Chemical Engineering Journal 493 (2024) 152717

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Chemical Engineering Journal

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

High-Efficient photocatalytic degradation of Levofloxacin via a novel

ternary Fe2O3/CeO2/ZnO Heterostructure: Synthesis Optimization,
Characterization, toxicity assessment and mechanism insight
Zhongjie Fei a, Mohammed A. Alghassab b, *, Pradeep Kumar Singh c, *, Barno
Sayfutdinovna Abdullaeva d, Mahidzal Dahari e, *, Amr S. Abouzied f, g, Ibrahim Albaijan h,
Hadil faris Alotaibi i, Albara Ibrahim Alrawashdeh j, k, Merwa Alhadrawi l, m, n
a
Key Laboratory of Animal Diseases Diagnostic and Immunology, Ministry of Agriculture, College of Veterinary Medicine, Nanjing Agricultural University, Nanjing,
China
b
Electrical Engineering Department, College of Engineering, Shaqra University, Riyadh 11911, Saudi Arabia
c
Department of Mechanical Engineering, Institute of Engineering & Technology, GLA University, Mathura, U.P, 281406, India
d
Department of Mathematics and Information Technologies, Vice-Rector for Scientific Affairs, Tashkent State Pedagogical University, Tashkent, Uzbekistan
e
Deparment of Electrical Engineering, Faculty of Engineering, Universiti Malaya, 50603 Kuala Lumpur, Malaysia
f
Department of Pharmaceutical Chemistry, College of Pharmacy, University of Hail, Hail 81442, Saudi Arabia
g
Department of Pharmaceutical Chemistry, Egyptian Drug Authority, Giza, Egypt
h
Mechanical Engineering Department, College of Engineering at Al-Kharj, Prince Sattam Bin Abdulaziz University, Al Kharj 16273, Saudi Arabia
i
Department of Pharmaceutical Sciences, College of Pharmacy, Princess Nourah bint AbdulRahman University, Riyadh 11671, Saudi Arabia
j
Department of General Subjects, College of Engineering, University of Business and Technology, Jeddah 21361, Saudi Arabia
k
Department of Chemistry and Chemical Technology, College of Science, Tafila Technical University, Tafila 66110 Jordan
l
Department of Refrigeration and air Conditioning Techniques, College of Technical Engineering, the Islamic University, Najaf, Iraq
m
Department of Refrigeration and air Conditioning Techniques, College of Technical Engineering, the Islamic University of Al Diwaniyah, Al Diwaniyah, Iraq
n
Department of Refrigeration and air Conditioning Techniques, College of Technical Engineering, the Islamic University of Babylon, Babylon, Iraq

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

Keywords: Considering the serious problem of lack of freshwater worldwide and the effectiveness of the photocatalysis
Wastewater treatment process in water purification, we prepared a novel Ternary Fe2O3/CeO2/ZnO photocatalyst toward degradation
Photocatalysis of Levofloxacin (LEF) antibiotic. In this study, the CeO2 was synthesized through the hydrothermal route and the
Degradation
nanocomposite was prepared using a simple-impregnation method. Then the synthesized materials with various
Levofloxacin
weight percentages 5 %FeCe (10, 20, 30 and 40 %) on the ZnO were completely characterized in the aspects of
Fe2O3/CeO2/ZnO Photocatalyst
structural, morphological and optical properties with the aid of XRD, XPS, BET, TEM, SEM, EIS, ESR, Band-gap,
Photocurrent, Mott Schottky, etc. The XPS analysis depicts the successful construction of required bonds among
FeCe/ZnO materials. The enhancement of LEF decomposition was investigated utilizing RSM-CCD method,
considering factors such as the amount of catalyst used, irradiation time, pH levels, and the initial concentration
of LEF. The trapping experiments of free radicals highlight the significant contributions of the •OH and •O–2
radicals. A notable degradation rate of 98.9 % was achieved under optimal operational conditions, which
included catalyst dosage of 0.69 g/L, irradiation period of 83.64 min, initial LEF concentration of 37.9 mg/L, and
pH of 6.18. Furthermore, the findings of EIS, photocurrent, and Mott-Schottky analyses allowed for proposing a
suitable charge transfer mechanism and demonstrated effective separation of photo-generated electron-hole
pairs. Additionally, LC-MS analysis was utilized to elucidate the intermediate products generated during the
photodegradation of LEF, leading to the proposal of plausible degradation pathways. The exceptional efficiency
of the 30FeCe/ZnO photocatalyst highlights its promising potential for the efficient treatment of persistent
organic pollutants on a large scale in wastewater treatment plants.

* Corresponding authors.
E-mail addresses: [email protected] (M.A. Alghassab), [email protected] (P.K. Singh), [email protected] (M. Dahari).

https://doi.org/10.1016/j.cej.2024.152717
Received 26 March 2024; Received in revised form 11 May 2024; Accepted 30 May 2024
Available online 31 May 2024
1385-8947/© 2024 Elsevier B.V. All rights are reserved, including those for text and data mining, AI training, and similar technologies.
Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

