Materials Research Bulletin 161 (2023) 112176

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Materials Research Bulletin

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Research Papers

Zeolite supported CdS/TiO2/CeO2 composite: Synthesis, characterization

and photocatalytic activity for methylene blue dye degradation
Mohammedsani Mahamud, Abi M. Taddesse, Yiheyis Bogale *, Zewdu Bezu
Department of Chemistry, College of Natural and Computational Sciences, Haramaya University, Ethiopia

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

Keywords: A novel ternary composite CdS/TiO2/CeO2 and its zeolite-support were synthesized and characterized using
Degradation XRD, SEM, UV–Vis DRS and PL spectroscopy. The photocatalytic performance of the synthesized nanocomposites
Zeolite was investigated using an aqueous solution of Methylene Blue (MB) dye and a real sewage sample solution.The
Composite
photocatalytic activity of the zeolite-supported composite was superior to the naked CdS/TiO2/CeO2, binary, and
Photocatalysis
single counter constituents. The effect of operational parameters on MB dye degradation was evaluated, and a
Wastewater
Visible light significant photodegradation was recorded by a zeolite-supported CdS/TiO2/CeO2 composite. The supported
composite showed significantly higher performance on the discoloration of MB (99.9%) than the real sewage
sample solution (78.7%) based on the optimized parameters. The recyclability study of the spent photocatalyst
exhibited 86.0% degradation of MB after four consecutive cycles, indicating the stability of the composite. Based
on the findings, this research offers insight into a new and efficient visible-light-driven photocatalyst for the
degradation of organic dyes in wastewater.

1. Introduction increased attention and has replaced other methods for treating waste
water [8,9]. Among the developed methods of waste water treatment,
In the recent decade, the rate of population growth has increased heterogeneous photocatalysis is the most effective way for degrading
with the expansion of industrialization. In the year of industrialization, organic dye pollutants [8,9]. The photocatalytic oxidation process is
the living standard of the human being is improving. However, the thought to mineralize organic pollutant compounds into carbon dioxide
industry’s disposal or wastage has posed a series of problems related to and metal salts by releasing numerous and powerful reactive oxidants
environmental pollution [1]. On the other side, due to the intensification like as hydroperoxyl radicals (HO2•), hydroxyl radicals (•OH), and su­
of agricultural production, releasing chemicals into the environment is peroxide ions (O2•), all of which are important in the organic degra­
another source of environmental pollution [2]. In connection to this, the dation process [10].
dye manufacturing industries are one of the main causes of water TiO2 has become the most extensively studied photocatalyst due to
pollution [3]. Due to their aromatic amine group nature, organic dyes its strong solubility, good catalytic activity, excellent chemical and op­
used in dyeing, printing, textile, photography, and cosmetics are tical stability, and nontoxic and affordable price [11]. However, because
particularly hazardous [4]. One of the dyes that are frequently used in of its wideband gap (3.2 eV), it is limited to visible light absorption and
the textile industry is methylene blue, which contains a variety of aro­ thereby exhibits low photocatalytic efficiencies. A variety of approaches
matic amine groups that are extremely harmful to aquatic ecology and have been used over the years to solve these drawbacks, including the
challenging to degrade [5]. Before releasing it into the environment, it coupling of TiO2 with semiconductors with small band gaps like CdS and
must be degraded from contaminated water since it is detrimental to the CeO2 [12]. CdS has a lower band gap (2.42 eV) which enables much
ecosystem [6]. Reverse osmosis, aerobic oxidation, membrane filtration, stronger photo-oxidative capability and higher efficiencies for photo­
liquid-liquid extraction, absorption, ion exchange, and advanced catalytic degradation when coupled with TiO2 [13]. The difficulty, un­
oxidation process are some of the development methods for treating fortunately, is the quick recombination of e− -h+ charge carriers, and the
industrial effluents [7]. effective sequence of a photocatalytic transferring electron is insuffi­
In recent years, the advanced oxidation process has received cient. To overcome this, the binary system was extended to the ternary

* Corresponding author.
E-mail address: [email protected] (Y. Bogale).

https://doi.org/10.1016/j.materresbull.2023.112176
Received 7 December 2022; Received in revised form 22 January 2023; Accepted 23 January 2023
Available online 28 January 2023
0025-5408/© 2023 Elsevier Ltd. All rights reserved.
M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

