RESEARCH ARTICLE

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Nanostructured Composite of Starch/Silica Hybrid

Decorated with Titanium Oxide Nanoparticles for
Photocatalytic, Sonocatalytic, and Sonophotocatalytic
Emad Tolba, Mohamed S. Hasanin,* and Reda M. Abdelhameed

because of their harmful impacts on the en-

Nanocomposite-based heterostructure plays an important role in both vironment and living beings including hu-
industrial and advanced applications. A series of TiO2 nanoparticles decorated mans, animals, plants, and even microor-
on silica/starch hybrid material (TiO2(x) @SiO2(x) @Starch nanocomposites) is ganisms. In this sense, the pharmaceutical
synthesized using a facile sol–gel method. The intrinsic characteristics of the industry provides a large amount of wastew-
ater that needs highly ecient and proper
as-prepared nanocomposites are studied using a variety of techniques. In this
treatment.[1,2] Large quantities of drug com-
study, the degradation of paracetamol (PCT) is investigated in the presence of pounds are detected in wastewater, which
TiO2(x) @SiO2(x) @Starch nanocomposites. Photocatalysis and sonocatalysis aects the environment and human health
systems are used separately and simultaneously in presence of sunlight and greatly.[3] Paracetamol, an antipyretic, anal-
low-power ultrasound. The adsorption results are essential factor in the gesic, and anti-rheumatic drug, has caused
water pollution because of the accumula-
degradation process. The non-linear transform of the kinetics is further used
tion in the water environment.[4] Seriously,
to determine the characteristic parameters of TiO2(x) @SiO2(x) @Starch terrible phenomena happen, such as dam-
nanocomposites. The obtained results confirm that the experimental kinetic aging the blood system, cell necrosis, and
data follow the pseudo-first order model in photocatalytic, sonocatalytic, and degeneration. Paracetamol is an antibiotic
sonophotocatalytic processes but the rate constant of sonophotocatalysis is whose presence in aqueous environments,
higher than the sum of it at photocatalysis and sonocatalysis process. This even in trace concentrations, is unsafe for
living beings.[2,5]
work develops a new sono-photo active hybrid process for potential
Over the past years, numerous treat-
application in wastewater treatment. Additionally, the prepared TiO2 ment approaches have been reported to
nanoparticles with silica/starch hybrid material perform antimicrobial activity. remove PCT from wastewaters using pow-
The antimicrobial activity is increased parallel with the TiO2 percent. The erful oxidation processes including ozona-
broad-spectrum antimicrobial activity of nanocomposites is noticed at the tion, UV photolytic processes using per-
oxides or metal oxides and sonochemical
highest percentage of TiO2 in TiO2(0.8) @SiO2(0.2) @Starch.
methods. Today, the combined methods in-
cluding the coupling of photocatalysis and
ultrasounds are highly recommended to
provide more ecient ways to destroy PCT and even its degra-
1. Introduction dation products. Sonication induces physical and chemical
eects, such as promoting mass transfer and active radical forma-
Today, the extraction of contaminants from wastewater is posi- tion that can be harnessed for process intensication in numer-
tioned as a major worldwide concern because of overexploita- ous elds, including photocatalysis. Ultrasonic was used to boost
tion and irreversible climate change. Water contaminations by photocatalytic eciency (with enhancements up to 400%).[6] The
organic materials (i.e., dyes, aromatic compounds, and drugs) combination of sonication and photo reactions can boost photo-
and inorganic materials (mainly heavy metals), have attracted catalytic activity. This enhancement has some challenges that re-
the huge attention of both scientic and public communities, main to be addressed. The synthesis and design of non-precious

E. Tolba M. S. Hasanin
Polymers and Pigments Department Cellulose and Paper Department
National Research Centre National Research Centre
Cairo 12622, Egypt Dokki, Cairo 12622, Egypt
E-mail: [email protected]
R. M. Abdelhameed
Applied Organic Chemistry Department
Chemical Industries Research institute
The ORCID identication number(s) for the author(s) of this article
National Research Centre
can be found under https://doi.org/10.1002/star.202300203
Scopus aliation ID 60014618, 33 EL Buhouth St., Dokki, Giza 12622,
DOI: 10.1002/star.202300203 Egypt