1. Introduction ZnO was successfully synthesized for the first time through a sequential
procedure involving hydrothermal treatment and impregnation. The
Nowadays, there has been a remarkable increment in the amount of manufactured materials, incorporating different weight ratios of FeCe
industrial waste that contaminates the water bodies in the environment. (5 %, 10 %, 20 %, 30 %, and 40 %) on ZnO, underwent comprehensive
Pharmaceutical antibiotics are widely utilized in both human and vet­ structural, morphological, and optical analysis utilizing a range of
erinary medicine around the world, making them one of the most crucial techniques such as XRD, XPS, BET, TEM, SEM, EIS, ESR, band-gap
pharmaceutical compounds [1–3]. Levofloxacin is a highly chemically measurements, photocurrent, and Mott-Schottky analysis, etc. An
stable third-generation fluoroquinolone antibiotic that has a wide range investigation into the efficacy of the synthesized composite in decom­
of antibacterial effects, used for the treatment of bacterial infections, posing a target pollutant, namely LEF, was carried out using the RSM-
osteomyelitis, and other medical conditions [4]. However, the incom­ CCD approach. Key parameters considered included the catalyst
plete metabolism of levofloxacin in human and animal bodies has led to dosage, irradiation duration, pH levels, and initial LEF concentration
its frequent release into the environment, consequently contributing to were optimized. The proposed photocatalytic mechanism of the devel­
the emergence of antibiotic resistance. This not only poses a significant oped ternary photocatalyst was derived from the analysis of band
threat to natural ecosystems but also jeopardizes drinking water safety structures of its constituent materials and was validated through reac­
and human health [5,6]. Hence, there is an immediate need to develop tive species capture studies and optical property evaluations. The
efficient wastewater treatment technologies capable of effectively degradation routes of LEF were then identified using LC-MS assessment.
removing levofloxacin from contaminated water sources while safe­ Furthermore, an assessment of the toxicity of the degradation byprod­
guarding water resources. ucts was conducted via toxicity testing. The findings obtained from this
Various conventional techniques, including ion exchange, adsorp­ in-depth exploration provide valuable insights into the environmental
tion, coagulation, precipitation, and membrane filtration have been implications and practical applications of the newly formulated photo­
utilized for wastewater cleaning [7–11]. However, these methods catalytic system.
possess several drawbacks, including significant consumption, high
operating costs, and the generation of significant secondary contami­ 2. Experimental
nants, which restrict their widespread implementation [12]. Therefore,
there is a pressing need to find alternative approaches to removal of 2.1. Materials
antibiotics from wastewater. Advanced oxidation processes (AOPs) have
gained recognition as highly effective technologies for wastewater This part listed in Text S1.
treatment, particularly in the decomposition of organic pollutants
[13–15]. Among these processes, semiconductor-based photocatalytic 2.2. Preparation of CeO2 nanoparticles
technology has emerged as a promising approach to address environ­
mental issues because of its cost-effectiveness, reusability, high effi­ In a standard experiment, 50 mL of distilled water was used to
ciency, and sustainability [12,16,17]. This technology is a desirable one dissolve 0.5 g of (NH4)2Ce (NO3)6. Next, while stirring, 0.15 mL of
because it uses solar radiation to degrade and mineralize organic pol­ ethylenediamine that had been dissolved in 50 mL of distilled water was
lutants, rendering it a desirable option for various applications. added drop by drop to the mixture. Then, 0.13 mL of hydrazine
Cerium oxide (CeO2) has been identified as a semiconductor with an (N2H4H2O) that had been dissolved in 50 mL of distilled water was
n-type feature that holds potential for use in photocatalytic applications added dropwise. After being transferred into an autoclave, the resulting
due to its favorable properties, containing low toxicity, high chemical solution was heated for five hours at 120 ◦ C. Subsequently, the autoclave
durability, and availability [18,19]. Nevertheless, the material also was allowed to cool to ambient temperature. After centrifuging and
possesses certain limitations, such as a poor surface area, rapid electron/ repeatedly washing the resulting white precipitate with ethanol and
hole recombination, and high energy gap. To address these shortcom­ distilled water, it was dried at 60 ◦ C. Lastly, it was calcined for two hours
ings and enhance the photocatalytic performance of CeO2, the integra­ at 500 ◦ C.
tion of another semiconductor through heterojunction construction has
been proposed [20–22]. In this regard, Hematite (α-Fe2O3) is a widely 2.3. Preparation of α-Fe2O3/CeO2 composite
available material with a narrow bandgap ranging from 1.9 to 2.1 eV.
Due to its facile and cost-effective synthesis, high resistance to corrosion, 1 g of CeO2 particles were sonicated into suspension in 100 ml of
and non-toxic properties, it has been extensively employed as a het­ C2H5OH. A suitable quantity of Fe (NO3)3⋅9H2O was then added to the
erogeneous photocatalyst [23–25]. The introduction of Fe2O3 through suspension and stirred for a duration of 1 h. Following this, stirring and
incorporation or doping has been shown to create trapping sites for letting the C2H5OH evaporate, the suspension was dried for the entire
photo-generated charge carriers, thereby reducing their recombination night at 110 ◦ C. The loading optimization of Fe2O3 on CeO2 was
rate [26–28]. This results in a nanocomposite with an extended ab­ meticulously conducted in accordance with the details provided in the
sorption band and a reduced bandgap compared to pure CeO2. As a Table S1. Then, it was subjected to calcination at 500 ◦ C for 3 h to
result, α-Fe2O3/CeO2 nanocomposites have emerged as promising pho­ produce nanocomposites consisting of 5 wt% Fe2O3/CeO2 (FeCe)
tocatalytic materials, owing to their efficient light harvesting, sup­ nanocomposites.
pressed recombination of photo-generated charge carriers, and
significantly boosted photocatalytic performance [24,29–31]. 2.4. Synthesis of α-Fe2O3/CeO2/ZnO nanocomposite
Moreover, zinc oxide (ZnO) has emerged as a promising candidate
due to its high photoactivity, desirable redox properties, biocompati­ The synthesis of α-Fe2O3/CeO2 nanoparticles involved the impreg­
bility, environmental and thermal stability, and facile synthesis nation of these particles onto the surface of ZnO particles at varying FeC
[32–34]. Moreover, the existence of oxygen vacancies within the concentrations (10, 20,30, and 40 wt%), followed by annealing at
structure of ZnO serves as a form of self-doping without the introduction 400 ◦ C. Generally, 100 mL of ethanol was mixed with 1 g of ZnO
of foreign atoms, thereby contributing to an improvement in its photo­ nanoparticles, and magnetic stirring was used to introduce the appro­
catalytic effectiveness under sunlight/visible-light irradiation. Addi­ priate amount of FeC over the course of an 3 h. Following the ethanol’s
tionally, the utilization of ZnO as a support in this composite system evaporation, the outcoming powder was overnight dried at 110 ◦ C. The
effectively limits the recombination of electron-hole pairs and improves α-Fe2O3/CeO2/ZnO powder was then annealed for 3 h at 400 ◦ C to
the stability of the photocatalyst [35,36]. produce mesoporous FeCe/ZnO nanocomposites (10FeCe/ZnO,
In this particular investigation, a heterostructure composite of FeCe/ 20FeCe/ZnO, 30FeCe/ZnO, and 40FeCe/ZnO).