system and evidenced better efficiencies than the TiO2 [14]. 2.2.3. Preparation of CdS nanoparticle
In this connection, the synthesis of TiO2-based ternary systems such In separate beakers, equimolar of (0.1 M/2.6 g) Cd(CH3COO)2. 2H2O
as ZnS–TiO2/RGO [15], MoS2/CdS/TiO2 [16], and g-C3N4/TiO2/CdS and Na2S⋅9H2O (2.4 g) solutions in 100 mL deionized H2O were pre­
[17] have been reported. The fabrication of ternary composite may pared for the synthesis of CdS nanoparticles. Following that, a clear
result in a large role of hetero interface with matching band potential, solution was formed by adding drop-wise Na2S⋅9H2O solution to the Cd
allowing for multi-step charge transfer and further interfacial charge, (CH3COO)2 solution while continuously stirring for 2 h at 24 ◦ C. The
resulting in greater photocatalytic activity than binary composite. subsequent yellow precipitate was centrifuged to collect it, and the
Additionally, several approaches have been established to use the right residue was then removed by washing it three times with deionized H2O
support to increase the photocatalyst efficiency of the nanocomposites. and C2H5OH. The resulting CdS was then dried for 5 h at 70 ◦ C and the
Among them, Zeolite has been successfully used to load a variety of solid product was heated in a furnace to 300 ◦ C for 2 h, crushed into
nanoparticles [18]. Zeolites are porous inorganic materials with uniform powder, and stored in a container [16].
pore size, a high surface area of the internal active site, and strong
adsorption capabilities [19]. The photocatalytic efficiency of 2.2.4. Preparation of CdS/TiO2 composite
CdS–TiO2/L-zeolite was more competent than bare CdS/TiO2 [13]. In a specific synthesis, 0.63 g of the as-produced TiO2 nanoparticle
Zeolite with its well-defined structure and micro-porous cavities works was mixed with 100 mL of deionized H2O and sonicated for 30 min
as a good candidate for nanoparticle supporting and hosting [20,21]. before being agitated for 30 min. Then, appropriate amounts of the
Herein, the better photocatalytic efficiency of ternary CdS/TiO2/CeO2 precursors for CdS (0.266 g, 1 mmol Cd(CH3COO)2⋅2H2O mole) and
composite was hypothesized. The ternary system’s adsorption capacities sodium sulfide nonahydrate (Na2S⋅9H2O) (0.24 g, 1 mmol) were mixed
facilitate trapping pollutants to the surface, improving the effectiveness to the suspension and cooled to 24 ◦ C (RT). Following centrifugation, the
of the dispersed nanoparticles. Hitherto, a variety of photocatalysts white precipitate was rinsed with deionized H2O, dried in a 60 ◦ C oven,
based on TiO2, CdS, and CeO2 nanomaterials were synthesized. To the and then calcined for 2 h at 300 ◦ C [24].
best of our knowledge, no research has been reported so far concerning
the zeolite-supported ternary CdS/TiO2/CeO2 nanocomposite for pho­ 2.2.5. Preparation of TiO2 /CeO2 composite
tocatalysis application. Hence, in this study, a novel zeolite-supported Under this investigation, a TiO2/CeO2 hybrid nanocomposite was
CdS/TiO2/CeO2 photocatalyst was prepared and characterized to synthesized from CeO2 powder and TiO2 precursor using the following
investigate its catalytic capacity for the degradation of methylene blue approach. First, 0.28 g CeO2 powder was sonicated in 80 mL propanol
(MB) as a model pollutant. with 16 mL deionized H2O for 30 min before adding 8 mL Ti(BU)4 to the
solution. The formed solid residue was separated and dried in an oven at
2. Materials and methods 100 ◦ C for around 5 h after the suspension solution was thoroughly
agitated for 24 h. The dried solid was then heated for 3 h at 400 ◦ C [25].
2.1. Chemicals and reagents
2.2.6. Synthesis of CdS/TiO2/CeO2composite
Ce(NO3)3⋅6H2O (Sigma Aldrich, USA) and NH3 solution (25% Loba The ternary composite was synthesized by combining the proper
chemicals Ltd, India), Ti(OC4H9)4 (Aldrich, reagent grade) and 2-propa­ quantity of TiO2/CeO2 binary powder with different molar ratios of the
nol solvents (ACS, reagent grade), Cd(CH3COO)2⋅2H2O (Sigma Aldrich, precursors of CdS nanoparticle (Cd(CH3COO)2⋅2H2O and Na2S⋅9H2O) in
reagent grade), Na2S⋅9H2O) (ACS, reagent grade), used as the starting deionized H2O. Accordingly, 1 g of TiO2/CeO2 powder was dispersed in
materials for the synthesis of CeO2, TiO2, and CdS, respectively and 100 mL of deionized H2O and sonicated for 2 h. After 1.5 h of sonication,
zeolite (CBV 400, SiO2/Al2O3 ratio of 5:1 ratios) were used. NaHCO3, Cd(CH3COO)2⋅2H2O was mixed and the solution was sonicated again.
(reagent grade, adhere Mumbai), HNO3 (69% LR, Breck land Scientific The aforesaid mixture was stirred continuously for 3 h while the same
Supplies, UK), NaOH (97.5% BDH Chemicals Ltd, England), NaNO3 molarity of Na2S⋅9H2O was added drop-wise. For all ratios, the pro­
(Sigma, S5506, Assay 99.5%), CH3OH (ACS reagent, 99.8%), C2H5OH cedures used were the same except for the amount of CdS precursor. For
(97% fine chemical, Ethiopia), double distilled H2O, deionized water, the preparation of 2:1 ration, 0.66 g Cd(CH3COO)2⋅2H2O and 0.6 g
and methylene blue (MB) dye were used. Na2S⋅9H2O was added to 1 g TiO2/CeO2; for the preparation of 3:1
ration, 0.99 g Cd(CH3COO)2⋅2H2O and 0.9 g Na2S⋅9H2O was added to 1
2.2. Preparation of as-synthesized composites g TiO2/CeO2; for the preparation of 4:1 ratio, 1.33 g Cd
(CH3COO)2⋅2H2O and 1.2 g Na2S⋅9H2O was added to 1 g TiO2/CeO2.
2.2.1. Preparation of CeO2 nanoparticle The final product was supposed to be a CdS/TiO2/CeO2 composite and
Ceria nanoparticle was synthesized via the precipitation approach was done in three molar ratios of CdS: TiO2/CeO2 (2:1, 3:1, and 4:1).
with a slight modification of the procedure reported earlier [22]. In Following filtration, each precipitate was separated and rinsed three
deionized water, 0.1 M of Ce(NO3)3⋅6H2O was mixed and stirred for 30 times with deionized H2O and C2H5OH before drying for 12 h at 100 ◦ C
min. Aqueous NH4OH was gradually dropped to the above mixture and heating for 2 h at 200 ◦ C, and the powder was ground into fine
while being stirred constantly until precipitation was completed. For particles.
another 2 h, the stirring was continued and the pH of the reaction was
kept at 10. The precipitation process was then completed by agitating 2.2.7. Synthesis of zeolite supported CdS/TiO2/CeO2 photocatalyst
the sample solution for 12 h. After 1 h of stirring, the ash-colored so­ The zeolite-supported ternary composite was synthesized by the
lution was changed into a yellow mixture. The product was therefore left impregnation method. About 2 g of CdS/TiO2/CeO2 (2:1) was added to a
to settle for 12 h before decanting the resulting yellow slurry. The 0.3 g of zeolite (CBV400 SiO2/Al2O3 5.1) in 100 mL of deionized H2O.
remaining precipitate was filtered and washed with C2H5OH and Then, the solution was thoroughly stirred using a magnetic stirrer at 84
deionized H2O several times. After drying in a 140 ◦ C oven for 12 h, the ◦
C for 2 h and the solvent was evaporated. The obtained solid was dried
obtained product was calcined at 500 ◦ C for 3 h. and pulverized with a mortar and pestle. The powdered product was
then sintered for 1 h at 300 ◦ C to yield the zeolite-supported nano­
2.2.2. Preparation of TiO2 nanoparticle composite [26].
TiO2 nanoparticle was synthesized using the previously described
sol-gel process [23]. 2.3. Characterization

