Ceramics International xxx (xxxx) xxx

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Comparative study on the photocatalytic efficiency of ZnO nanoparticles

synthesized via chemical and eco-friendly coprecipitation methods
Sonia Cherif a,*, Hynda Rezzaz-Yazid a , Sabra Hemidouche a,b, Asma Farsi a, Sarra Mostefaoui a ,
Mohamed Belmedani c , Hayet Djelal d, Zahra Sadaoui a
a
Laboratory of Reaction Engineering, Faculty of Mechanical Engineering and Process Engineering, USTHB, BP 32 Al Alia, 16111, Algiers, Algeria
b
Centre de Recherche Scientifique et Technique en Analyse Physico-Chimique (CRAPC), BP 384, Siège ex-Pasna Zone Industrielle, Bou-Ismail, CP, 42004, Tipaza,
Algeria
c
Laboratory of Transfer Phenomena, Faculty of Mechanical and Processes Engineering, USTHB, El Alia, BP n◦ 32, 16111, Algiers, Algeria
d
UniLaSalle Rennes-Ecole Des Métiers de L’Environnement, CYCLANN, Campus de Ker Lann, 35 170, Bruz, France

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

Handling Editor: Dr P. Vincenzini This study compares ZnO nanoparticles (NPs) synthesized via eco-friendly coprecipitation (ZnOE) using cactus
juice and chemical coprecipitation (ZnOC). XRD analysis confirmed the high purity of ZnOC with a crystallite size
Keywords: of 18 nm, while ZnOE consisted mainly of zincite (ZnO) with an amorphous organic phase and trace amounts of
Cactus juice albite (NaAlSi₃O₈) and calcite (CaCO₃), with a smaller crystallite size than ZnOC: 15 nm. FTIR spectroscopy
Eco-friendly synthesis
confirmed ZnO NPs formation in both methods and identified organic residues in ZnOE. The optical band gap of
ZnO nanoparticles
ZnO nanoparticles, calculated from the diffuse reflectance, was observed to be 3.2 eV for ZnOC and 3.14 eV for
photodegradation
phytotoxicity ZnOE, respectively. SEM and EDX analyses were conducted for further investigation.
Both ZnOE and ZnOC were applied to the photocatalytic degradation of Basic Yellow 28 textile dye (BY28)
under solar and artificial UV light. ZnOE exhibited superior photocatalytic performance in removing BY28
compared to ZnOC under both irradiation sources. Under optimal conditions (1 g L− 1 semiconductor, 10 mg/L
BY28), ZnOE showed superior degradation rates: 100 % and 94.71 % under solar and UV light, respectively (rate
constants: 0.0169 min⁻1 and 0.0127 min⁻1). ZnOC achieved 73.68 % and 42.61 % degradation under solar and
UV light (rate constants: 0.007 min⁻1 and 0.0037 min⁻1). The treated BY28 solution demonstrated improved
biodegradability and no phytotoxicity, indicating its environmental safety.

1. Introduction photocatalytic capacity allows for the transformation of contaminants

into simpler and less toxic molecules [7]. Metallic nanoparticles, such as
The intensification of human and industrial activities in recent de­ zinc oxide, have significant biological activity that can be applied in
cades has led to an alarming increase in environmental pollution, various fields such as food packaging, synthetic fabrics, wastewater
affecting waterways, soils, and ecosystems. Contaminants of concern treatment, dentistry, and medical equipment [8].
include pharmaceuticals, textile dyes, and discharges from the petro­ The synthesis of zinc oxide can be accomplished by various methods
leum industry [1–4]. Faced with this major challenge, it becomes [9–11], with two main approaches attracting our attention: classical
imperative to seek sustainable solutions for the treatment of contami­ chemical methods and alternative eco-friendly methods. While chemical
nated water. The goal is to develop effective technologies to eliminate methods are often effective, they pose environmental challenges due to
organic pollutants while minimizing the environmental impact of the use of harmful chemicals and energy-intensive processes.
treatment processes by reducing the use of harmful chemicals [5,6]. Conversely, eco-friendly methods using natural biomaterials, mainly
In this context, zinc oxide (ZnO) emerges as a promising material due plant leaves, fruit peels, bark, and flowers, offer a more environmentally
to its remarkable photocatalytic properties. Under the action of solar or friendly approach at a lower cost [12].
ultraviolet light, ZnO can decompose polluting organic molecules, of­ Scientific interest in the biosynthesis of zinc oxide nanomaterials has
fering an attractive alternative to traditional treatment methods. This grown significantly in recent years [13]. Many plant extracts are used in

* Corresponding author.
E-mail addresses: [email protected], [email protected] (S. Cherif).

https://doi.org/10.1016/j.ceramint.2024.11.448
Received 9 October 2024; Received in revised form 20 November 2024; Accepted 26 November 2024
Available online 28 November 2024
0272-8842/© 2024 Elsevier Ltd and Techna Group S.r.l. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

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S. Cherif et al. Ceramics International xxx (xxxx) xxx