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2.5. Instruments 3. Results and discussion

The characterization of the manufactured Fe2O3/CeO2/ZnO nano­ 3.1. Crystal phase and surface properties
composites has been provided in Text S2.
The X-ray diffraction (XRD) patterns of the FeCe/ZnO nano­
2.6. Experimental design composite, as well as the individual CeO2 and ZnO nanoparticles, were
depicted in Fig. 1a over a 2θ range from 10˚to 70˚. The distinct and well-
This section appears in Text S3. defined peaks present in the patterns for both materials signify the ex­
istence of the CeO2 and ZnO phases in the synthesized nanocomposites.
2.7. Photocatalytic activity Specifically, the diffraction peaks observed at 31.6◦ , 34.5◦ , 36.3◦ , 47.6◦ ,
54.5◦ , 56.5◦ , 62.8◦ , 68.05◦ , and 69.15◦ are attributed to specific crys­
A UV–visible (UV–vis) detector was utilized to measure the elimi­ tallographic planes of the ZnO particles (JCPDS No. 01–080-0075) [39],
nation of LEF solution in order to determine the photodegradation while the peaks at 28.8◦ , 33.3◦ , 47.5◦ , and 56.6◦ are identified as planes
performance of the photocatalysts. A solution containing 50 ml of LEF of the cerium oxide cubic structure (JCPDS No. 34–0394) [40]. Addi­
(10 mg/L) was mixed with 20 mg of photocatalyst. To guarantee full tionally, a diffraction peak located at 54.5◦ was associated with Fe2O3
adsorption/desorption between the LEF solution and the catalyst sur­ particles. Moreover, it was noted that the peak intensity of ZnO dimin­
face, the suspension was vigorously shaken for thirty minutes in the dark ished with the incorporation of CeO2 and Fe2O3 in the photocatalysts.
prior to irradiation. The solution containing the photocatalyst was then Furthermore, the absence of additional peaks within the range observed
exposed to light radiation 300 W Xe light (Fig. S1a) [37,38]. After that, by the instrument suggests the high purity of the materials.
photodegradation experiments were conducted for a predetermined The composite’s morphology, dimensions, and configuration were
amount of time in direct sunshine, and a UV–vis detector was applied to thoroughly examined utilizing scanning electron microscopy (SEM). As
assess the LEF content. The removal degree was computed using the depicted in Fig. 1b and Fig. S1, it was apparent that FeCe/ZnO nano­
following formula (Eq. (1)): composites tended to link together, displaying a consistent morphology.
The combination of wet impregnation and the appropriate method in the
Degradation(%) = (C0 − Ci )/C0 × 100 (1)
synthesis process facilitated the particle formation. Additionally, CeO2
where c0 and ci are the initial and final concentrations, respectively. and Fe2O3 species were observed to be deposited on the surface of ZnO
To determine which species of radicals partiated in the photo­ particles. Further magnification of the SEM image revealed that the
catalytic activity of the ternary FeCe/ZnO photocatalyst for the elimi­ surface of the ZnO was adorned with numerous nanoscale protrusions of
nation of LEF, a scavenger experiment was used. CeO2, signifying the creation of FeCe/ZnO composites. The identified
FeCe/ZnO structures efficiently disperse FeCe, leading to a heightened
photocatalytic activity. EDX study was conducted to examine the surface
chemical compositions of the samples. As illustrated in Fig. 1c, the
samples were found to contain Ce, Fe, O, and Zn elements, with no
impurities detected. This observation confirms the coanchoring of FeCe

Fig. 1. A) xrd pattern of 30fece/zno, zno, ceo2 samples b) SEM image of 30FeCe/ZnO composite, c) EDS of 30FeCe/ZnO, d) TEM image of 30FeCe/ZnO e) Nitrogen
gas adsorption–desorption isotherm and f) corresponding pore size distribution curve of nanocomposites.

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Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

with the ZnO nanostructures, aligning with the findings from the XRD contributing to a higher overall pore volume. Furthermore, well-
analysis. dispersed FeCe particles on the outer surface of ZnO can also
The TEM image in Fig. 1d shows the nanocomposite (30FeCe/ZnO). contribute to the measured surface area. These particles act like small
The TEM result shows dark spots, depicting the penetration of FeCe bumps on the surface, and when measuring the total surface area, these
particles into the pores of the ZnO structure, likely due to capillary force bumps are taken into account, leading to a higher value compared to the
drawing the cerium particle-containing solution into the pores flat surface of bare ZnO.
[24,41,42]. Notably, the presence of cerium oxide not only impacts the X-ray photoelectron spectroscopy (XPS) study was utilized to vali­
size of the crystallites but also the shape of the particles. Moreover, the date the elemental composition and chemical states within the fabri­
SEM finding confirms the effective deposition of CeO2 particles onto the cated 30FeCe/ZnO composite material. The comprehensive XPS survey
ZnO surface. These findings provide compelling evidence of the suc­ scan revealed distinct peaks at specific binding energies, affirming the
cessful incorporation of CeO2/Fe2O3 particles into the ZnO structure. presence of elements including Cerium (Ce), Zinc (Zn), Iron (Fe), and
The surface characteristics of the ZnO and FeCe/ZnO nanocomposite Oxygen (O) within the 30FeCe/ZnO material (Fig. 2a). Detailed exam­
were assessed using the Brunauer–Emmett–Teller (BET) study to deter­ ination of the individual XPS spectra with Zn 2p deconvolution exhibi­
mine their surface area and mesoporous volume (Fig. 1e, f). Based on the ted two resolved peaks at approximately 1022 eV and 1045 eV,
IUPAC categorization, type-IV isotherms with H3 hysteresis loops at corresponding to the ZnO 2p states, as depicted in Fig. 2b. Notably, a
particular relative pressures (P/P0 = 0.8 and 1.0) were found. These significant peak in the O1s spectra at 529.6 eV indicated cerium-oxygen
loops show that all samples include a slit-like mesoporous structure. As bonding, while a peak at 531.8 eV was likely due to surface-adsorbed
shown in Table S3, the specific surface areas of ZnO and the 30FeCe/ radical hydroxyl groups (•OH) (Fig. 2c). Furthermore, high-resolution
ZnO nanocomposite were measured to be 17.34 and 50.48 m2/g, imaging of the cerium 3d orbitals through XPS analysis (Fig. 2d)
respectively. The observed boost in specific surface area for the 30FeCe/ revealed distinct peaks for the 3d3/2 and 3d5/2 orbitals, indicative of
ZnO composite over pristine ZnO can be attributed to the appropriate Ce4+ species predominantly governing the valence states of cerium
loading percentage and homogeneous distribution of FeCe nanoparticles oxide. Additionally, the presence of multiple peaks corresponding to
on the ZnO surface. Conversely, the elevated loading of FeCe binary Ce3+ species was identified. Moreover, the observed peaks associated
photocatalyst may lead to pore blockage in ZnO. These characteristics with Fe 2P3/2 and Fe 2P1/2 were consistent with previous investigations,
are anticipated to have a significant positive impact on the overall highlighting the reliability and reproducibility of the findings (Fig. 2e)
photocatalytic activity. It should be noted that, even though FeCe par­ [24,43].
ticles penetrate the pores of ZnO, their presence can lead to a higher
overall surface area due to several factors. The FeCe particles may de­
3.2. Investigation of photocatalysis process
posit on the pore walls of the ZnO, increasing the surface roughness
within the pores, thus creating more accessible surface area compared to
Without the introduction of any extra agents, the elimination of LEF
the smoother walls of bare ZnO pores. Additionally, during the
solution was applied to assess the photocatalytic performance of the
impregnation process, the interaction between FeCe and ZnO could lead
recently synthesized photocatalyst under comparable operating cir­
to the creation of new, smaller pores within the existing ZnO structure,
cumstances (Fig. S2). The pristine ZnO displayed a low LEF degradation