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and ecient sonophotocatalyts by an environment-friendly tech- environmental systems due to their high photocatalytic activity,
nique are requisites for environmental remediation.[7] By regu- facile preparation, and limited toxicity.[23–27] Nevertheless, it is
lating the properties of materials, we try to overcome the exist- important to mention that their application is hindered by some
ing photocatalytic challenges in the photocatalytic treatment of limitations such as small surface area, agglomeration tendency,
wastewater, which are high rate of electron–hole recombination, and poor adsorption property.[26–29] Therefore, the purpose of this
wide bandgap, low activity in the presence of visible light, and work is to develop a novel hybrid material by the direct the forma-
instability of photocatalysts in process conditions.[8] tion and growth and of SiO2 and TiO2 metal oxides using starch
Khan et al.,[9] illustrate that the sonophoto activities mea- as a structure-directing agent, and evaluate their application in
sured at 40 kHz frequency demonstrated for silver/zinc oxide mi- photocatalytic, sonocatalytic, and sonophotocatalytic activities
crosphere exhibited 55-times improved sonophoto activities for in degrading paracetamol. Indeed, this novel insight provides a
acid red 17 (AR-17) degradation compared with virgin ZnO mi- safe and viable approach for the preparation of nanostructured
crosphere. These unprecedented sonophoto activities are cred- titania-silica hybrids using starch which has no environmental
ited to ultrasonic waves, rapid charge separation, and promoted risks associated with traditional surfactant-type templates. In
O2 activation.[7] Otherwise, Ali et al.[8] reported that Bi2 O3 –ZnO this study starch/silica and starch–silica hybrid modied with
photocatalysts with various amounts of copper phthalocyanine titanium oxide nanoparticles hybrid were synthesized by a
used as photosensitizer agent photocatalysts in sonophotocat- deposition–precipitation technique. The eects on the crystal
alytic degradation of methyl orange (MO). The results showed structure and morphology were investigated. The degradation
that the decomposition performance was in the following or- of drug contaminate (paracetamol) was used to investigate the
der: sonophotocatalysis (30 W ultrasonic power) photocataly- sonophotocatalytic activities of the prepared composites.
sis sonophotocatalysis (60 W ultrasonic power) sonolysis.[10] In addition to, antimicrobial activity of formulated materi-
In addition, carbon quantum dots dopped graphitic carbon als a plays an important role in a the materials performance
nitride used as a novel sonophotocatalyst for the degradation and usability in dierent applications.[30,31] SiO2 and TiO2
of diverse recalcitrant pollutants were evaluated using Tetra- are recorded an excellent antimicrobial activity with supposed
cycline (TC) antibiotic, where photocatalysis and sonocatalysis synergetic activity could be remarked. Indeed, this novel insight
showed 68% and 0.2% degradation in 120 min, respectively. provides a safe and viable approach for the preparation of
Remarkably, sonophotocatalysis exhibited 84% TC degradation nanostructured titania-silica hybrids using starch which has no
with a synergy index of 1.2 and complete degradation within environmental risks associated with traditional surfactant-type
180 min.[11] Sonophotocatalyst, graphene nanoribbon-cerium templates.[32,33] In this study starch/silica and starch–silica
oxide (GNR@CeO2 ) heterojunction, for the UV-light driven hybrid modied with titanium oxide nanoparticles hybrid were
sonophotocatalytic degradation of tetracycline hydrochloride synthesized by a deposition–precipitation technique. The eects
(TCH). The GNR, CeO2 and GNR@CeO2 heterojunction cat- on the crystal structure and morphology were investigated.
alyzed sonophotocatalytic modes recorded the highest TCH The degradation of drug contaminate (paracetamol) was used
removals with 72.9%, 68.3%, and 91.2% respectively in 120 min to investigate the sonophotocatalytic activities of the prepared
duration.[12] Additionally, the sonophotocatalytic performance composites.
of the FeVO4 /BiVO4 heterojunction catalyst was evaluated as
it is better than that of sonocatalysis and photocatalysis for the
degradation of levooxacin where it has good stability in the 2. Results and Discussion
degradation of levooxacin after ve cycles.[13]
Recently, there were more challenges persist due to limited 2.1. Characterizations
surface-active sites and poor electronic properties of common
materials. Besides, polysaccharides are a promising renewable Using the sol–gel synthesis method, it was possible to per-
for diverse applications and environmental related processes.[14] form hetero-condensation of silica and titania, in the pres-
Moreover, starch is one of the most functionalized biopolymers ence of starch as a matrix structure, to produce starch-silica-
belonging to polysaccharides.[15,16] titania multi-compartment hybrid nanoparticles. Figure 1 shows
In this context, silicate-based nanoparticles are promising TEM image of SiO2 @Starch, TiO2(0.2) @SiO2(0.8) @Starch and
nanostructured materials for the development of ecient cat- TiO2(0.8) @SiO2(0.2) @Starch NPs, as can be seen, the SiO2 @Starch
alytic materials and can be tailored to reveal a unique feature NPs, in fact, exhibit spherical shape with an average diame-
for a wide variety of technical and biomedical applications, ter of 945 μm and a standard deviation of 275 nm, whereas
mainly because of the availability, diversity, chemical stability, TiO2(0.2) @SiO2(0.8) @Starch NPs exhibit a spherical morphology
surface reactivity, ease functionalization, as well as excellent with an average diameter of 476 nm and a standard deviation of
biocompatibility.[15–19] Among them, mesoporous silica nanopar- 143 nm. On the other hand, TiO2(0.8) @SiO2(0.2) @Starch NPs ex-
ticles, which is a subclass of silicate-based material with a hibit irregular spherical morphology with an average diameter of
huge surface area, high porosity, and interconnected porous 196 nm and a standard deviation of 83 nm. The inserted SAED
structure,[18,20] have been used to enhance the catalytic perfor- images reveal a diraction pattern indicating the amorphous na-
mance of dierent metal oxide nanoparticles[19,21] including ture of prepared hybrid nanoparticles.
zinc oxide[20,22] and gallium oxide,[21,23] cobalt oxide.[22,24] In The phase identication was carried out using X-ray diraction
this sense, titanium dioxide nanoparticles, which are commer- and the results are shown in Figure 2. The XRD patterns of the as-
cially produced in large amounts for industrial products, have prepared samples showed no crystalline phases which reveal the
emerged as highly safe photoactive materials for biological and amorphous nature of silica and titania NPs.[34] The as-prepared