the literature, such as extracts of orange peel, neem leaf, and cherry [12, 2.2. ZnO NPs synthesis
14,15]. Studies have revealed that plants rich in antioxidants, such as
phenolics, carbohydrates, saponins, tannins, and flavonoids, can act as 2.2.1. Chemical synthesis of ZnO NPs
powerful reducing agents when extracted in water [15–17]. It has been Temperature and pressure conditions were maintained at ambient
shown that ZnO nanoparticles (NPs) synthesized using plant extracts levels throughout this operation. The synthesis of ZnO nanoparticles
exhibit significantly stronger antibacterial activity compared to chemi­ commenced with the preparation of two solutions: a zinc acetate solu­
cally synthesized ZnO NPs, with a reduced risk of developing antibiotic tion by dissolving 20 g of zinc acetate in distilled water and a 5M NaOH
resistance [18]. Beyond being free of harmful chemicals, plant materials solution. A volume of 43 mL of NaOH was added dropwise to the zinc
themselves boast impressive properties, including anti-malarial, anti-­ acetate solution, resulting in precipitate formation. This NaOH volume
cancerous, and wound-healing effects, further amplifying the advan­ was determined based on the stoichiometry of the reaction (Eq. (1)):
tages of this eco-friendly synthesis approach [15].
Zn(CH3COO)2 + 2NaOH → Zn(OH)2 + 2CH3COONa (Eq.1)
In our study, we focus on the eco-friendly synthesis of zinc oxide
using cactus (Opuntia ficus-indica) juice. The reason for this choice is To precipitate 20 g of zinc acetate, twice the molar quantity of NaOH
based on several major advantages. Its resistance to arid environments (5M) was required, corresponding to a volume of 43 mL. The final pH of
and its abundant presence in many regions of Algeria make it a sus­ the solution was 13.15. The obtained product was washed multiple
tainable and plentiful source of raw material. Its skin is rich in minerals times with distilled water and dried at 80 ◦ C for 24 h using Memmert
like iron, calcium, magnesium, potassium, manganese, sodium, and se­ oven. The resulting powder was subsequently ground and calcined at
lenium. Additionally, its low cost and promising functional properties, 420 ◦ C for 3 h using a Nabertherm muffle furnace. A final wash with
including its reducing and coagulating properties due to mucilage, make distilled water was performed to eliminate any residual calcination
it attractive for large-scale applications [19,20]. The edible pulp is byproducts. The quantity of ZnOC recovered was 7,10 g.
packed with antioxidants, including biothiols, taurine, flavonols, to­
copherols, and carotenoids, which are known bio-reductants that 2.2.2. Synthesis of ZnO NPs via eco-friendly route
directly convert zinc ions into nanoparticles [21–23].
Phytochemical analysis of the fruit extract shows positive tests for 2.2.2.1. Preparation of Cactus Juice Extract. To prepare the cactus juice,
biomolecules such as alkaloids, terpenoids, glycosides, carbohydrates, the following protocol was applied: Cactus pads were harvested from a
saponins, tannins, steroids, and amino acids, which function as capping cactus field near the Douera Dam west of Algiers. They measured be­
and reducing agents. These biomolecules play a critical role in acceler­ tween 35 and 50 cm in length, 20 and 30 cm in width, and 3–4 cm in
ating the stabilization and reduction processes during nanoparticle thickness. After being freed from their thorns and rinsed, the pads were
formation [24,19]. cut into small cubes and blended. The mixture was then filtered through
The originality of this work, compared to existing studies on the a fine-pored cloth to remove solid particles. The resulting cactus juice,
green synthesis of zinc oxide (ZnO) using Opuntia ficus-indica (cactus) with a slightly acidic pH of 5.3, appeared cloudy with a greenish tint and
extract [23], lies in its comparative approach. This study assesses ZnO had a medium viscosity that gave it a gelatinous texture. It was stored at
synthesized via an eco-friendly, plant-based method against ZnO ob­ 4 ◦ C to preserve its properties. The steps of for preparing cactus juice
tained through conventional chemical coprecipitation. By analyzing the extract are shown in Fig. 2.
distinct properties of each material, we aim to highlight the specific
advantages of using cactus extract. Specifically, the photocatalytic per­
2.2.2.2. Preparation of ZnO NPs. In the eco-friendly synthesis of ZnO
formance of ZnO nanoparticles (NPs) synthesized by both methods is
nanoparticles, two solutions were prepared: 20 g of zinc acetate dis­
evaluated to determine which approach yields ZnO with superior effi­
solved in 200 ml of distilled water and 40 g of NaOH dissolved in 200 ml
ciency in degrading the textile dye Basic Yellow 28 (BY28).
of distilled water to obtain a 5M concentration. Unlike the conventional
chemical method, which requires 43 ml of NaOH, the eco-friendly
2. Materials and methods
method uses only 19 ml less than half the amount. The NaOH solution
was added dropwise to the zinc acetate solution using a burette. Sub­
2.1. Chemicals utilized
sequently, 200 ml of cactus juice were introduced to enhance ZnO
nanoparticle precipitation, and the mixture was stirred for 24 h.
Zinc acetate dihydrate (Zn(CH3COO)2⋅2H2O) obtained from PRO­
The resulting precipitate was then washed with distilled water to
LABO and sodium hydroxide (NaOH, 97 % pure) from SPECILAB were remove impurities, filtered, and dried at 80 ◦ C for 24 h in a Memmert
used as reagents in this Study.
oven. The dried product was ground to achieve a uniform particle size
Basic Yellow 28 is a cationic azo dye commonly used in the dyeing of and subsequently calcined at 420 ◦ C for 3 h using a Nabertherm muffle
cotton and polyacrylonitrile textiles due to its low cost. This extensive
furnace. A final wash and filtration were performed to eliminate residual
use makes it a prevalent contaminant in industrial wastewater [25,26]. impurities, yielding a total of 9.36 g of ZnO.
It was obtained from a local textile industry FITAL located in
In this eco-friendly method, a reduced amount of NaOH was used
Algiers-Algeria and used without purification. alongside cactus juice to ensure the complete conversion of zinc acetate
The BY28 dye has the following molecular structure (Fig. 1).
to zinc hydroxide. When cactus juice alone was used as the reducing
agent, the conversion remained partial, leaving unreacted zinc in the
solution. By including NaOH, we achieved full conversion, maximizing
zinc utilization and yield. This approach allowed us to recover approx­
imately 9 g of zinc oxide, slightly higher than the 7 g obtained via the
conventional coprecipitation method. The difference in mass may be
due to washing process variations: in the conventional method, nine
washes were required to adjust the pH from 12 to 7, while only two
washes were needed in the eco-friendly method to remove organic
residues.

Fig. 1. The molecular structure of the dye [27].

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S. Cherif et al. Ceramics International xxx (xxxx) xxx

Fig. 2. Preparation of cactus juice extract.