Fig. 2. XPS spectra of 30FeCe/ZnO composite.

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efficiency of about 35.2 %, associated to the rapid recombination of spectroscopy, photocurrent, photoluminescence, and electrochemical
electron-hole pairs and limited absorption of visible light. Furthermore, impedance spectroscopy demonstrate that its increased photocatalytic
the decomposition performance of ZnO was only 51.6 %. Among the efficiency is the result of enhanced light absorption capabilities, which
newly prepared FeCe/ZnO ternary photocatalysts, the 30FeCe/ZnO speed up electron transfer and separation.
heterostructure depicted the highest photocatalytic efficiency,
achieving 89.6 % LEF degradation under visible light after 60 min.
3.3. ANOVA results and operational parameters
However, an excessive loading of FeCe diminished the degradation
capability of the ternary nanocomposite, possibly due to the excessive
The study explored and simulated the photocatalytic breakdown of
FeCe nanoparticles covering the active sites of the ZnO surface. These
LEF in the presence of 30FeCe/ZnO utilizing the RSM-CCD that incor­
findings underscore the significance of the appropriate FeCe loading
porated four independent factors: catalyst dosage (g/L), pH, time (min),
content for efficient elimination of the target pollutant. The successful
and initial LEF concentration (mg/L) at five different levels. The rela­
creation of a schematic at the interface between the three components is
tionship between the efficiency of LEF degradation and the independent
responsible for the increased photocatalytic activity of the 30FeCe/ZnO
factors was represented by an empirical second-order polynomial
ternary photocatalyst. Studies using UV–vis diffuse reflectance
equation (Eq. (2) expressed in terms of the actual factors:

Fig. 3. A) predicted vs actual values and b) normal probability as a term of actual amounts, one factors c) catalyst dose, d) ph, e) time, f) lef concentration and rsm 3d
plots for degradation efficiency of lef g) time with catalyst dose, h) time with ph, i) lef concentration with time.

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Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

