP2023R156), Princess Nourah bint Abdulrahman University, Riyadh, Saudi Arabia.
Conflicts of Interest: The authors declare no conflict of interest.

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