2.3. Catalyst characterization 2.5.2. Biochemical Oxygen Demand (BOD5)

Biochemical Oxygen Demand (BOD5) is a measure of the oxygen
The crystalline structure and phase composition of the ZnO films consumed by microorganisms to decompose organic matter in a water
were determined using X-ray diffraction (XRD) with a PANalytical sample over a five-day period at 20 ◦ C. This parameter serves as a key
EMPYREAN diffractometer (Cu Kα radiation, λ = 1,5418 Å). Fourier- indicator of organic pollution levels, as higher BOD values correlate with
transform infrared spectroscopy (FTIR) was performed on a BRUKER increased biodegradable organic matter.
spectrometer to identify the presence of hydroxyl groups and other To determine BOD5, a sample is introduced into an Oxitop device
impurities within the ZnO samples. The morphology and particle size containing a nutrient-rich medium, buffer, nitrate inhibitor, and acti­
distribution of the prepared powders were characterized using scanning vated sludge. The pH is adjusted to 7.0 ± 0.2 using Hanna HI22091-01
electron microscopy (SEM) with a Quanta 250 microscope. Energy- pH meter, and NaOH is added to the bottle cap. After incubation for five
dispersive X-ray spectroscopy (EDX) was performed using a SDD days in the dark, the oxygen consumption is measured and multiplied by
Bruker analyzer to determine the elemental composition of the samples. a dilution factor to calculate the final BOD5 value [29].
The UV–Visible spectra of the samples were recorded using spectro­
photometer (UV–Vis DRS, Specord 210 PL) in reflectance mode in a 2.5.3. Phytotoxicity assessment on watercress seed
wavelength range of 250–800 nm. A phytotoxicity assessment was conducted using watercress seeds
(Caillard). Ten Petri dishes were prepared, each containing ten water­
2.4. Photocatalytic activity cress seeds moistened with 5 mL of the sample solution. A control group
of Petri dishes was prepared similarly using tap water. All Petri dishes
The photocatalytic activity of the prepared materials was evaluated were incubated at 25 ◦ C for 48 h. The Germination Index (GI) was
using Basic Yellow 28 textile dye under both solar irradiation in June calculated as a ratio of the seed germination and average root length in
and UV light to compare their performance. UV irradiation was provided the sample to those in the control, expressed as a percentage (Eq. (3))
by Philips lamps emitting UV-A radiation at 365 nm with a power of 36 [30].
W. Initially, photolysis experiments were performed in the absence of a (
seed germination (%) × average root length of the sample
)
catalyst under both solar and UV conditions to assess the dye’s suscep­ GI (%) = *100
seed germination (%) × average root length of the control
tibility to direct photodegradation. Subsequently, the adsorption ca­
(Eq. 3)
pacity of the synthesized materials was determined in the dark until
equilibrium was reached. The same solutions were then subjected to This formula provides a quantitative measure of the sample’s po­
both solar and UV irradiation. To optimize degradation efficiency, the tential phytotoxic effects on seed germination and early seedling
effects of catalyst mass and dye concentration was investigated. Under growth.
optimal conditions, degradation kinetics were studied by collecting
samples at regular intervals and analyzing them using a UV–Visible 3. Results and discussion
spectrophotometer (OPTIZEN 2120UV). The degradation yield for each
experiment was calculated using Equation (2): 3.1. Characterization of synthesized materials
( )
C0 − Cf
Degradation yield (%) = × 100 (Eq. 2) 3.1.1. X-ray diffraction (XRD) and Fourier transform infrared spectroscopy
C0
(FTIR)
X-ray diffraction (XRD) was used to determine the crystal structure,
where C₀ is the initial dye concentration and Cf is the final concentration.
phase composition, and average crystallite size of the synthesized ZnO
materials. Particle size, morphology, and surface defects are crucial
2.5. Analytical methods
factors influencing a photocatalyst’s activity. Nano-sized ZnO provides
an increased number of active sites for dye adsorption and facilitates
2.5.1. Chemical oxygen demand (COD)
mass transfer during the photocatalytic process. Oxygen vacancies
Initially, 2 mL of each sample was added to COD tubes containing a
within the ZnO lattice can act as electron traps, promoting charge sep­
specified amount of Ag2SO4/H2SO4/K2Cr2O7 reagent for the 0–40 mg/L
aration and enhancing photocatalytic efficiency.
range. The tubes were then placed in a digester set to 150 ◦ C for 120 min
In order to study the crystallinity of the prepared ZnO NPs,
to ensure complete oxidation of organic matter. After cooling the vials to
Figure (3a) presents the XRD spectra of the synthesized samples:
room temperature for approximately 15 min, the digested samples were
Chemically synthesized ZnO (ZnOC) and Eco-friendly ZnO (ZnOE). The
analyzed using a Hanna HI93754A-25 GB COD spectrophotometer to
diffractograms, obtained using an X-ray diffractometer, were inter­
determine COD values, which represent the concentration of organic
preted. The positions and intensities of the observed peaks were
matter in each sample [28].

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Fig. 3. (a): XRD spectrum of ZnO nanoparticles, (b): FTIR spectra of the prepared samples, (d) direct optical transitions of ZnO samples.

compared to the PDF-2 and ICSD (Powder Diffraction File - Inorganic creates a unique chemical environment that promotes the formation of
Crystal Structure Database) reference files to identify the mineralogical calcite and albite. The minerals provide essential ions needed for min­
phases present. All the diffraction peaks of the two synthesized materials eral formation, while the organic compounds may stabilize these ions in
can be indexed to the ZnO (Wurtzite) structure (Fig. 3a). The ZnOC peaks solution, enhancing their availability and influencing crystallization
at 2θ = 31◦ , 34◦ , 47◦ , 56◦ , 62◦ , 66◦ , 67◦ , 68◦ and 74◦ were assigned to processes.
the (100), (002), (101), (102), (110), (103), (200), (112) and (201) The ZnOC sample is composed of zincite. XRD analysis was used to
planes, respectively. No impurities were detected in this ZnOC sample. calculate the crystallite size of the catalysts. The Scherrer equation,
The peaks in ZnOC are more intense than ZnOE indicating the high purity widely used for such calculations [31], which relates the average crys­
of this sample. tallite size of the particles to the width of a peak in the diffraction pattern
As for the ZnOE sample, mineralogical analysis by X-ray diffrac­ (Eq. (4)):
tometry revealed the presence of the following phases (Fig. 3a): an Crystallite size calculations using the Scherrer equation yielded
amorphous organic phase likely originating from cactus juice, Zincite values of 18.70 nm and 15.16 nm for ZnOC and ZnOE, respectively.
(ZnO), Albite (AlNaO8Si3), and Calcite (CaCO3). These small crystallite sizes indicate a nanocrystalline structure with a
Following these analyses, it can be concluded that the ZnO sample is potentially large specific surface area. The obtained crystallite size (D)
composed mainly of zincite, with incidental presence of albite and trace values are smaller than those reported in the literature [32–34].
amounts of calcite. As we mentioned in the introduction, cactus juice is Limited literature compares chemically and eco-friendly synthesized
rich in minerals such as iron, calcium, magnesium, potassium, manga­ zinc oxide (ZnO). Maijan et al. (2024) synthesized ZnO using two
nese, sodium, and selenium, as well as organic biomolecules including methods: a chemical approach with NaOH (ZnO-NaOH) and an eco-
alkaloids, terpenoids, glycosides, carbohydrates, saponins, tannins, ste­ friendly method employing NaOH and para rubber leaf extract (ZnO-
roids, and amino acids. Extract/NaOH). XRD analysis indicated a smaller crystallite size for
ZnO-Extract/NaOH (40 nm) compared to ZnO-NaOH (69 nm) [32].
• Calcite (CaCO₃): This mineral can form from calcium ions present in Benitez-Salazar et al. (2021) synthesized ZnO nanoparticles (NPs)
cactus juice, which contribute to its formation when carbonate ions using both a chemical (polymeric complex) and a green (controlled
are available. These carbonate ions can often be sourced from precipitation) method. The green method employed garlic (Allium sat­
organic compounds or dissolved CO₂ in the solution. ivum) and chili (Capsicum annuum) suspensions as solvents, and NaOH as
• Albite (NaAlSi₃O₈): Sodium from cactus juice can participate in a reducing agent. XRD analysis revealed a pure ZnO phase with a 33.20
forming albite (NaAlSi₃O₈). If silica is present in the solution, sodium nm crystallite size for the chemically synthesized NPs. In contrast, the
can combine with it and aluminum (which may also be present) to green method using chili pepper extract yielded an amorphous phase
form albite. with incipient peaks suggesting the presence of basic zinc acetate and
zinc acetate with ammonia. ZnO NPs synthesized using garlic extract
The combination of organic compounds and minerals in cactus juice were also amorphous and containing no other crystalline phases [34].