Y = 96.68 + 7.03 × X1 + 1.97 × X2 + 3.68 × X3 − 6.40 × X4 + 3.60 LEF molecules. Conversely, at pH values higher than 7 or lower than 5,
both the catalyst surface and LEF molecules carry opposing charges,
× X1 X2 + 1.50 × X1 X3 + 1.55 × X1 X4 − 3.58 × X2 X3 + 2.37
resulting in electrical repulsion and limiting the photocatalytic degra­
× X2 X4 − 0.0764 × X3 X4 − 10.06 × X21 − 12.24 × X22 − 4.77 dation process.
× X23 − 6.38 × X24 (2) As depicted in Fig. 3e, prolonging the duration of illumination results
in a heightened degradation efficiency. The extended illumination time
where Y (LEF degradation (%)) is a function of catalyst dose (A:X1), pH facilitates the generation of additional reactive species, consequently
(B:X2), irradiation time (C:X3), and LEF concentration (D:X4). The co­ allowing for an increased duration of interaction between these reactive
efficient of determination (R2) value of 0.98 indicates that a verified species and the pollutants (Table S5). This prolonged interaction, in
polynomial model was used to represent the experimental responses turn, culminates in a greater degree of photodegradation of antibiotics.
within the given operational parameter ranges. Fig. 3a depicts a com­ However, over time, the electron and hole can recombine with each
parison of experimental and model-predicted data for LEF degradation other, wasting the energy and hindering degradation. On the other hand,
efficiency. The points representing the experimental and expected at longer light exposure the pollutant or byproducts from the degrada­
values are evenly distributed around the diagonal line, indicating that tion process can sometimes deactivate the catalyst surface, reducing its
the average error between the experimental and predicted responses is ability to capture light or pollutants. Moreover, there are only a limited
small. The normal probability plot of residuals (Fig. 3b) shows that they number of active sites on the photocatalyst. As pollutant molecules are
follow a normal distribution pattern. Collectively, these findings support degraded, these sites can become saturated, meaning new pollutant
the proposed model’s applicability for estimating LEF degrading effi­ molecules can’t bind and be broken down, even with continued
ciency. Table S4 contains full findings of the analysis of variance illumination.
(ANOVA). A high F-value and a small p-value (p < 0.05) show statistical In Fig. 3f, I, the influence of the initial concentration of LEF pollutant
significance of the independent variables. As a result, the model’s non- on its decomposition efficiency by 30FeCe/ZnO nanocomposite is pre­
significant Lack of Fit and substantial F-value indicate that it is highly sented. When the initial concentrations are low, the photocatalyst’s
accurate in predicting LEF degradation under varied operating condi­ surface absorbs the pollutant molecules and interacts with the reactive
tions. Additionally, all independent parameters have a considerable radicals generated on the surface. However, as the initial LEF concen­
impact on LEF degradation efficiency. Notably, catalyst dosage and LEF tration increases with time, the efficiency of degradation declines
concentration exhibit the highest F-value, indicating their utmost (Table S5). This diminishing pattern is attributed to a rise in contami­
importance among the operational parameters, while Time and pH exert nant levels saturating the active sites of the photocatalyst, resulting in
a relatively lower influence on the degradation efficiency. Indeed, unabsorbed contaminant and a slower reaction rate. The presence of
considering the ANOVA results (Table S4) and empirical second-order unabsorbed pollutant molecules inhibits light penetration, photocatalyst
polynomial equation (Eq. (2), the higher coefficient of each param­ excitation, and the formation of active radicals, which reduces the
eter, the more effective in the efficiency of the process. Fig. 3 and generation of reactive species.
Table S5 display the one-factor plots and three-dimensional (3D) To attain optimal LEF degradation efficiency, operational parameters
response surface methodology plots that show the interaction between were fine-tuned through numerical analysis of a model using RSM
operational variables and LEF deterioration efficiency. method. Under the identified optimum conditions (catalyst dosage =
The influence of changing the photocatalyst amount on the LEF 0.69 g/L, pH = 6.18, time = 83.64 min, and LEF concentration = 37.95
elimination performance was investigated in Fig. 3c, g by increasing the mg/L), 98.9 % of the LEF pollutant was degraded using the 30FeCe/ZnO
photocatalyst dose between 0.15 and 1.15 g/L. It was observed that as photocatalyst, as demonstrated in Fig. S3. Moreover, the kinetic rate
the catalyst dose was augmented from 0.15 to 0.65 g/L, the decompo­ constants (k) for the decomposition of LEF pollutants can be computed
sition efficiency improved. However, a further increase beyond the using the first-order model equation. The relative effectiveness of
optimal dosage (0.69 g/L) resulted in a decrease in decomposition various photocatalysts is revealed by the kinetic linear fitting curves,
performance (Table S5). This is described by the fact that enhancing the which are displayed in Fig. 4a, and the associated k values, which are
dosage of the catalyst to its optimal level boosts the number of active compiled in Table S6. Specifically, it is observed from Fig. 4a that the
sites in the photocatalyst and the area in which the catalyst and LEF 30FeCe/ZnO ternary photocatalyst exhibits a notably higher k value of
molecules come into contact, producing more reactive species that aid in 0.058 min− 1 in comparison to 5 % FeCe/ZnO (0.011 min− 1) and ZnO
the breakdown of LEF molecules. However, an excessive increase in (0.007 min− 1) for the degradation of LEF pollutant. These findings
catalyst dose causes aggregation of catalyst particles and obstruction of affirm the substantial augmentation in the photocatalytic activity of
active sites, resulting in turbidity in the solution and inhibiting light single-phase ZnO due to the existence of the FeCe/ZnO ternary
penetration. Considering the provided 3D graph (Fig. 3g), as the amount photocatalyst.
of catalyst dosage increased until its center point beside the central time
irradiation, the efficiency reached the maximum percentage. Moreover,
further increase in these values resulted in a decline in the rate of LEF 3.4. Photocatalytic degradation of other contaminants
degradation due to the blocking of active sites of the catalyst during the
provided time. Generally, the optimum amount of each parameter plays Additionally, the versatility of the 30FeCe/ZnO composite was
a crucial role in this matter. verified through detoxification evaluations of other harmful organic
The pH and charge surface features of the pollutant and photo­ contaminants under visible light, yielding degradation efficiencies of
catalyst influence photodegradation efficiency, which is reliant on their 96.6 % for methylene blue (MB), 93.2 % for cefixime (CFX), 86.4 % for
respective pKa and pH zpc values (Fig. 3d, h). The pH drift method was tetracycline (TC), 77.6 % for norfloxacin (NOR), and 81.9 % for an
used to measure the pH zpc value of the FeCe/ZnO ternary photocatalyst azithromycin (AZ) contaminant, as displayed in Fig. 4b. The effective­
in this study, which was approximately 6.94. The photodegradation ness of the 30 FeCe/ZnO photocatalyst on different pollutants can be
efficiency of the pollutant, LEF, showed the highest degradation at pH 6, seen in the kinetic linear fitting curves shown in Fig. S4, along with the
with approximately 98 % efficiency (Table S5). The LEF molecule ex­ corresponding k values. Moreover, variations in degradation efficiency
hibits varying charge states based on its pKa values (5.57 and 7.95), among pollutants may be attributed to variances in molecular functional
transitioning from cationic to zwitterionic to anionic as the pH changes. group structures. In conclusion, while differences in degradation activity
At pH 6, the zwitterionic form of the LEF molecules is present, leading to were observed, these favorable outcomes underscore the broad utility of
enhanced photodegradation due to the interaction between the positive the 30FeCe/ZnO composite for the degradation of diverse harmful
charge on the FeCe/ZnO photocatalyst and the negative charge on the organic pollutants.

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Fig. 4. A) kinetic linear fitting curves of various photocatalysts under visible light after60 min of irradiation, b) Degradation of different organic pollutants under
optimal conditionsc), Photocatalytic degradation using various inorganic salts as interference, d) Assessment of photocatalytic degradation using different water
sources, e) Observation of LEF degradation efficiencies across four consecutive cycles, f) Analysis of X-ray diffraction (XRD) pattern.