Phase, purity, and size of the primary crystallite materials were

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

determined with an X’pert PRO diffractometer (XRD) (PANalytical). The

particle size was determined using the Scherrer formula based on the
width of the X-ray peaks [27].
Kλ
D= (1)
βcosθ
In which D was the crystallite size in nm in size, K was the form factor
constant assumed to be 0.9, β was the full width at half maximum
(FWHM) in radians, λ was the X-ray wavelength (0.15406 nm) for Cu
target K α1 radiation, and θ was the Bragg’s angle.
Photoluminescence(PL)intensity of the as-synthesized nano­
composite was carried out using RF-5301 PC Shimadzu photo­
luminescence under an excitation λ of 280 nm. Scanning-Electron
Microscopy (SEM) (Hitachi H-7500, Tokyo, Japan) with a voltage of
10 kV was used to determine the surface morphology and particle size
dispersion of the solids. The size of the as-synthesized composites was
determined from the micrographs using Nano-Measurer software. The
absorption maximum estimation of as-synthesized composite samples Fig. 1. XRD pattern of TiO2, CdS/TiO2 and TiO2/CeO2, CdS/TiO2/CeO2, and
was determined by Ultraviolet-visible Diffuse Reflectance Spectropho­ Zeolite-CdS/TiO2/CeO2.
tometer (UV–vis DRS) (Shimadzu UV-3600, Kyoto, Japan) using a quartz
cuvette by scanning in a wavelength range of 200–800 nm. 36.7◦ , 36.84◦ , 37.8◦ , 43.9◦ , 47.5◦ , 47.9◦ , 50 0.8◦ , 51.8◦ , 53◦ , 53.9◦ , 55◦ ,
56◦ , 59.1◦ , 62.7◦ , 68.8◦ , 69.4◦ , 69.5◦ , and 76.7◦ Among these patterns,
2.4. Determination of point of zero charge the diffraction peaks at 2θ values of 28.65◦ , 33.09◦ , 56◦ , 59.1◦ , 69.4◦ ,
and 76.7◦ referred to crystal face (111), (200), (311), (222), (400) and
The previously mentioned approach was used to find the point of (331) could be accountable for the structure of cubic fluorite of the
zero charges [28]. crystal CeO2 (JCPDS card no 96–434–3162) [31], while peaks at 2θ
value of 26.35◦ , 36.7◦ , 43.9◦ , 50.8◦ , 51.6◦ , 53◦ , and 69.5◦ are in good
2.5. Photocatalytic degradation studies accordance with the (002), (102), (110), (112), (201), (004) and (211)
and could be responsible for the greenockite structure of CdS nano­
The catalytic efficiency of a zeolite-CdS/TiO2/CeO2 for the discol­ particle (JCPDS card no 96–101–1055) [12]. Whereas the peaks at the
oration of MB dye solution was investigated. In this experiment, 100 mL 2θ value of 25.23◦ , 36.8◦ , 37.8◦ , 48.07◦ , 53.9◦ , 55◦ , 62.7◦ , and 68.8◦ are
of MB dye aqueous solution was mixed in the beaker with 0.15 g of in good accordance with the (101), (103), (004, 200), (105), (211) (204)
zeolite-CdS/TiO2/CeO2. The MB aqueous solution was kept in the and (166) (JCPDS card no 96–101–0943) and these could be associated
absence of light for 30 min to establish adsorption-desorption equilib­ for the formation of anatase in the ternary system [32]. This indicated
rium. Following that, the catalyst was homogenized using a magnetic the presence of the three phases in the as-synthesized ternary composite
stirrer in the dark. The mixture was then exposed to a tungsten lamp system. Among the ternary systems, the ratio (2:1) was selected for the
(TORCH) light source (85 W, 50–60 Hz) placed perpendicular to the subsequent photocatalytic experiment based on evidence obtained from
reactor. The length between the top of the reactor and the bulb was 12 UV–vis and preliminary photocatalytic experiment. This ternary system
cm. A 10 mL sample was taken every 20 min to monitor the photo­ was then immobilized to zeolite support.
degradation reaction of MB solution, and the absorption range of 664 PXRD pattern of the supported ternary system displayed peaks at 2θ
nm was recorded as a function of irradiation time and centrifuged at values of 6.4◦ , 10.4◦ , 18.88◦ , 23.82◦ , 25.34◦ , 27.34◦ , 31.74◦ , 38.18◦ ,
3000 rpm for 20 min before getting analysed. A UV–Visible instrument 48.16◦ , 54.12◦ , 55.36◦ , 62.96◦ , 68.89◦ , 70.48, and 75.36◦ Here, the peak
was used to measure dye absorbance at the maximum of the MB dye appeared at 2θ values of 6.4, 10.34, 18.88, and 23.84◦ (111), (220),
solution [29]. (331), and (620) could be assigned to the zeolite. The rest of the peaks
`Using the equation, the photo removal percentage was obtained represent the three components CeO2, TiO2, and CdS in the ternary
(Eq. (2)). system. The average crystal sizes of the photocatalysts were computed
A0− At via the Scherer equation as indicated in Table 1. The result revealed that
% Degradation = × 100 (2) all of the materials prepared were in the nano range.
A0
Where A0 is the initial absorbance of MB dye in solution and At is the 3.1.2. UV–vis diffuse reflectance study
absorbance at the time (t). UV–vis DRS scans were utilized to evaluate the optical features of the
as-prepared photocatalysts. The diffuse absorption edge was calculated
3. Results and discussion by intersecting the line of tangency with the descending component of
the absorption peak at the wavelength axis (nm) [33]. Eq. (3) was
3.1. Characterization employed to calculate the band gap energy of the photocatalyst (Eg).