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D = 0.9λ /βcos (Eq. 4) biomolecules that may act as capping or stabilizing agents [39]. Plant
extracts and other biological components commonly used in green
Where: D is the crystallite size of the catalyst, λ is the wavelength of the synthesis can leave behind organic contaminants identifiable through
X-rays which is equal to 1.5418 (Å), β is the full width at half maximum FTIR analysis [18].
(FWHM) of the most intense peak (rad), and θ is the diffraction angle of Our findings align with the observations of Alia et al. (2016), which
the peak (Bragg angle). highlight the critical role of proteins in the synthesis and stabilization of
The FTIR analysis reveals that both synthesis methods exhibit the ZnO nanoparticles (NPs). Proteins are known to form a protective
presence of Zn-O stretching vibrations (555 cm⁻1/485 cm⁻1 in ZnOE, and corona around NPs, enhancing their dispersibility and preventing ag­
565 cm⁻1/486 cm⁻1/in ZnOC), confirming the formation of ZnO nano­ gregation in aqueous environments. The interaction between the free
particles (Fig. 3b) [35–37]. amino and carboxylic groups of proteins and the zinc oxide surface
The FTIR spectrum of ZnOC displays a peak at 2165 cm⁻1, which may further contributes to the stability of ZnO NPs [40]. The peak at 781
correspond to C ≡ C or C ≡ N stretching vibrations, suggesting residual cm⁻1 could be attributed to out-of-plane C-H bending vibrations in ar­
organic compounds or unreacted precursors. Additionally, a peak at omatic compounds [41].
1601 cm⁻1 is observed, likely associated with O–H bending vibrations, The band gap energy of the nanoparticles was calculated using Tauc
potentially from adsorbed water or hydroxyl groups on the ZnO surface, plot method, as outlined in previous studies [42,43]. The band gap
which can remain from the NaOH environment in the coprecipitation represents the energy difference between the valence band (VB) and the
process [38]. conduction band (CB) of a material, defining its ability to absorb and
The eco-friendly method (ZnOE) shows peaks at 1619 cm⁻1, 1412 emit light, which is critical for its optical and electronic properties [44].
cm⁻1, 1314 cm⁻1, and 1034cm⁻1 related to organic compounds such as The Tauc plot was generated using the following equation:
carbohydrates, polysaccharides, and proteins, likely correspond to C=O (αhν)1/n = A(hν− Eg)
stretching, C-H bending, and C-O stretching vibrations. These peaks
might originate from cactus juice, indicating the presence of where αis the absorption coefficient, A is the proportionality constant,

Fig. 4. SEM images of ZnOE (a and b) and ZnOC (c and d), Elemental composition spectra of ZnOE (e) and ZnOC (f).