3.5. Evaluation of photocatalytic degradation employing various high as 80 %. These findings indicate that the 30FeCe/ZnO photo­
inorganic salts and water sources catalyst has practical application in the purification of real water
samples.
It is commonly known that a range of coexisting ions, such as Cl–,
SO2–
4 , HCO3–, and Ca2+, can occur in natural water and can make pho­
3.6. Investigation of stability
tocatalytic difficult to achieve to a desirable degree. These ions react
with oxidizing species, obstruct charge carriers, and compete with target
To assess the endurance and potential for repeated usage of the
contaminants for adsorption on the catalyst’s surface. The decomposi­
30FeCe/ZnO photocatalyst, its ability to catalyze under visible irradia­
tion rate of LEF in the existence of various ions is depicted in Fig. 4c,
tion was investigated. Then each cycle experiment, the photocatalyst
with the associating decomposition performance order as follows: no
powder was centrifuged and then rinsed multiple times with deionized
reagent > SO24 – > Cl- > Ca2+ > HCO–3. The addition of SO24 – and Cl– ions
water. The findings, showed in Fig. 4e, represent that the photocatalytic
had a minimal impact on the elimination of LEF. Moreover, the Ca2+
performance of 30FeCe/ZnO did not display significant deterioration
ions compete with LEF contaminants for the limited active sites of the
after four cycles in the degradation of LEF. The slight diminution in
surface of photocatalyst, which hinders the photodegradation of LEF.
photocatalytic activity was attributed to the loss of the photocatalyst
Furthermore, the inclusion of HCO–3 in the LEF solution considerably
during the recovery process. Hence, it can be concluded that the
slowed the degradation process, most likely due to its effect on the pH of
30FeCe/ZnO composites possess attributes of a sturdy and long-lasting
the solution via hydrolysis and its ability to react with h+/•OH radicals,
photocatalyst. Additionally, in Fig. 4f, the XRD data of the composite
reducing the photocatalytic system’s efficiency. Thus, HCO–3 had a
material is presented both before and after undergoing cyclic degrada­
remarkable inhibitory effect on the photocatalytic elimination of LEF
tion. Analysis of the XRD diffraction peaks indicates that there was no
molecules.
discernible shift following the cyclic degradation experiment, in com­
To examine the potential effectiveness of the 30FeCe/ZnO photo­
parison to the characteristics of the original, unaltered sample.
catalyst, different types of water including river water, wastewater,
deionized water, and tap water were applied as the solvent for the
comparison of light-induced degradation of the pharmaceutical com­ 3.7. Optical and charge transfer properties
pound LEF. In the presented data (see Fig. 4d), the decomposition effi­
ciency of LEF was found to decline from 98 % to 90 %, 88 %, and 84 % The optical properties of pure, pristine Fe2O3, CeO2, ZnO, and
when employing deionized water, river water, tap water, and waste­ 30FeCe/ZnO samples were studied using UV–Vis diffuse reflectance
water effluents, respectively. It is noteworthy that the degradation of spectroscopy (DRS) and the following Eq. (3):
LEF remained at approximately 90 % even in the presence of other
components in DI and river water. In the case of tap water, the elimi­ F.(R) = (Î ± hν) = A(hν-Eg )n (3)
nation of LEF was slightly inhibited, presumably due to the presence of
In this context, “hν” represents the photon energy, “A” signifies a pro­
common decreasing components leading to competitive and/or scav­
portional constant, “Eg” denotes the band gap, and “n” characterizes the
enging effects. The degradation of LEF was significantly reduced in
nature of the sample’s transition. Notably, different values of “n” such as
wastewater effluents, while the ultimate removal efficiency remained as
1/2, 3/2, 2, and 3 correspond to distinct types of transitions: direct

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Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

allowed, direct forbidden, indirect allowed, and indirect forbidden formula ENHE = Ag/AgCl + 0.197, yielding quantities of 0.25 eV, − 0.45
transitions, respectively. The Kubelka–Munk function, denoted as “F. R” eV, and − 0.62 eV relative to NHE, respectively. Furthermore, the energy
is formulated in terms of the Kramers–Kronig transformation, repre­ levels of the valence bands (EVB) for the composite materials were
sented by Eq. (4): determined using the formula EVB = ECB + Eg, where Eg denotes the band
gap energy. As a result, the EVB values were established to be 2.51 eV for
1 − R2
F.R = (4) Fe2O3, 2.46 eV for CeO2, and 2.60 eV for ZnO, each measured against the
2R
normal hydrogen electrode (NHE).
In this equation, “R” denotes the reflectance, which is typically deter­ The prepared samples were analyzed using photoluminescence (PL)
mined utilizing a UV/Vis spectrophotometer. Furthermore, the bandgap to study the effectiveness of separating the photo-generated charge
energies (B.E) of Fe2O3, CeO2, ZnO, and 30FeCe/ZnO were found to be carriers, as depicted in Fig. 5e. Subsequently, PL assessment was carried
2.26 eV, 2.91 eV, 3.2 eV, and 2.86 eV respectively, as depicted in Fig. 5a. out for both the ZnO material and the prepared composite materials. It
Notably, the activity of ZnO semiconductor is little under visible light was observed that the 30FeCe/ZnO composite displayed the weakest PL
due to its higher band gap energy same as TiO2. Therefore, with the signal intensity, suggesting that it was the most effective and possessed
addition of Fe2O3 and CeO2, the band gap shifts to the visible region in superior capability to facilitate the separation of photogenerated charge
the 30FeCe/ZnO ternary photocatalyst. carriers. EIS analysis was utilized to survey the charge transport mech­
Mott-Schottky analysis was used to determine the flat band poten­ anism. Analysis of the Nyquist plot at elevated frequencies displayed a
tials (EFB) of Fe2O3, CeO2, and ZnO semiconductors. The Mott-Schottky semicircular pattern, with the diameter of this semicircle attributing to
plots for these samples are shown in Fig. 5b, c, and d, with each plot the charge transfer resistance (Rct). As depicted in Fig. 5f, it is apparent
exhibiting a positive slope, confirming the n-type nature of these semi­ that the 30FeCe/ZnO sample demonstrated the least semicircle size
conductors. The EFB values for Fe2O3, CeO2, and ZnO were found to be during illumination, indicating a more effective dissociation of photo­
0.06 eV, − 0.65 eV, and − 0.82 eV, respectively, when measured against induced electron–hole pairs and a swifter charge transport mechanism
the Ag/AgCl electrode. This is equivalent to + 0.84 eV and − 0.41 eV in comparison to pristine ZnO and Fe2O3/CeO2. To validate the ability of
against the normal hydrogen electrode (NHE). The conduction band the photoinduced charge carriers to separate and migrate in the nano­
energy (ECB) of Fe2O3, CeO2, and ZnO was determined employing the composites and pure ZnO, a photocurrent analysis was conducted.
Among the synthesized catalysts, 30FeCe/ZnO showed the most

Fig. 5. A) band gap energy of fe2O3, CeO2, ZnO, b-d) mott-schottky plot of substances, e) PL analysis, f) EIS analysis, g) Trapping test, h-i) ESR analysis.