3.1.1. X-ray diffraction study

Fig. 1 depicts the distinctive peaks on the XRD patterns of the as- Table 1
produced photocatalysts: TiO2, CdS/TiO2, TiO2/CeO2, CdS/TiO2/ Average crystallite size of the as-synthesized materials: TiO2, CdS/TiO2, TiO2/
CeO2, and zeolite-supported CdS/TiO2/CeO2. Diffraction peaks found at CeO2, CdS/TiO2/CeO2 and zeolite supported CdS/TiO2/CeO2.
scattering angles of 2θ of 25.38◦ , 36.9◦ , 37.8◦ , 38.6◦ , 48.1◦ , 52.1◦ , 54◦ , As fabricated composite 2θ (degree) β(radian) D(nm)
62.3◦ , 68.8◦ , and 70.4◦ are indexed to the (101), (103), (004), (112), TiO2 25.32 0.00857 16.59
(200), (202, 105), (213), and (116). (220). These peaks were responsible CdS/TiO2 25.4 0.010289 13.86
for TiO2 anatase [30] (JCPDS card No 96–500–0224). TiO2 /CeO2 25.26 0.00644 21.55
In the case of the as-synthesized ternary system, the peaks of CdS/TiO2/CeO2 24.98 0.02800 5.00
Zeolite-CdS/TiO2/CeO2 25.45 0.00811 17.5
diffraction exhibited were at 2θ values of 25.23◦ , 26.35◦ , 28.65◦ , 33.09◦ ,

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

1240 by SEM (Fig. 4). The typical SEM images of bare ternary CdS/TiO2/CeO2
Eg = (3)
λmax composite demonstrated fluffy-like morphology (Fig. 4a) with some
incidents of agglomerations. In sharp contrast, the distinct morphology
While Eg and λmax were the bandgap energy (eV) and the absorption
of some of the components of the composite was observed in the zeolite-
wavelength (nm), respectively.
supported case. For example, the octahedral units of the anatase struc­
The optical absorption characteristics of the as-prepared catalysts
ture of TiO2 and cubic structure of CeO2 were well discernible from the
were measured using a UV–Vis DRS at λ ranging from 200 to 900 nm.
micrograph shown although the morphology of CdS was obscured. The
Tauc’s equation (Eq. (4)) was employed to precisely determine the Eg of
average particle size calculated for Figures (4a) and (4b) by using the
the samples [34].
ImageJ software analysis were 130 nm and 230 nm, respectively.
( )
(αhν)n = A hν − Eg (4)
3.1.5. Determination of point of zero charge
Such that, α, hv, Eg, and A were the absorption coefficient, light In this study, the PZC was estimated to be at a pH of 5.04. The
frequency, band gap, and constant, respectively, and n was 2 or 1/2 for interaction of photocatalysts and cation of MB dye (positively charged)
direct or indirect transitions. was very low because of the existence of electrostatic repulsion force
Based on the indirect transition, a plot of (hv)1/2 vs hv (Fig. 2) in­ between them (cation-cation repulsion force) [34]. Thereby, the pho­
dicates for TiO2, CdS/TiO2, TiO2/CeO2, CdS/TiO2/CeO2, and Zeolite- tocatalytic degradation efficiency of photocatalysts at pH below the
CdS/TiO2/CeO2. The absorption band gap energy was obtained by point of zero charges showed relatively less efficiency. Conversely, at the
extrapolating hv to (αhv)1/2. The Eg values for TiO2, CdS/TiO2, and pH above the PZC, the photocatalyst surface becomes negatively po­
TiO2/CeO2 were calculated to be 3.2 eV, 2.44 eV, and 2.75 eV, respec­ larity, and hence, the interaction of cation MB dye and photocatalyst
tively. Furthermore, the Eg values of the CdS/TiO2/CeO2 and Zeolite- appeared to be higher because of the existence of an attractive force
CdS/TiO2/CeO2 composites were 2.12 eV and 2.10 eV, respectively, between them. The other reason is the availability of more OH− which
when compared to TiO2, indicating the successful electronic combina­ oxidized to form highly active •OH radicals [16]. The values of pHinitial,
tion of TiO2, CdS, and CeO2. This suggests that the composite could serve pHfinal, and pHfinal versus pHfinal-initial were shown in Fig. 5. The PZC
as an efficient catalyst in the photodegradation reactions of MB when value for the Zeolite supported ternary system has acidic nature below
exposed to visible light. 5.04, basic nature above 5.04, and neutral at a pH of 5.04. According to
the photodegradation results, greater adsorption and photocatalysis
3.1.3. Photoluminescence (PL) study were attained at pH levels higher than the catalyst’s PZC.
The PL intensity of TiO2, CdS/TiO2, TiO2/CeO2, CdS/TiO2/CeO2 and
zeolite supported CdS/TiO2/CeO2 were measured. Fig. 3 depicts the
3.2. Photocatalytic studies
intensity order: S1 > B1 ≈ B2 > TA1 > ZAST.
In the case of binary and ternary photocatalysts, the charge pair
3.2.1. Photocatalytic activities of photocatalyst
electrons, and holes delayed recombination rate was formed and hence
The photodegradation efficiency of the as-synthesized nano­
excitation PL intensity is de-escalated. This is due to a combination of
composites was assessed using the water-soluble MB dye with the pro­
factors including a decrease in excitation PL intensity, a greater ability of
cedure reported earlier [29]. Methylene blue dye was selected as a
coupled composite materials to effectively segregate photoinduced
model pollutant since it is commonly used in different industries and
electrons, a higher delayed rate of recombination, and improved pho­
expected to be there in the effluents. In addition to this, most of the
tocatalytic activity. In this investigation, it was indicated that the lower
industries in developing countries do not have a proper facility for
PL emission spectra were recorded for B1, B2, TA1, and ZAST. As a
effluent treatment. The experiment used visible light as an irradiation
result, it was discovered that single systems had greater PL intensities
source, and the photodegradation of the as-synthesized catalyst was
than binary systems, and binary systems intern had higher PL intensities
measured using MB, which exhibited a specific absorbance at 664 nm.
than their ternary photocatalyst.
Accordingly, the photocatalytic efficiencies of TiO2, CdS/TiO2, TiO2/­
CeO2, CdS/TiO2/CeO2, and zeolite-supported CdS/TiO2/CeO2 nano­
3.1.4. SEM image analysis
composites were measured under visible light irradiation. UV–vis
The surface morphology appearances of the as-synthesized hetero­
analysis of aliquots at regular intervals was used to track changes in the
structure, CdS/TiO2/CeO2, and zeolite-CdS/TiO2/CeO2 were obtained
relative amount of MB over time.
The discoloration of MB dye was facilitated as the irradiation time
was prolonged in the presence of the as-synthesized nanocomposite.
This was indicated by decreasing the absorption peak of MB. By
graphing Ct/Co with irradiation time, the removal rate was calculated.
An adsorption process under dark settings was permitted to take place
for 30 min before the photocatalytic reaction. Meanwhile, under the
same experimental settings, blank tests were performed without
photocatalysts.
The result obtained for the discoloration of the dye in the absence of
the photocatalyst was negligible (less than 12%) for the entire duration
of the experiment revealing the importance of the photocatalysts in a
such study [35]. Generally, the following trend was exhibited for the
experiment: TA1 > B1 > B2 > S1 > MB blank. The binary composites
CdS/TiO2 and TiO2/CeO2 exhibited improved degradation for MB dye
under visible light irradiation than the pristine TiO2 possibly because of
the delay of back reaction between CdS and CeO2 with TiO2 which
produces more number of charge carriers that would enhance the
degradation performances (Fig. 6). Thereby, the efficiency of
photo-generated e− -h+ in CdS/TiO2 and TiO2/CeO2 was greater than
Fig. 2. Tauc plot photocatalyst of TiO2 (S1), CdS/TiO2 (B1) TiO2/CeO2 (B2) bare TiO2. Furthermore, the combination of TiO2 with CdS and CeO2
CdS/TiO2/CeO2 (TA1) Zeolite CdS/TiO2/CeO2 (ZAST) based on Tauc’s plot. provides a method for raising the abundance of exciting species (e− -h+