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Figure 1. TEM image of prepared starch-silica-titania hybrid NP: A) SiO2 @Stach, B) TiO2(0.2) @SiO2(0.8) @Starch, and C) TiO2(0.8) @SiO2(0.2) @Starch,
as well as selected area electron diraction (SAED) pattern, D) SiO2 @Stach, E) TiO2(0.2) @SiO2(0.8) @Starch, and F) TiO2(0.8) @SiO2(0.2) @Starch.

nanoparticles were also examined by SEM and EDAX and shown 2.1.1. Eect of Adsorption Process
in Figure 3. The SEM image indicates the presence of spherical
nanoparticles for all the samples, however, the SiO2 @Stach sam- To reveal the eect of the adsorption process on the re-
ple nanoparticles were highly dispersed. Titania modied sam- moval of paracetamol, adsorption experiments were con-
ples (TiO2 @SiO2 @Starch) were highly agglomerated and exhib- ducted at starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch,
ited nanosize diameter, as indicated by TEM measurements. Sur- and TiO2(0.8) @SiO2(0.2) @Starch composites at the dosage of
face chemical elements of the fabrics after and before treatment (1000 mg L−1 ). As shown in Figure 4, the content of paracetamol
were determined by EDX measurements. Figure 3A shows the was changed in the experiments with the addition of catalyst,
EDS spectra of the SiO2 @Stach NPs. A strong peak of Si at ca. indicating that the amount of paracetamol was reduced by
1.74 keV was related to the precipitated silica structure.[35] For 6.6%, 8.3%, 10%, and 12%, respectively, after 10 min.[36] While,
the titanium modied sample, a new peak appeared at ca. 5 keV after 60 min, the reductions were increased by 9.8%, 11.6%,
corresponding to titanium atoms (Figure 3B,C). 14.9%, and 18%, respectively. This may be because when the
catalyst is added to the paracetamol solution, the number of
active sites available for adsorption reaction increases and the
adsorption rate is accelerated. Moreover, a signicant amount of
paracetamol was adsorbed on the surface of starch, SiO2 @Stach,
TiO2(0.2) @SiO2(0.8) @Starch, and TiO2(0.8) @SiO2(0.2) @Starch
composites reached 50, 58, 74, 89 mg g−1 , respectively
(Table 1).