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hν is the incident light frequency, and Eg represents the band gap en­ and other cations can enhance photocatalytic activity by modifying the
ergy. The transition type is determined by the exponent ’n’: n = ½ for material’s band structure, creating defect sites, and facilitating charge
direct transitions and n = 2 for indirect transitions. For ZnO, a direct carrier separation [52–54]. Consequently, incorporating calcium into
transition was identified by extrapolating the linear region of the curve the ZnO structure during synthesis is expected to improve its perfor­
to the hv axis [45] (Fig. 3c). mance in pollutant degradation.
The calculated band gap energies for ZnOC and ZnOE were 3.2 eV
and 3.14 eV, respectively. ZnOE exhibited the lower band gap, which 3.2. Evaluation of the photocatalytic performances of the synthesized
may enhance its photocatalytic efficiency for the degradation of BY28 materials
dye.
3.2.1. Photocatalytic activity of the synthesized NPs
3.1.2. Scanning electron microscopy (SEM) and energy dispersive X-ray In order to evaluate the adsorption, photoactivity and direct
spectroscopy (EDX) photolysis capacities of BY28 by the synthesized ZnO nanoparticles,
Scanning Electron Microscopy (SEM) was used to examine the three series of experiments were carried out under solar light, as pre­
morphology of the ZnO samples. The obtained micrographs reveal sented in Fig. 5.
distinct morphologies for ZnOE and ZnOC. ZnOE exhibits an irregular, Adsorption in the Dark: ZnO nanoparticles were contacted with a
flaky structure with noticeable particle agglomeration (Fig. 4a and b). In solution of BY28 (10 mg L− 1) in the dark for 60 min. The adsorption rate
contrast, ZnOC displays a more spherical particle morphology with of BY28 on ZnO NPs did not exceed 6.11 % for ZnOE and 4 % for ZnOC,
agglomerated clusters (Fig. 4c and d). indicating a low affinity between BY28 and the surface of the
An analysis of studies in the literature reveals that zinc oxide derived nanoparticles.
from plant sources can exhibit diverse morphologies, comparable to Photolysis of BY28 under UV irradiation: The solution of BY28 (10
those produced by conventional chemical methods [12,46,47]. These mg L− 1) was exposed to sunlight for 90 min. The degradation rate of
morphological variations are significant because they can influence the BY28 by direct photolysis did not exceed 2.9 %, suggesting a high sta­
photocatalytic degradation efficiency, as highlighted by Weerathunga bility of this molecule.
et al. (2022) [48]. Several studies have reported that the catalyst’s Photocatalysis: The solution of BY28 (10 mg L− 1) previously con­
performance strongly depends on its morphology. Nano-flakes, in tacted with ZnO nanoparticles in the dark was exposed to solar radiation
particular, provide a larger surface area, enhancing junction formation for 1 h and 30 min. ZnOC and ZnOE nanoparticles showed high photo­
and improving photocatalytic performance [49]. activity for the degradation of BY28 under solar irradiation. The
It’s important to note that the specific morphology of ZnO nano­ degradation efficiencies of BY28 were 49.86 % for ZnOC and 65.15 % for
particles is significantly influenced by various synthesis parameters, ZnOE. ZnOE exhibited the best degradation efficiency among the two
including plant extracts, concentration, temperature, pH, and calcina­ synthesized materials.
tion time [50].
EDX analysis was performed to determine the elemental composition 3.2.2. Effect of catalyst mass
of the ZnO samples. Dispersive spectra were generated to identify and The catalyst concentration is a very important parameter, especially
quantify the elements present in the samples. The results are presented for systems where the catalyst is in suspension. It must be sufficient to
in Fig. 4. adsorb a maximum amount of pollutants, without being excessive to the
EDX analysis of the ZnOC sample reveals distinct peaks with atomic point of reducing the transparency of the solution to radiation. An
percentages of 54.06 % for zinc and 45.95 % for oxygen, without optimal balance is necessary for each situation [47].
detection of contaminants. This observation confirms the high purity of The effect of the mass of the two prepared catalysts was tested in a
the NPs synthesized by the chemical co-precipitation method. range of 0.25–1 g L− 1. (Fig. 6).
In contrast, EDX analysis of the ZnOE sample highlights the presence Fig. 6 shows that the photocatalytic activity of ZnOE is higher than
of trace amounts of calcium (2.105 % atomic percentage), in addition to that of ZnOC for both irradiation sources. We also observe that solar
zinc (45.40 %) and oxygen (52.48 %). The calcium is believed to orig­ radiation is more effective than UV radiation from the lamp in degrading
inate from the biological compounds present in the cactus. It is plausible the target pollutant. The analysis of the effect of the catalyst mass in­
to suggest that calcium ions were doped into the ZnO matrix by cactus dicates that the degradation efficiency increases with the increase in the
juice.
Zinc oxide nanoparticles synthesized using plant extracts often
contain trace impurities. A previous study by Sadiq et al. (2021) re­
ported the synthesis of ZnO nanoparticles from Syzygium cumini leaf
extract. EDX analysis of these biosynthesized nanoparticles revealed the
presence of carbon (23.11 %), zinc (65.43 %), oxygen (9.82 %), and
aluminum (1.64 %) - elements originating from the leaf compounds
employed in the synthesis [47].
Brishti et al. (2023) synthesized ZnO nanoparticles (NPs) using an
extract from Epipremnum aureum leaves as a stabilizing agent and zinc
acetate dihydrate as a precursor. Energy-dispersive X-ray spectroscopy
(EDS) analysis of the NPs indicated a composition of 57.95 % zinc,
23.29 % oxygen, 14.91 % carbon, 2.80 % nitrogen, and 1.04 % sulfur
[15].
In a study conducted by Davar et al. (2015), zinc oxide (ZnO)
nanoparticles were synthesized using lemon juice as a reducing and
stabilizing agent, with zinc acetate as the zinc precursor. Energy-
dispersive X-ray spectroscopy (EDX) analysis confirmed the primary
composition of the nanoparticles as zinc and oxygen. The presence of
carbon, magnesium, and calcium impurities in the EDX spectra was
attributed to residual components from the lemon juice [51]. Fig. 5. Degradation efficiency of catalysts under solar light (C0 = 10 mg.L− 1,
Previous studies have demonstrated that doping ZnO with calcium pH = 6.75 CZnO = 0.5 mg L− 1, UV index = 8/11, time = 90min).

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Fig. 6. Effect of catalyst mass on the degradation efficiency of BY28 (a): Solar irradiation (pH = 6.85, C0 = 10 mg L− 1, UV index = 9/11, time = 90min), (b): UV r
irradiation (pH = 6.85, C0 = 10 mg L− 1, UV-A, time = 90min).

catalyst mass for both synthesized materials. The optimal mass of the 3.2.3. Effect of BY28 concentration
ZnO semiconductor is 1 g L− 1 for both types of catalysts and for both The initial concentration of the dye is a key variable to examine, as it
radiation sources. At this mass, the degradation efficiencies were 93.78 strongly impacts the results of photocatalysis. By optimizing this con­
% under UV radiation and 100 % under solar radiation for ZnOE. For centration, the efficiency of the process can be improved and the
ZnOC, the degradation efficiencies were 60.04 % under UV radiation and degradation of pollutants can be maximized.
86.69 % under solar radiation. We studied the effect of the concentration of BY28 in the of range
While ZnO NPs are known to have a band gap of about 3.2 eV, which from 10 to 100 mg L− 1, the degradation efficiencies obtained are shown
primarily facilitates their photocatalytic activity under UV irradiation, in Fig. 7.
our experiments revealed better photocatalytic performance under solar The results showus an inverse correlation between the initial con­
light. This phenomenon can be attributed mainly to the intensity of solar centration of the dye and the degradation efficiency, regardless of the
irradiance. In Algeria, the intensity of solar irradiance during June is type of solar irradiation, UV lamp, or the catalyst used ZnOE and ZnOC.
typically high, often exceeding 800–1000 W/m2 [55], which signifi­ The optimum concentration was 10 mg L− 1. The degradation efficiencies
cantly enhances the photocatalytic process by providing more total en­ recorded for a concentration of 30 mg L− 1 were 77.11 % under solar
ergy than the 0.935 W/cm2 emitted by the UV lamp. irradiation and 67.68 % under UV lamp for ZnOE, surpassing ZnOC,
Mousavi et al. (2015) studied the effect of ZnO mass on the degra­ which reached 73.68 % under solar irradiation and 40.74 % under UV
dation of Congo Red dye, in the range of 0.1–0.5 g L− 1. They found that lamp.
the degradation efficiency increased with the catalyst dose, due to better At higher concentrations of 50, 70 and 100 mg L− 1, the photo­
accessibility of the active sites on the catalyst surface, an increase in the degradation efficiencies decrease for both types of catalysts with the
number of adsorbed photons, as well as the increase in the number of increase in the initial concentration of the dye. ZnOE maintains a su­
adsorbed dye molecules [56]. perior performance compared to ZnOC. Solar irradiation yields better
results compared to UV radiation.