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

Fig. 3. (a) The PL emission spectra of (S1), (B1), (B2), (TA1) and (ZAST) Photocatalyst (b) The PL emission spectra of (B1), (B2, TA1) and (ZAST) photocatalyst.

Fig. 4. SEM image of CdS/TiO2/CeO2 (a) and zeolite CdS/TiO2/CeO2 (b).

pairs), hence prolonging their lifespan and promoting photocatalytic (3:1) TA2 and CdS: TiO2/CeO2 (4:1) TA3, were evaluated to achieve the
activity toward the dye [36,37]. optimum point. Among these ratios, the 2:1 form of CdS/TiO2/CeO2 has
In the particular instance of TiO2/CeO2 under visible light irradia­ shown the highest photocatalytic activity. Hence, the ratio 2:1 has been
tion, photogenerated electrons in the CB of CeO2 could be easily moved selected for the subsequent immobilization to zeolite support. However,
to the surface of TiO2 via the heterojunction (n-p), while photoinduced in terms of photocatalytic performances, all of the as-synthesized
h+ in the VB of TiO2 could also migrate to the surface of CeO2, implying ternary composites performed better than their binary and single
that the different transfer path of e− and h+ can successfully account for counterparts. This could be the reason for having a high transfer ability
prolonged recombination [38]. In such a way, the photogenerated e− -h+ of electrons, and more than one junction point of interface which is
pairs are isolated effectively by the n-p junction formed in the hetero­ responsible for effectively separating electron-hole pair [26].
structures TiO2/CeO2 interface, and the activity of the photocatalyst was Comparing the single (host), binary, and naked ternary counterparts, the
enriched [39]. In an A-type heterojunction system (CdS/TiO2), however, zeolite-supported CdS/TiO2/CeO2 composite showed a much greater
the enhanced catalytic activities of TiO2 could be initiated by CdS CB percentage degradation (99.9%) than the others (Fig. 7). This could be a
electrons involved in the photoreduction process [40]. In the CdS/TiO2 result of the actual charge separation between e− and h+ pairs in excited
band gap configuration, electrons formed in CdS migrate from the CB of states, which keeps the recombination of charge pairs for an extended
CdS to the CB of TiO2, while h+ remains in the VB of CdS, preventing period when subjected to visible light irradiation. The synergistic
e− -h+ pair recombination. function of significant visible light absorption and improved charge
The comparisons of ternary composites which have been synthesized transfer efficiency between components in zeolite-CdS/TiO2/CeO2
by different molar ratios of CdS: TiO2/CeO2 (2:1) TA1, CdS: TiO2/CeO2 composite leads to outstanding photocatalytic activity against MB

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

discoloration [13]. For comparison, the synthesized nanomaterials were

compared with other reported studies on methylene blue degradation
(Table 2).
The zeolite acts as a support for the composite, enhancing its
adsorption capacity and resulting in a higher percentage of pigment
molecules around the composite. Good composite dispersion, on the
other hand, increases the active sites around the adsorbed molecules,
resulting in a higher pollutant breakdown rate [26]. Furthermore, the
zeolite framework’s strong electrostatic field could successfully separate
the e-h+ created during photoexcitation of the ternary composite. In
comparison to the naked ternary composite, this resulted in a reduced
recombination rate and a higher photodegradation efficiency. Overall,
the results demonstrated that zeolites have a dual role in promoting the
photocatalytic activity of the composite (by decreasing e¡-hþ recom­
bination and enhancing adsorption capacity) [23,44].