2.1.2. Eect of Sonocatalysis Process

The sonocatalytic investigations were performed in batch mode

using quartz beakers containing 100 mL of paracetamol and
100 mg starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch and
TiO2(0.8) @SiO2(0.2) @Starch composites catalyst. The reaction
mixture was initially stirred using a magnetic stirrer and kept
under dark conditions as investigated in the adsorption section
and subsequently subjected to ultrasound assisted sonocatalytic
degradation. Figure 5 shows the results of sonocatalytic degrada-
Figure 2. XRD patterns of as-prepared A) SiO2 @Stach, B) tion of paracetamol. After 10 minutes of insertion of mixtures in
TiO2(0.2) @SiO2(0.8) @Starch, and C) TiO2(0.8) @SiO2(0.2) @Starch. ultrasound, 10, 12.9, 15.2, and 17.2% reductions of paracetamol

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Figure 3. SEM and EDAX micrographs of A) SiO2 @Stach, B) TiO2(0.2) @SiO2(0.8) @Starch, and C) TiO2(0.8) @SiO2(0.2) @Starch.

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Figure 4. Eect of adsorption in the removal of paracetamol. A) Removal percentage, B) pseudo rst order tting, C) pseudo second order tting, and
D) comparison in the removal quantity of dierent composites for degradation of paracetamol.

appeared for starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch and 2.1.3. Eect of Photocatalysis Process
TiO2(0.8) @SiO2(0.2) @Starch composites, respectively. The maxi-
mum degradation observed under sonocatalytic conditions after Once the sonocatalytic process was found to be limiting in
60 min for starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch and terms of percentage removal, the photocatalysis was initiated
TiO2(0.8) @SiO2(0.2) @Starch composites were 15, 17, 22.5, 27%, under the irradiation of a UV source. For the photocataly-
respectively. The amount of paracetamol degraded upon ultra- sis, dierent starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch,
sound was 73, 87, 111, and 134 mg g−1 , for starch, SiO2 @Stach, and TiO2(0.8) @SiO2(0.2) @Starch composites catalysts were
TiO2(0.2) @SiO2(0.8) @Starch, and TiO2(0.8) @SiO2(0.2) @Starch used. Individually, the catalysts were applied to paracetamol
composites, respectively (Table 2). Here, the high degradation solution under UV irradiation and the degradation was mon-
with TiO2(0.8) @SiO2(0.2) @Starch composites may be due to itored spectrophotometrically. Interestingly, the percentage
the high electrical conductivity of TiO2(0.8) @SiO2(0.2) @Starch degradation of paracetamol in this mode was higher than
composites that delays recombination of •OH radicals.[37] in the sonocatalytic mode. Specically, starch, SiO2 @Stach,
The results of the sonocatalytic process indicate that the TiO2(0.2) @SiO2(0.8) @Starch and TiO2(0.8) @SiO2(0.2) @Starch com-
proposed sonocatalytic system could not eciently min- posites showed 12.6%, 19.8%, 28.1%, and 34.9% paracetamol
eralize the paracetamol under the explored experimental removal after 10 min of irradiation, whereas starch, SiO2 @Stach,
conditions. TiO2(0.2) @SiO2(0.8) @Starch, and TiO2(0.8) @SiO2(0.2) @Starch

Table 1. Kinetics parameters for the adsorption of paracetamol.

Sample Qe exp. [mg g-1 ] Pseudo-rst order Pseudo-second order

Qe [mg g−1 ] K1 [min−1 ] R2 2 Qe [mg g-1 ] K2 *10−4 R2 2

(L mg min)

Starch 50 48.45 ± 0.369 0.134 ± 0.004 0.996 0.692 54.91 ± 0.91 34.01 ± 3.37 0.993 1.377
SiO2 @Starch 58 83.45 ± 2.56 0.126 ± 0.017 0.951 32.363 94.89 ± 2.43 18.5 ± 2.77 0.985 9.312
TiO2(0.2) @SiO2(0.8) @Starch 74 72.77 ± 0.73 0.115 ± 0.005 0.995 2.454 84.01 ± 0.74 17.9 ± 0.85 0.998 0.746
TiO2(0.8) @SiO2(0.2) @Starch 89 56.55 ± 0.37 0.142 ± 0.004 0.997 0.772 63.69 ± 0.92 31.7 ± 2.85 0.995 1.502