8
Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

significant photocurrent response, indicating a higher rate of dispersion than the standard potential of O2/•O–2 (− 0.33 eV), providing this op­
for the electron-hole pairs. This finding corresponds with the EIS and PL portunity to electrons to significantly diminish chemisorbed oxygen to
data, implying that the incorporation of FeCe and the utilization of ZnO anion superoxide radicals, particularly associating to degradation of
as a support improve the capacity for charge transfer and the efficiency molecules.
of separating electron-hole pairs. The proposed mechanism of the 30FeCe/ZnO composite’s photo­
The active species were identified through trapping experiments, and catalytic activity was described using the following equations (Eqs. (5)–
the mechanism of the photocatalytic reaction was investigated (Fig. 5g). (14)):
To demonstrate the impact of reactive oxygen species (ROS) on the
Fe2 O3 /CeO2 /ZnO + hv→e− + h+ (5)
selectivity of the photocatalytic reaction, compounds including 1 mM
isopropyl alcohol (IPA, •OH quencher), triethanolamine (TEA, h+
CeO2 (e− )→CeO2 (e− ) (6)
quencher), p-benzoquinone (BQ, •O–2 quencher), and AgNO3 (e-
quencher) were utilized in the testing process. The findings indicate that Fe2 O3 + hv→Fe2 O3 (e− + h+ ) (7)
the addition of BQ and IPA notably inhibited the photocatalytic effi­
ciency, suggesting that •O–2 and OH radicals have a vital role in LEF ZnO + hv→ZnO(e− + h+ ) (8)
elimination. This suggests that anion superoxide and hydroxyl radical
were the primary ROS in the 30FeCe/ZnO composite photocatalytic CeO2 (e− ) + O2 →O•− (9)
system when exposed to visible light. Besides, Electron spin resonance
(ESR) study was employed to detect the production of ROS in the ZnO(e− ) + O2 →O•− (10)
30FeCe/ZnO photocatalyst (Fig. 5h, i). The absence of ESR signals for
both DMPO- •OH and DMPO- •O–2 in the dark condition contrasted with O•− + LEF→CO2 + H2 O (11)
the distinct observation of four characteristic peaks of the DMPO- •O–2
and DMPO- •OH adducts under visible light, implying the excitation of ZnO(h+ ) + H2 O(OH− )→HO• (12)
O2 and •OH free radicals by simulated sunlight. Of significance, the
• –

signal intensity of these characteristic peaks indicated the generation of Fe2 O3 (h+ ) + H2 O(OH− )→HO• (13)
O2 and •OH free radicals, highlighting their prominent role in the
• –
HO• + LEF→CO2 + H2 O (14)
photocatalytic degradation of the LEF pollutant. The ESR findings were
consistent with the outcomes of the ROS capture analysis.
The LC-MS study was employed to survey the intermediates formed
during the degradation of LEF (Fig. S5). Drawing upon the findings of
3.8. Mechanism, photodegradation pathways and toxicity study this study as well as existing literature, we have developed four pro­
spective degradation pathways, illustrated in Fig. 7 [44,45]. In the first
According to analysis results, Fig. 6 proposes a probable charge pathway, LEF undergoes hydroxylation to yield P1 (m/z = 378).
transfer path and photocatalytic process for the 30FeCe/ZnO ternary Following the piperazine ring breaking and decarboxylation, P2 (m/z =
photocatalyst. When exposed to visible light, all three components are 277) is formed; P2 is then extensively defluorinated to produce P3 (m/z
capable of generating photo-induced hole-electron pairs. However, the = 258). Reactive radicals contribute to the destruction of the residual
CB potential of Fe2O3 (0.25 eV) is not high enough to manufacture •O–2 piperazine ring moiety and quinolone portion of P3, leading to the
radicals due to the standard reduction potential of O2/•O–2 (− 0.33 eV vs. fabrication of P4 (m/z = 135) [46]. Path II produces P5 (m/z = 375) by
NHE), leading to electron recombination on the EVB of CeO2. The ECB of substituting a hydroxyl group for the fluorine in LEF. After that, P5′s
cerium oxide and ZnO were measured as − 0.45 eV and − 0.60 eV, piperazine ring fragment breaks to become P6 (m/z = 333). P6 dem­
respectively, and these materials can react with O2 to produce •O–2 onstrates the steps involved in decarboxylation and demethylation to
radicals. Notably, some electrons in ZnO have a tendency to move from create P7 (m/z = 261), which then demethylates to create P10 (m/z =
their CB to the CB of CeO2.Additionally, the EVB for Fe2O3 and ZnO were 245). Pathway III involves a carboxylation step to remove the methyl
assessed to be 2.51 eV and 2.60 eV, respectively. The EVB of CeO2 was group from the LEF molecule, producing P8 (m/z = 391). Decarboxyl­
positioned strategically to increase charge separation by facilitating the ation subsequently yields P9 (m/z = 303). P10 (m/z = 245) is ultimately
recombination of photoinduced electrons. Consequently, recombination formed by demethylation and piperazine ring breaking of P9. P11 (m/z
of electrons from Fe2O3 with the holes of CeO2 occurs in the EVB of = 391) is produced in route IV when the piperazine ring opens [47]. P14
CeO2, while the generated electrons remain in the conduction band of (m/z = 295) is the result of P11′s quinolone and aldehyde ring opening
CeO2. We observe that the existence of ESR signals associating to DMPO and demethylation procedures. P15 (m/z = 72), P16 (m/z = 85), P17
•
OH in the 30FeCe/ZnO photocatalyst indicates that Fe2O3 and ZnO (m/z = 60), and P18 (m/z = 114) are examples of small molecule
holes are more efficient at oxidizing OH– to produce hydroxyl radicals structures that show a steady breakdown of macromolecular structures.
due to their greater valence band potential. Furthermore, the ECB of Eventually, this leads to partial mineralization, which produces NH+ 4,
CeO2 (− 0.45 eV) and ZnO (− 0.6 eV) had a higher negative potential CO2, and H2O, among other tiny molecules [48].
The products formed during the breakdown of organic pollutants
may pose potential risks to the ecosystem. Consequently, it is imperative
to assess the toxicity of these products and contrast of them to that of the
primary contaminant. Utilizing software, we estimated the toxicity of
LEF and its intermediates in various dimensions (such as fathead
minnow LC50-96hr, bioconcentration factor, developmental toxicity,
and mutagenicity), as depicted in Fig. S6 and Table S7. Generally, a
lower quantity of LC50-96hr shows high-level of toxicity. Our analysis
indicated that all identified intermediates, with the exception of P6, P8,
and P13, exhibit lower toxicity than the original LEF. Particularly, the
last intermediates (P15, P16, P17, and P18) have LC50-96hr levels that
are considerably higher than LEF’s. Comparing most intermediates to
LEF, they all show lower bioconcentration factors. Significantly,
Fig. 6. Schematic of the potential charge transfer and degradation of LEF with compared to LEF, all intermediates showed less toxicity to development,
30FeCe/ZnO photocatalyst.