3.2.2. Effect of some operational parameters on photocatalytic degradation

Fig. 5. A plot of the point of zero charges of zeolite-CdS/TiO2/CeO2
photocatalyst.
3.2.2.1. Effect of pH. The pH of the solution influenced dye decolor­
ization. The surface charge of the zeolite-CdS/TiO2/CeO2 particles was
affected by the pH of the solution, altering the potentials of catalytic
processes. As a consequence, the surface adsorption of dye varies,
causing the reaction rate to alter. In acidic or basic conditions, the
surface of the as-synthesized photocatalyst could be protonated or
deprotonated. As a result, the influence of pH on the surface of the
photocatalyst was examined by fixing the quantity of photocatalyst at
0.15 g/L and the amount of MB at 10 mg/L. As demonstrated in Fig. 8,
the degradation efficiency of the photocatalyst decreased from pH 2 to
pH 4 possibly because the later pH is near the isoelectric point where the
interaction between dye and photocatalyst is less. However, from pH 4
to pH 6, the percentage of degradation increased. This could be a result
of the negatively charged surface of the photocatalyst at this pH range,
which makes methylene blue’s capacity to adsorb to the surface of the
photocatalyst somehow more effective.
The maximum percentage efficiencies of photocatalytic degradation
of the photocatalyst was found at pH 8 herein, the more availability of
OH− , and higher columbic attraction force between methylene blue
solution and the photocatalyst could be the possible reason for the
higher percentage efficiency. Whereas from pH 8 to pH 12, the per­
Fig. 6. Values of Ct/Co as a function of irradiation time for a comparison of centage degradation declined perhaps due to alkaline conditions
single and binary as-synthesized photocatalyst and MB under visible light (load favouring less the complexation process seemingly due to viable
at 0.15 g/L, Initial dye amount at 10 mg/L, and pH at 8). adsorption by hydroxyl groups with the dye molecules [45,35]. The
percent degradation rate of zeolite-supported CdS/TiO2/CeO2 over MB
solution was 90.04, 88.7, 93.81, 99.3, 92.13, and 73.56% at solution pH
2, 4, 6 8, 10, and 12 with a rate constant of 0.0177, 0.014, 0.023, 0.041,
0.0201, and 0.0130 min− 1, respectively.

3.2.2.2. Effect of initial concentration. The initial amount of MB dye in a

specific photocatalytic process is a critical aspect that must be consid­
ered. In this study, the impact of the concentration of MB was investi­
gated by increasing the amount of dye from 10 mg/L to 50 mg/L, while

Table 2
Comparison of photocatalytic degradation of MB by different nanocomposites.
Materials MB degradation Efficiency (%) References

TiO2 28@120 min This work

TiO2/CeO2 47.52@120 min This work
CdS/TiO2 52.8@120 min This work
CdS/TiO2/CeO2 83.2@120 min This work
Zeolite CdS/TiO2/CeO2 99.9@120 min This work
CdS/TiO2 85.9@120 min [41]
CeO2/g-C3N4 90.1%@180 min [42].
Zeolite WO3/Fe3O4 97.3%@120 min [43].
Fig. 7. Values of Ct/Co as a function of irradiation time for a comparison MoS/CdS/TiO2 95%@180 min [16].
ternary of as-synthesized photocatalyst and MB under visible light (load at 0.15 L zeolite CdS/TiO2 98%@ 120 min [13].
g/L, initial dye amount at 10 mg/L, and pH at 8). Zeolite ZnO/Fe2O3/MnO2 97%@120 min [26].

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

In this study, the catalyst was tested at concentrations ranging from

0.05 to 0.3 g/L.The degradation rate of MB rises remarkably from 77.09
to 99.9% with the increase in catalyst dosage. The conforming rate (k-
constant) for 0.05, 0.1, 0.15, 0.2, and 0.3 g/L were 0.0102, 0.0146,
0.0158, 0.0184, and 0.0126 min− 1, respectively for 120 min irradiation
time. The factor that indicates the increase of dye adsorption with the
increase of adsorbent dosage could be explained by the higher number of
exchangeable sites accessible for interaction with dye molecules [47].
Fig. 10 depicts the effect of increasing catalyst concentrations from
0.05 to 0.3 g/L on MB degradation. Removal efficiencies exhibit a
characteristic of the heterogeneous photocatalytic regime and increase
with increasing catalyst quantities [48]. So the catalyst absorbs more
light and destroys more contaminants, the higher degradation efficiency
when more catalyst was added to the MB solution. After the catalyst
concentration exceeds 0.15 g/L, the degradation efficiency increases to
97.8%. After 120 min of photocatalytic activity, the percentage degra­
dation was 100% for 0.2 g/L, which was most likely due to enhanced
dispersion [13,49]. The de-escalation observed after a catalyst load of
0.3 g/L, on the other hand, was explained by a reduction in the number
Fig. 8. Values of Ct/Co as a function of irradiation time using ZAST photo­ of accessible active sites for generating free •OH radicals. Light blocking
catalyst at different pH under visible light (ZAST load at 0.15 g/L and Initial caused by an increase in water turbidity due to the high number of
concentration of MB at 10 mg/L). suspended photocatalyst particles and active site blocking induced by
catalyst concentration aggregation were the most common causes of
keeping a fixed mass of catalyst load [46]. these features.
In the present study, a consistent decrease in decolorization effi­
ciency is observed with an increase in dye amount (Fig. 9). This could be 3.2.2.4. Identifying pre-dominant radical. Scavenger in solution was
owing to the increased concentration of MB and hence, more organic widely used as a ROS acceptor in photocatalysis processes to ensure
contaminants were adsorbed on the surface of zeolite-CdS/TiO2/CeO2 which reactive oxygen species play a vital role in MB degradation. ROS
however, less number of photons were accessible to reach the catalyst were those that prevent the excited CB electron from recombination,
surface and therefore less •OH are formed, thus resulted in a lesser hence increasing the catalyst’s degradation efficiency [50]. The meth­
amount of degradation percentage. So, the maximum efficiencies of odology utilized to assess the pure photocatalyst was radical scavengers
ZAST photocatalyst were observed at 10 mg/L among the different to detect the reactive oxygen species that perform on the photocatalysis
amounts of the initial amount of MB dye because of high adsorption and of MB.
good dispersion of dye on the surface of the catalyst. To further understand the photocatalytic process, photocatalytic
activity was compared in the presence of radical scavengers was per­
3.2.2.3. Effect of photocatalyst load. The photodegradation of dye was formed utilizing AgNO3 as the O−2 , CH3OH as the •OH, and NaHCO3 as
enhanced with increasing concentrations of catalyst, which was a hole (h+) scavengers. The results (Fig. 11) showed that the addition of
characteristic of heterogeneous photocatalysis. The number of active methanol reduces the catalytic efficiency of MB, indicating that meth­
sites on the photocatalyst surface increased as the amount of catalyst anol might consume •OH to limit the catalytic activity under visible
increased, resulting in the creation of more •OH radicals, which may light [4]. These findings show that •OH played a role in the photooxi­
contribute to the actual removal of the dye solution. After a specific dation of the zeolite-CdS/TiO2/CeO2 composite. In the absence of a
amount of catalyst was added, the solution becomes turbid and so in­ scavenger, photocatalytic degradation of MB was 99.9%. However,
hibits UV–vis rays, resulting in a decrease in percentage degradation
[46].