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Figure 5. Sonocatalysis eect in the removal of paracetamol. A) Removal percentage, B) pseudo rst order tting, C) pseudo second order tting, and
D) comparison in the removal quantity of dierent composites for degradation of paracetamol.

composites accounted for 18%, 32.6%, 42.2%, and 48.8% lution (10 mg L−1 ) and 100 mg catalyst to simultaneous ul-
removal within 60 min (Figure 6). Table 3 showed the kinetic pa- trasound agitation (40 kHz, 27 °C) and UV irradiation. The
rameters of prepared compounds toward photolysis of paraceta- experimental paracetamol degradation data based on UV–
mol. The synergistic eect in TiO2(0.8) @SiO2(0.2) @Starch compos- visible spectroscopic measurements is shownin Figures 6
ite marks it as an ecient photocatalyst against paracetamol. The and 7. The data showed the highest paracetamol removal af-
high removal rate of paracetamol by TiO2(0.8) @SiO2(0.2) @Starch ter 60 min, the percentages of removal were 26%, 48%, 71%,
composite may be attributed to the small band gap of prepared and 96% when starch, SiO2 @Stach, TiO2(0.2) @SiO2(0.8) @Starch
materials. The limited degradation observed during photocat- and TiO2(0.8) @SiO2(0.2) @Starch composites were used, respec-
alytic mode is possibly due to the reduction in the active surface tively. The time evolution of sonophotocatalytic degrada-
area of the photocatalysts due to adsorption and accumulation tion of paracetamol in the presence of starch, SiO2 @Stach,
of intermediates and the products of degradation.[12] This limi- TiO2(0.2) @SiO2(0.8) @Starch, and TiO2(0.8) @SiO2(0.2) @Starch com-
tation can be overcome by combining the sonolysis process with posites were depicted as UV–visible spectrophotometric pro-
photocatalysis. le and is shown in Figure 7 and Table 4. The high degrada-
tion recorded under the sonophotocatalytic process in the pres-
2.1.4. Eect of Sonophotocatalysis Process ence of TiO2(0.8) @SiO2(0.2) @Starch composite is a combined ef-
fect of UV-irradiation with ultrasound.[38] The heterogeneous
The sonophotocatalytic degradation of paracetamol was inves- character of the semiconducting catalyst improved the acous-
tigated by subjecting a mixture of 100 mL paracetamol so- tic cavitations by catering to additional nuclei that hydrolyze

Table 2. Kinetics parameters for sonocatalysis in the removal of paracetamol.

Sample Qe exp. [mg g−1 ] Pseudo-rst order Pseudo-second order

Qe [mg g−1 ] K1 (min−1 ) R2 2 Qe [mg g−1 ] K2 × 10−4 R2 2

[L mg-1 min]

Starch 73 72.68 ± 0.54 0.134 ± 0.004 0.996 1.55 82.37 ± 1.37 22.6 ± 2.251 0.993 3.1
SiO2 @Starch 87 127.48 ± 3.07 0.106 ± 0.01 0.974 39.15 148.15 ± 2.34 9.22 ± 0.75 0.995 6.7
TiO2(0.2) @SiO2(0.8) @Starch 111 109.16 ± 1.103 0.115 ± 0.005 0.995 5.52 126.01 ± 1.11 11.9 ± 0.57 0.998 1.6
TiO2(0.8) @SiO2(0.2) @Starch 134 84.92 ± 0.606 0.142 ± 0.005 0.997 2.003 95.70 ± 1.361 21.1 ± 1.8 0.995 3.2

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Figure 6. Photocatalysis eect in the removal of paracetamol. A) Removal percentage, B) pseudo rst order tting, C) pseudo second order tting, and
D) comparison in the removal quantity of dierent composites for degradation of paracetamol.