Fig. 7. Effect of BY28 concentration on degradation efficiency (a): Solar irradiation (CZnO = 1 g L− 1, UV index = 9/11, time = 90min), (b): UV irradiation (CZnO = 1
g L− 1, UV-A, time = 90min).

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S. Cherif et al. Ceramics International xxx (xxxx) xxx

This behavior is explained by the fact that as the initial concentration 180 min under natural irradiation. This proves that the textile dye
increases, more organic substances are adsorbed onto the ZnO surface. studied is a very stable molecule, and solar/UV irradiation alone is not
This leads to a reduction in the generation of hydroxyl radicals, as the enough to decompose it (Fig. 8).
number of active sites available for the adsorption of hydroxyl ions and From the results obtained, we observed that degradation occurred
the formation of hydroxyl radicals is limited. In addition, at higher dye more rapidly under solar radiation compared to the UV irradiation from
concentrations, photons are intercepted before reaching the catalyst the lamp was observed during the study of the decomposition kinetics of
surface, which reduces the photon absorption by the catalyst. As a result, BY28. ZnOE proved to be more efficient than ZnOC under both radiation
the formation of hydroxyl radicals is decreased, leading to a reduction in conditions.
the degradation percentage [32]. During the initial phase of the experiment, the adsorption equilib­
Our results are consistent with those reported in the literature, as rium shows negligible degradation efficiencies of BY28: of3% for ZnOE
shown in the works of Pavithra et al. (2017) and Chemingui et al. and 2 % for ZnOC after 60 min. The photocatalysis process under UV
(2019). irradiation reveals a degradation efficiency of BY28 of 94.71 % for ZnOE
Pavithra et al. (2017) investigated the photocatalytic degradation of and 42.61 % for ZnOC. Under solar radiation, the degradation efficiency
Methylene Blue (MB) dye using ZnO nanoparticles synthesized from of JB 28 with ZnOE reaches 100 %, while that with ZnOC is 73.68 %.
Citrus maxima (Pomelo) juice under UV irradiation. The study examined These results highlight the superior efficiency of ZnOE compared to
MB concentrations ranging from 5 to mg.L− 1. Results revealed that the ZnOC in the photocatalytic degradation of BY28, both under sunlight
percentage of MB degradation decreased with increasing initial con­ and UV irradiation, with significantly higher degradation efficiencies.
centration. This phenomenon can be attributed to reduced light pene­ The data presented in Fig. 9 visually confirm the conclusions of the
tration and competition between MB molecules for active sites on the kinetic study.
ZnO surface at higher concentrations. Consequently, the degradation The rate constant of the BY28 degradation was determined from the
efficiency of ZnO nanoparticles diminishes in more concentrated solu­ first-order kinetic equation (Eq. (5)): Ln(C/C₀) = -kt (Eq. (5)).
tions due to increased light absorption. The photocatalytic rate constants (k) for ZnOC and ZnOE were
According to the study by Chemingui et al. (2019), the photo­ determined under both solar and lamp irradiation: kaC = 0.007 min⁻1,
catalytic activity of ZnO biosynthesized from Laurus nobilis (noble bay) kaE = 0.0169 min⁻1 under solar radiation; kbC = 0.0037 min⁻1, kbE =
leaves with zinc nitrate as the precursor was evaluated for the degra­ 0.0127 min⁻1 under lamp irradiation. These results indicate that ZnOE
dation of Remazol Brilliant Red F3B (Reactive Red 180) dye. An exhibited a faster photocatalytic degradation rate than ZnOC under both
experiment was conducted by keeping the catalyst amount constant (0.5 experimental conditions.
g L− 1) and varying the dye concentration from 50 mg L− 1 to 150 mg L− 1 Our results are in agreement with those reported in the literature
to study its influence on the degradation efficiency. The results indicate (Table 1):
that at the end of the process, all experiments, except the one with 150 Table 1 demonstrates that the efficiency of dye photodegradation is
mg L− 1 (where the efficiency was 61.81 %), achieved close to 100 % influenced by various experimental parameters, including the precursor
color removal, with faster degradation observed for the lowest concen­ and plant employed in catalyst synthesis, catalyst loading, initial
tration (50 mg L− 1). These results suggest that the degradation of the dye pollutant concentration, type of irradiation, and reaction time.
is concentration-dependent [57]. As TiO₂ is widely regarded as one of the most effective photo­
catalysts, the photocatalytic performance of ZnO obtained in this study
3.2.4. Degradation kinetics is comparable to that reported by Singh et al.(2020), where a photo­
The degradation kinetics of BY28 were studied under optimal con­ degradation rate constant of 0.05984 min⁻1 was achieved for methylene
ditions (CZnO = 1 g L− 1, C0 = 10 mg L− 1) to examine the evolution of blue dye removal within 80 min using Cu-doped TiO₂. This comparison
residual concentrations of BY28 and to determine the rate constants of highlights ZnO’s competitive efficiency as a photocatalyst, even against
the reactions involved. The results obtained are presented in Fig. 8. optimized TiO₂-based systems [38].
We note that the photolysis of BY28 under both irradiation sources Photodegradation of dyes using semiconductors as catalysts involves
shows negligible degradation, with an efficiency not exceeding 5 % after the absorption of UV light energy, which excites electrons from the

Fig. 8. Photodegradation of BY28 as a function of time (a): Solar irradiation (CZnO = 1g.L− 1, C0 = 10 mg L− 1, pH = 6.60, UV index 9/11), (b): UV irradiation (CZnO =
1g.L− 1, C0 = 10 mg L− 1, pH = 6.60, UV-A).

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S. Cherif et al. Ceramics International xxx (xxxx) xxx

Fig. 9. Photographs showing the color change of BY28 solution before and after photocatalysis. (For interpretation of the references to color in this figure legend, the
reader is referred to the Web version of this article.)