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Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

Fig. 7. The degradation pathways of LEF with 30FeCe/ZnO composite are under speculation.

indicating that the environmental toxicity of LEF pollutant may be 3.9. Comparison of degradation with the previous studies
successfully reduced by treatment with 30FeCe/ZnO photocatalyst.
Moreover, the ultimate intermediates demonstrated significantly This research meticulously describes the development of a photo­
reduced mutagenicity in comparison to LEF, suggesting that the envi­ catalytic nanocomposite (Fe2O3/CeO2/ZnO) using a straightforward
ronmental risks associated with decomposition products diminish pro­ synthesis approach. Table 1 offers a detailed comparison of the experi­
gressively as the catalytic reaction advances. In light of these findings, mental findings, providing insights into the LEF elimination efficiency
we can conclude that the 30FeCe/ZnO photocatalyst system not only achieved in this study compared to those reported elsewhere. Various
efficiently degrades LEF molecules but also substantially reduces their factors, including catalyst type, dosage, pollutant concentration, pH,
environmental toxicity. and reaction time, significantly impacted the catalyst’s degradation
performance. A thorough examination of existing literature underscores
the superiority of the 30FeCe/ZnO photocatalyst in terms of removal
efficiency. Notably, this catalyst demonstrates the ability to degrade

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Z. Fei et al. Chemical Engineering Journal 493 (2024) 152717

Table 1
Comparison of the current work results with different synthesized photocatalysts for LEF degradation.
Photocatalyst Pollutant Light source Operational Condition Efficiency Stability Ref.
(cycle)

rGO-Bi2WO6 LEF Visible light Catalyst dosage: 0.25 g/L, Time: 120 min, LEF concentration: 10 mg/L, 74.3 % − [49]
and pH: 6
Ag3BiO3/ZnO/BC LEF UV–visible Catalyst dosage: 0.02 g/L, Time: 120 min, LEF concentration: 5 mg/L, and 78.9 % 5 [50]
light pH: 5
g-C3N4/TiO2 LEF Visible light Catalyst dosage: 0.02 g/L, Time: 50 min, LEF concentration: 5 mg/L, and 100 % − [51]
pH: 5
5 wt% Cu2O/WO3 LEF Visible light Catalyst dosage: 0.02 g/L, Time: 80 min, LEF concentration: 20 mg/L, and 97.9 % 4 [52]
pH: 7
ZIF67/N, P-WO3 LEF Visible light Catalyst dosage: 0.03 g/L, Time: 100 min, LEF concentration: 10 mg/L, 91.2 % 5 [53]
(ZNPW) and pH: 9
Fe2O3/CeO2/ZnO LEF Visible light Catalyst dosage: 0.69 g/L, Time: 83.64 min, LEF concentration: 37.9 98.9 % 4 Current
mg/L, and pH: 6.18 study

higher concentrations of the antibiotic compared to previous studies. Declaration of competing interest
Moreover, a noteworthy aspect of this research is the utilization of a pH
value near the intrinsic pH of the LEF solution. These results clearly The authors declare that they have no known competing financial
show the 30FeCe/ZnO nanocomposite’s exceptional photocatalytic ac­ interests or personal relationships that could have appeared to influence
tivity for LEF decomposition, outperforming other previously docu­ the work reported in this paper.
mented catalysts. By utilizing the selected materials’ large surface area,
non-toxic nature, and increased stability in photocatalytic systems, their Data availability
inclusion provides clear benefits. This configuration inhibits electron-
hole pair recombination and promotes higher surface charge transfer The authors do not have permission to share data.
rates. Consequently, the 30FeCe/ZnO photocatalyst presents a compel­
ling strategy for the elimination of LEF from wastewater streams. Acknowledgments

4. Conclusion The authors extend their appreciation to Princess Nourah bint

Abdulrahman University, Riyadh, Saudi Arabia for supporting this work
In summary, a novel Fe2O3/CeO2/ZnO photocatalyst responsive to under the researcher supporting project number (PNURSP2024R205).
visible light were successfully fabricated using a facile hydrothermal The author extend their appreciation to the deanship of scientific
method coupled with impregnation for the first time. The ternary research at Shaqra university for support this research work. FRGS
composite underwent comprehensive characterization via XPS, SEM, FP082-2023.
XRD, BET, TEM, and DRS analyses. The degradation efficiency of
30FeCe/ZnO was evaluated through LEF testing, focusing on the roles of Appendix A. Supplementary data
•
OH and •O–2 radicals in catalytic degradation. Noteworthy degradation
rates, reaching 98.9 %, were achieved with specific operational pa­ Supplementary data to this article can be found online at https://doi.
rameters, such as a catalyst dosage of 0.69 g/L, an irradiation time of org/10.1016/j.cej.2024.152717.
83.64 min, an initial LEF concentration of 37.9 mg/L, and a pH of 6.18.
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