H2 O molecules and lead to enhancedproduction of •OH rad- crobial activity against all tested microbial strains. The antimi-
icals under ultrasonic conditions. Explicitly, the low band gap crobial activity of nanocomposite TiO2(0.2) @SiO2(0.8) @Starch was
of TiO2(0.8) @SiO2(0.2) @Starch composite coupled with a high observed a moderate antimicrobial activity in comparison with
quantum eciency of UV-light and ultrasonic energy deemed it standard antibiotic and antifungal. Otherwise, the nanocompos-
more eective and ecient in degrading paracetamol in aqueous ite TiO2(0.8) @SiO2(0.2) @Starch showed high antimicrobial activ-
medium. ity with broad spectrum activity in comparison with another low
percentage sample as well as the standards. These observations
2.2. Antimicrobial Study could be referred to titanium oxide nanoparticles antimicrobial
activity which has action against ROS that can damage bacte-
The antimicrobial activity of the prepared samples with dif- rial proteins and DNA and cause bacterial membrane breakdown
ferent concentrations of TiO2 as well as the blank starch and and these take place in yeast cases as well.[39] Moreover, the sil-
SiO2 @Starch were studied via CFU methods against dier- icon oxide nanoparticles play an important role in synergetic
ent pathogenic microorganisms as tabulated in Table 5. The the titanium oxide nanoparticle antimicrobial activity this means
starch sample observed no antimicrobial activity against all tested that the quantum dote size has more eciency against microbial
strains. However, the SiO2 @Starch appeared to a weak antimi- cells.[40,41]

Table 3. Kinetics parameters for photocatalysis in the removal of paracetamol.

Sample Qe exp. [mg g−1 ] Pseudo-rst order Pseudo-second order

Qe [mg g−1 ] K1 [min−1 ] R2 2 Qe [mg g−1 ] K2 × 10−4 R2 2

[L mg−1 min−1 ]

Starch 92 87.22 ± 0.65 0.134 ± 0.004 0.999 2.2436 98.84 ± 1.64 18.9 ± 1.87 0.993 4.464
SiO2 @Starch 162 153.70 ± 3.41 0.102 ± 0.009 0.979 46.077 179.76 ± 2.38 7.135 ± 0.47 0.997 6.508
TiO2(0.2) @SiO2(0.8) @Starch 211 203.52 ± 2.25 0.116 ± 0.005 0.994 23.341 234.42 ± 1.86 6.54 ± 0.28 0.998 4.817
TiO2(0.8) @SiO2(0.2) @Starch 239 238.09 ± 1.76 0.138 ± 0.005 0.996 16.689 268.95 ± 4.08 7.23 ± 0.67 0.994 28.545

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Figure 7. Sonophotocatalysis eect in the removal of paracetamol. A) Removal percentage, B) pseudo rst order tting, C) pseudo second order tting,
and D) comparison in the removal quantity of dierent composites for degradation of paracetamol.

Table 4. Kinetics parameters for sonophotocatalysis in the removal of paracetamol.

Sample Qe exp. [mg g−1 ] Pseudo-rst order Pseudo-second order

Qe [mg g−1 ] K1 [min−1 ] R2 2 Qe [mg g−1 ] K2 × 10−4 R2 2

[L mg−1 min−1 ]

Starch 131 130.83 ± 0.98 0.134 ± 0.004 0.99695 5.04 148.27 ± 2.46 12.6 ± 1.25 0.993 10.04
SiO2 @Starch 241 230.93 ± 4.88 0.101 ± 0.008 0.98197 92.85 270.77 ± 3.15 4.63 ± 0.25 0.997 11.09
TiO2(0.2) @SiO2(0.8) @Starch 355 349.77 ± 2.113 0.104 ± 0.002 0.99851 18.13 410.25 ± 6.78 3.122 ± 0.26 0.995 52.73
TiO2(0.8) @SiO2(0.2) @Starch 488 476.95 ± 4.86 0.107 ± 0.004 0.99559 98.54 555.95 ± 10.02 2.41 ± 0.22 0.994 120.87