Table 1
Photocatalytic degradation of organic dyes using ZnO nanoparticles synthesized from plant extracts under different experimental conditions.
Precursor Mediated plant Pollutant Dose of Irradiation Time Degradation Kinetic rate Reference
catalyst source (min) yield (%) (min− 1)

Zinc nitrate Ocimum gratissimum aqueous Rhodamine B Not Sunlight 120 Not mentionned Not [35]
extract mentionned irradiation mentionned
zinc acetate para rubber leaf extract and methylene blue (5 mg. 1000 mg L− 1 sunlight 300 90.6 % 0.0072 [32]
dihydrate wood ash extract L− 1)
− 1
Zinc Nitrate Averrhoe carrambola fruit Congo red (100 mg 500 mg L UV 180 93.0 0.002 [58]
extract + NaOH L− 1)
zinc acetate lemon extract Methylene Blue (31.98 100 mg UV 70 91.17 Not [59]
mg L− 1) mentionned
Congo Red (67.16 mg. 100 mg UV 35 90 Not
L-1) mentionned
Rhodamine B (4.790 100 mg UV 50 98 Not
mg.L-1) mentionned
− 1
zinc acetate extract of sorghum seed Methylene Blue (10 1000 mg L Sunlight 40 99.99 0.1348 [60]
dihydrate (Sorghum bicolor L. Moench) mg L− 1) irradiation
1
zinc acetate Senna siamea leaf extract reactive red 141 (10 250 mg L− Sunlight 40 100 0.081 [61]
dihydrate mg L− 1) irradiation
1
. Zinc nitrate Commelina beghalensis plant methylene blue (20 300 mg L− UV light 120 81 Not [62]
extract mg L− 1) irradiation mentionned
− 1
Zinc nitrate aqueous extract of Garcinia malachite green 1000 mg L sunlight 180 99 0.0245 [63]
hexahydrate ( mangostana fruit pericarp
1
Zinc nitrate leaf, stem and callus aqueous methylene blue (5 mg 200 mg L− UV light 120 90 Not [64]
hexahydrate extracts of Mussaenda frondosa L− 1) mentionned
1
Zinc acetate leaf, extract Moringa Oleifera titan yellow 1000 mg L− sunlight 60 96 Not [65]
dihydrate (83.47 mg L− 1) mentionned
− 1
zinc nitrate extract of h dried fruit Amomum methylene blue (15.99 1000 mg L UV light 60 66 0.014 [66]
hexahydrate longiligulare mg L− 1)
− 1
malachite green 1000 mg L UV light 60 31.1 0.008
(18.25 mg L− 1)
1
zinc nitrate seed extract of Moringa oleifera methylene blue (50 200 mg L− UV light 1440 71 Not [67]
hexahydrate mg L− 1) mentionned
1
Zinc nitrate seed extract of Lupinus albus L malachite green (30 75 mg L− visible 42 98 0.09 [68]
dihydrate mg L− 1) radiation
− 1
Without plant extract malachite green (30 75 mg L visible 42 89 0.04
mg L− 1) radiation
zinc acetate Cucumis maderaspatanus extract Coomassie Brilliant Not UV light 60 100 Not [69]
dihydrate Blue R-250 (50 mg mentionned mentionned
L− 1)

valence band to the conduction band, leaving behind holes. These holes
and electrons can then initiate oxidative reactions, such as the genera­ ZnO + hν → ZnO + e− + h+ () Eq. 6
tion of hydroxyl radicals (OH•), which can degrade contaminants. The
details of the mechanism can be summarized as displayed below [61, e− + O2 → O•−2 (Eq. 7)
64]:

9
S. Cherif et al. Ceramics International xxx (xxxx) xxx
O−2 + 2H2O + e− →2 OH• + 2OH− (Eq. 8)
structure.
h+ + OH− → OH• (Eq. 9)

OH• + contaminant→ products (Eq. 10)

3.3. Biodegradability assays and phytotoxicity tests
However, a significant challenge in photocatalysis is the rapid
recombination of electron-hole pairs, which reduces efficiency. In this The BOD5/COD ratio is a standard metric for assessing wastewater
study, we suggest that the existence of CaCO3 in ZnO could help to biodegradability. A ratio exceeding 0.4 generally indicates suitability for
mitigate this issue and enhance photocatalytic performance. biological treatment, while values between 0.3 and 0.4 suggest partial
The superior photocatalytic performance of ZnOE, synthesized via biodegradability [73]. To evaluate the impact of ZnOC and ZnOE on the
eco-friendly coprecipitation, over ZnOC, produced through chemical biodegradability of BY28 dye, their effects on the BOD5/COD ratio were
coprecipitation, can be attributed to ZnOE’s smaller crystallite size (15 examined under optimal conditions. The results showed a significant
nm versus 18 nm for ZnOC), which provides a larger specific surface increase in this ratio from 0.12 to 0.47 for ZnOC and from 0.12 to 0.56
area. Additionally, the presence of calcium atoms, as indicated by EDX for ZnOE, suggesting enhanced biodegradability (Fig. 10a). This
analysis, and CaCO₃, as identified in XRD analysis, further contribute to improvement is likely attributed to alterations in the dye’s structure and
ZnOE’s efficiency. The incorporation of CaCO₃ and calcium-doped ZnO properties, as well as the influence of the initial organic matter. These
has been shown to enhance photocatalytic degradation of pollutants by findings align with previous studies by Asgari et al. (2020), Sin et al.
facilitating electron transfer and reducing the recombination rate of (2024) and Madjene et al. (2020).
electron-hole pairs, which are essential for effective photocatalysis. Asgari et al. (2020) investigated the combined effects of ultrasound,
For instance, Visali et al. (2019) synthesized pure, 2 wt% aluminum- UV irradiation, zinc oxide, and persulfate (US/UV/ZnO/PS) on the
doped, 2 wt% calcium-doped, and co-doped ZnO nanoparticles. They degradation of real textile wastewater. The study found a significant
observed that calcium-doped ZnO achieved the highest degradation rate increase in the biodegradability of the wastewater, as indicated by the
of 89 % for methylene blue, attributed to the suppression of electron- increase in the BOD5/COD ratio from approximately 0.15 to 0.61 within
hole recombination at defect sites [52]. Similarly, Slama et al. (2016) the first 90 min of treatment [74].
found that calcium-doped ZnO exhibited higher photocatalytic activity Sin et al. (2024) developed a green method to synthesize ZnO
in methylene blue degradation than undoped ZnO [53]. nanosponge using Musa acuminata peel extract. This material was
These findings align with the work of Oliveira (2019), who reported employed for the photodegradation of real textile wastewater. The
that calcium-doped ZnO achieved a higher degradation rate of methyl wastewater’s low initial BOD5/COD ratio of 0.16 indicated poor
orange due to favorable modifications in the material’s textural prop­ biodegradability, necessitating advanced oxidation processes. A slight
erties, including surface structure, particle size, and morphology. Such improvement in biodegradability was observed after photodegradation,
changes improve the specific surface area and optical properties, with the BOD5/COD ratio increasing to 0.20 [75].
enhancing photocatalytic efficiency [70]. Madjene et al. (2020) investigated the photocatalytic degradation of
Chen et al. (2011) synthesized a CaCO₃/ZnO photocatalyst and Rhodamine B (RhB) using a Box-Behnken design to optimize the process.
demonstrated that its photocatalytic performance was superior to that of ZnO suspension was employed under artificial UV irradiation (24 W) to
pure ZnO. The extended photoabsorption into the visible light spectrum facilitate the reaction. After a 60-min treatment, a notable enhancement
significantly enhanced the utilization of solar energy for pollutant in biodegradability was observed, as indicated by a BOD5/COD ratio
degradation [71]. Similarly, Naknonhan (2024) confirmed the syner­ increase from 0.23 to 0.90 [76].
gistic effect between ZnO and CaCO₃ in the degradation of 2,4,5-trichlor­ To assess the efficacy and environmental safety of BY28 dye photo­
ophenol (TCP), showing higher photoactivity compared to pure ZnO catalytic degradation, phytotoxicity tests using watercress seeds were
[72]. conducted. The goal was to determine if the process effectively elimi­
Additionally, albite, identified through XRD analysis, plays a sup­ nated toxic compounds, including potentially hazardous by-products
portive role in stabilizing the composite structure. While albite itself generated through oxidation, reduction, and addition reactions. Initial
may not exhibit strong photocatalytic properties, its presence in the tests compared an untreated 10 mg L− 1 BY28 solution to a sample
composite material enhances the overall efficiency of pollutant degra­ treated for 240 min with 1 g L− 1 ZnOC and ZnOE catalysts. Figure (10b)
dation by maintaining the stability and integrity of the catalyst illustrates the germination index (GI) results. Unexpectedly, the