Fig. 10. Values of Ct/Co as a function of irradiation time using ZAST photo­
Fig. 9. Values of Ct/Co as a function of irradiation time using ZAST photo­ catalyst at different catalyst loads of MB (pH at 8 and initial amount of MB at
catalyst at varied initial MB amounts (ZAST load at 0.15 g/L and pH at 8). 10 mg/L).

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

time. Subsequently, the 2nd, 3rd, and 4th cycles degraded% decoloriza­
tion of 94.7, 90.3, and 86.7, respectively (Fig. 12). The kinetic rate of all
four cycles was evaluated and rate constants of 0.0418, 0.0226, 0.0194,
and 0.0159 min− 1 were achieved for the respective cycles. Approxi­
mately 14% of the drop was found between the first cycle and the fourth
cycle. The high stability of zeolite-CdS/TiO2/CeO2 photocatalyst in­
dicates its promising applications in degrading organic water pollutants.

3.4. Real sample analysis

The% degradation of the MB solution and the real sample was 99.9%
and 78.7% with a k value of 0.0418 and 0.0157 min− 1, respectively
(Fig. 13). The result showed that the efficiency of photocatalytic
degradation was decreased relative to the optimized one for the real
sample. This could be because of the various type of dye composition
contained in the wastewater and its higher concentration opaque of the
solution. This is accountable for the different types of anionic and
cationic dyes used together in the textile industry. It should be noted
that the higher concentration of both types of dyes in the real sample
Fig. 11. Graph of Ct/Co as a function of irradiation time in the presence and suppressed the degradation efficiency of ZAST due to the refrained of
absence of scavengers over MB dye under visible light (ZAST load at 0.15 g/L, visible light from arriving at the surface of the catalyst by particles of
an initial amount of MB at 10 mg/L, and pH at 8. dyes that resulted in a decreased number of active sites (photoinduced
holes and electrons) of the catalyst [52,44]. The degradation perfor­
when CH3OH, NaHCO3, and AgNO3 were added, the percentages fall to mance in the textile effluent was found to be lower than that of the MB
83.2, 92.0, and 78.90%, respectively. AgNO3 and methanol greatly solution since the effluent was quite complex and contains not only a
prevented MB degradation, implying that O.2 and •OH played important mixture of dyes but also additional chemicals from the decolorizing
roles in the photocatalytic activity (Fig. 11). procedures [26,52].
The effect of methanol and silver nitrate as effective scavengers of
•OH and ●O2 was studied to determine the mechanism of photo­ 3.5. Possible mechanism of photocatalytic degradation
degradation. The inhibitory effect of CH3OH and AgNO3 on the discol­
oration of MB was significant to suggest the photocatalytic mechanism The catalytic degradation analysis indicates that zeolite-CdS/TiO2/
of the ternary composite [51]. The presence of NaHCO3 affected the CeO2 photocatalyst exhibits high photocatalytic activity. The enhanced
photodegradation of the target dye slightly. Therefore, it could be activity was due to two factors. Zeolite, as a substrate for CdS/TiO2/
concluded that superoxide radical (●O2) and hydroxide radical (•OH) CeO2, was essential for boosting photocatalytic activity. CdS/TiO2/CeO2
were the primary species responsible for the photodegradation of the dispersion on zeolite enhances the surface area of CdS/TiO2/CeO2 while
pollutant [26,37]. preventing agglomeration, resulting in improved photocatalytic per­
formance. Zeolite’s large surface area and absorbent capacity work
3.3. Recyclability of the as-synthesized photocatalyst together to boost the effectiveness of the photocatalytic progression.
Furthermore, because of its polar surrounding and e− -acceptor/donor
The recyclability of as-synthesized photocatalysts was critical for qualities, zeolite facilitates charge separation [30].
their practical deployment. Four-cycle recycling tests were carried out in The photogenerated electrons were successfully transported from the
this study to explore the reusability of zeolite-CdS/TiO2/CeO2 photo­ ternary to the zeolite framework, which leads to a longer charge carrier
catalyst. The results showed that photocatalytic activity decreases lifetime. When the Zeolite-CdS/TiO2/CeO2 photocatalyst was subjected
considerably after four consecutive cycles (Fig. 12).
The 1st cycle removed 99.9% of the dye after 120 min of irradiation

Fig. 12. Values of Ct/Co as a function of irradiation time in different cyclic runs Fig. 13. Real and model sample (MB) degradation as a function of irradiation
over MB dye under visible light (ZAST load at 0.15 g/L, an initial amount of MB time using ZAST photocatalyst (ZAST load at 0.15 g/L, MB initial amount at 10
at 10 mg/L, and pH at 8). mg/L, and pH at 8).