3. Conclusions TiO2 and SiO2 nanoparticles were randomly anchored onto the
starch. It was found that TiO2(0.8) @SiO2(0.2) @Starch compos-
TiO2(0.8) @SiO2(0.2) @Starch composite was prepared via a sim- ite has stronger light absorption in the visible light region, it
ple sol method, the SEM, TEM, and HR-TEM show that the exhibited enhanced photocatalytic, sonocatalytic, and sonopho-
tocatalytic activity in degrading paracetamol, which can be at-
tributed to enhancing the electron–holes separation at the hetero-
Table 5. Colony formation unit determination of tested sample. interface and the formation of more reactive radicals as well as
the increase of the active surface area. Whereas, the antimicrobial
Samples E. coli S. aureus C. albicans
was aected by the titanium oxide percentage where the highest
composite titanium oxide percentage was referred to as a broad
Starch 0a) 0 0
spectrum antimicrobial activity. Additionally, silicon dioxide was
SiO2 @Starch 21 ± 1.4 23 ± 2.1 21 ± 1.1 synergetic the titanium oxide antimicrobial activity.
TiO2(0.2) @SiO2(0.8) @Starch 49 ± 2.2 34 ± 1.9 41 ± 1.8
TiO2(0.8) @SiO2(0.2) @Starch 89 ± 3.2 93 ± 2.9 94 ± 3.1
Streptomycin (Antibacterial) 672 ± 1.5 56 ± 2.1 NAb) 4. Experimental Section
Griseofulvin (antifungal) NA NA 76 ± 2.2
a) b)
Commercial maize starch was purchased sigma Aldrich, sodium
antimicrobial activity %. This antibiotic does not apply to this strain. silicate (meta) nonahydrate extra (Na2 O3 Si∙9H2 O: 13517-24-3,

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Loba Chemie) and Titanium(IV) isopropoxide (Ti[OCH(CH3 )2 ]4 : 97%, 4.0.0.5. Statistical Analysis: Statistical analyses were performed using
546-68-9, Sigma-Aldrich) were used without purication. All reagents and Minitab software 21.2, 2022. All samples were carried out in a triplicate
microbial media were purchased from Loba Chem., India, in analytical and the recorded results were the main value.
grad ready to use.
4.0.0.1. Synthesis of Starch/Silica Hybrid Nanoparticles: Starch/Silica
hybrid and Starch–silica hybrid modied with titanium oxide nanoparticles Acknowledgements
were synthesized through the sol–gel method[42] For starch–silica hybrid,
50 mL aqueous solution of starch was prepared with a mass concentra- The authors acknowledge the National Research Centre, Egypt, for nan-
tion of 4% w/w distilled water at 90 °C. After 30 min, 4.7 g sodium silicate cial support of the research activities.
powder was added to the starch solution. The mixture temperature was
controlled at 60 °C. Then, a hydrochloric acid solution (3 M) was slowly
added to the starch/sodium silicate mixture until pH = 7 to accelerate Conflict of Interest
hydrolysis and condensation of sodium silica for amorphous silica precip-
The authors declare no conict of interest.
itation. The obtained starch–silica hybrid was collected via ltration and
washed with water three times and dried at 70 °C for 12 h in a drying oven.
Then, the obtained starch-silica hybrid was ground and stored at 4 °C in a
refrigerator until further characterization. Data Availability Statement
For starch–silica hybrid modied with titanium oxide, Titanium (IV) iso-
propoxide (Titania precursor) was introduced into starch/sodium silicate The data that support the ndings of this study are available on request
solution to the expected weight proportion of 10:5:1 or 10:1:5 for starch: from the corresponding author. The data are not publicly available due to
silica: titania. In brief, the calculated amount of titanium (IV) isopropoxide privacy or ethical restrictions.
solution was rst dissolved in 20 mL of ethanol and added drop by drop to
starch/sodium silicate solution. The starch–silica hybrid obtained colloidal
mixtures were stirred for 20 min at 60 °C and then hydrochloric acid solu- Keywords
tion (3 M) was added to reach pH = 7. The formed hybrids were collected,
washed, and dried as described before. The prepared starch/silica hybrid adsorption, antimicrobial, paracetamol, photocatalysis, sonocatalysis,
sample was named SiO2 @Stach, while the starch–silica hybrid modied sonophotocatalysis
with titanium oxide samples was named “TiO2(0.2) @SiO2(0.8) @Starch and
TiO2(0.8) @SiO2(0.2) @Starch composites.” Received: August 29, 2023
4.0.0.2. Characterizations of Prepared SSONPs: The particle morphol- Revised: December 13, 2023
ogy and size of the prepared nanoparticles were examined using eld Published online:
emission scanning electron microscopy (FE-SEM) coupled with energy
dispersive X-ray analysis; Model Quanta 250 FEG (Field Emission Gun)
and high-resolution transmission electron microscopy (HR-TEM) (JEM-
2100, Jeol, Japan). Fourier transformer infrared spectrophotometer (FTIR)
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