Fig. 10. (a): Biodegradability evolution before and after solar photocatalytic treatment at optimal conditions (CZnO = 1g.L− 1, C0 = 10 mg L− 1, pH = 6.60, UV index
9/11, time 180 min) (b): Phytotoxicity evolution before and after solar photocatalytic treatment at optimal conditions (CZnO = 1g.L− 1, C0 = 10 mg L− 1, pH = 6.60,
UV index 9/11, time 180 min).

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S. Cherif et al. Ceramics International xxx (xxxx) xxx

untreated solution exhibited a GI exceeding 100 %, suggesting potential respectively.

hormesis–a phenomenon where low pollutant doses stimulate growth The degradation of JB 28 followed pseudo-first-order kinetics, with
[77]. However, the treated sample’s GI approached control levels, rate constants varying depending on the catalyst and irradiation type.
indicating successful the safety of the by-products for the environment ZnOE demonstrated a faster performance under solar irradiation (k =
(Fig. 10b). 0.0169 min⁻1) compared to ZnOC (k = 0.007 min⁻1). This difference was
Yashni et al. (2020) investigated the kinetics of Basic Red 51 (BR51) attenuated under lamp irradiation (ZnOE: k = 0.0127 min⁻1, ZnOC: k =
dye photodegradation using green-synthesized zinc oxide nanoparticles 0.0037 min⁻1).
(ZnO NPs) from Coriandrum sativum leaf extract and zinc acetate as the The biodegradability of the BY28 dye was significantly improved
precursor. Phytotoxicity tests on Vigna radiata seeds revealed that BR51 using ZnOE and ZnOC. The treated solution showed no phytotoxicity.
exhibited strong anti-germination properties at all concentrations, These findings have significant implications for water treatment,
attributed to its high phenolic content. This confirmed BR51’s toxicity, opening new avenues for the development of sustainable solutions.
aligning with previous studies on the inhibitory effects of phenolics on
plant growth. However, following photocatalytic treatment, the treated CRediT authorship contribution statement
solution demonstrated no significant difference in root and shoot length
compared to the control, indicating that BR51 degradation products Sonia Cherif: Writing – review & editing, Visualization, Validation,
were non-toxic [78]. Supervision, Software, Resources, Methodology, Investigation, Data
Gangwara et al. (2023) developed a green method to synthesize zinc curation, Conceptualization. Hynda Rezzaz-Yazid: Writing – review &
oxide nanoparticles (SB-ZnO-NPs) using Strobilanthes barbatus leaf editing, Supervision, Methodology, Investigation, Conceptualization.
extract. These nanoparticles effectively degraded Reactive Yellow 86 Sabra Hemidouche: Data curation. Asma Farsi: Software, Methodol­
(RY-86) and Reactive Yellow 145 (RY-145) textile dyes under UV irra­ ogy, Investigation, Data curation. Sarra Mostefaoui: Software, Meth­
diation. Phytotoxicity tests using Vigna radiata seeds demonstrated a odology, Investigation, Data curation, Conceptualization. Mohamed
significant reduction in germination index inhibition, indicating Belmedani: Resources, Investigation. Hayet Djelal: Writing – review &
decreased toxicity of the dye solutions after treatment with SB-ZnO-NPs editing, Resources, Investigation. Zahra Sadaoui: Resources,
[79]. Investigation.
Vithalani et al. (2024) utilized a low-cost garlic (Allium sativum) to
synthesize zinc oxide nanoparticles. The toxicity of Rhodamine B was
assessed before and after photocatalytic treatment using these nano­ Declaration of interest statement
particles in experiments with Vigna radiata L. seeds, a crucial agricul­
tural crop. Results indicated a significant reduction in the toxicity of The authors declare that they have no known competing financial
Rhodamine B following treatment, as evidenced by diminished adverse interests or personal relationships that could have appeared to influence
effects on plant and soil health when irrigated with treated water [80]. the work reported in this paper.
Green synthesis of ZnO using Opuntia ficus-indica offers a promising
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