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M. Mahamud et al. Materials Research Bulletin 161 (2023) 112176

to visible light, e− -h+ pairs in the CB and VB were formed. The pho­
togenerated e− -h+ pair would move to the catalyst’s surface and react
with species adsorbed there to make active radicals. Here is the calcu­
lation of the flat potential band for each TiO2, CeO2, and CdS nano­
particles. The values for the ECB and EVB edge positions could be
computed using the following equations from the literature [53].

EVB = χ − EC + 0.5Eg (7)

ECB = EVB − Eg (8)

Consider χ was the absolute electronegativity of TiO2, CeO2, and CdS

(5.81 eV, 5.56 eV, and 5.18 eV, respectively), EC was the free electron
energy on the H-scale (NHE, 4.5 eV), and Eg was the estimated band gap
of TiO2, CeO2, and CdS, which were 3.2 eV, 2.67 eV, and 2.2 eV,
respectively.
Consequently, TiO2’s calculated VB and CB potentials were +2.91 eV
(EVB) and − 0.29 eV (ECB), respectively. Similarly, the EVB and ECB of
CeO2 were calculated to be +2.36 eV and − 0.31 eV, respectively, and
+1.78 eV and − 0.42 eV for CdS. Using the aforementioned computation, Fig. 14. A plausible mechanism for photocatalytic degradation of methylene
the CB level of a CdS (− 0.42 eV) was on the more negative side than that blue reaction with zeolite-CdS/TiO2/CeO2.
of CeO2 (− 0.31 eV), and CeO2 was on the more negative side than TiO2
(− 0.29 eV). Since the CB level of the CdS was more negative than that of 4. Conclusions
the CeO2 and TiO2, photoexcited electrons in the CB of the CdS were
then carried to the CB of the CeO2, which would then be migrated to the The photocatalytic activities of the bare ternary and the supported
CB of the TiO2 driven by the inner electric field between them. As a photocatalysts were investigated for the discoloration of MB dye under
consequence, the electrons in the CdS CB might either initiate or visible light irradiation. The result suggested that the supported pho­
contribute to reduction or oxidation reactions [49]. tocatalyst (ZAST) exhibited maximum adsorption capacity and degra­
Simultaneously, the VB of TiO2 (+2.91 eV) was located on a more dation efficiency (99.9%) than the bare ternary photocatalyst. The
positive side than that of CeO2 (+2.36 eV), VB of CeO2 was placed on a solution pH, initial dye concentration, photocatalyst load, and presence
more positive side than that of CdS (+1.78 eV), the photocatalytic sys­ of various scavengers all affected the degradation of MB dye utilizing a
tem was denoted depletion region, so the h+ could transfer from TiO2 to zeolite-supported CdS/TiO2/CeO2 photocatalyst. Under ideal condi­
CeO2 then to CdS which limits the recombination of photo-induced e− - tions, zeolite-supported CdS/TiO2/CeO2 demonstrated exceptional
h+ pairs in the composite and hence, improves the separation of the photoelectrocatalytic performance for the decomposition of MB. The
pairs. Therefore, CdS/TiO2/CeO2 ternary nanocomposites with corre­ synergistic effect of zeolite, CdS, CeO2, and TiO2 was critical in boosting
sponding band potentials of the constituents would result in the efficient the active free radicals, reducing the rate of recombination of photo­
3-level transfer of photoexcited e− -h+ in CdS/TiO2/CeO2 ternary com­ generated e− -h+ pairs, and improving catalytic performance. Zeolite-
posites upon light irradiation, which was superior to 2-level e− -h+ supported CdS/TiO2/CeO2 had shown significant reusability and dura­
transfer in CdS/TiO2 binary composite and could further encourage e− - bility in dye degradation. The degradation performance result showed
h+ transfer, similar to the reported ternary composite [54]. that zeolite-supported CdS/TiO2/CeO2 would be a promising catalyst for
Because the CB (− 0.29 eV) of TiO2 was lower than E0 (O2/•O2), the the effective removal of methylene blue dye and some other organic
photo-generated electrons can be absorbed by O2 in the organic solvent contaminants under visible irradiation at the optimal value.
to form superoxide radical anions (O2 + e - O2), which could effectively
eliminate organic contaminants (0.13 eV vs. NHE). Yet, because the VB
Declaration of Competing Interest
position of CdS (1.78 eV) was substantially more negative than the po­
tential of the H2O/•OH (2.7 eV) couple, photogenerated holes could not
The authors approved the manuscript and the submission of the
mix with absorbed H2O molecules to make •OH radicals. As previously
revised manuscript. There is no conflict of interest among the authors
stated, the remaining holes would convert the H2O into •OH (H2O + h+ -
regarding the submission of the revised manuscript for publication.
•OH) and react with the organic pollutant to produce H2O and CO2 [55,
56]. Furthermore, because zeolite exhibits poor electrical conductivity,
Data availability
it can be considered an excellent electron acceptor-donor and trans­
porter. Given the above reasoning, the accessible electrons on TiO2
Data will be made available on request.
(e-CB) could be jumped over the surface of zeolite [19]. The electrons
gathered on the zeolite surface could then combine with H2O and O2
molecules to produce OH free radicals and superoxide radical anions
Funding
(O2). Concurrently, the accumulated holes on the CdS (hVB+) could
react with OH-, and the remaining holes can combine with H2O mole­
This research work was financially supported by Haramaya Univer­
cules to form more OH free radicals [57].
sity (HURG-2020–03–02–75, Ethiopia).
Ultimately, the reactive oxygen species generated might oxidize the
organic dye molecules adsorbed on the surface of the zeolite-CdS/TiO2/
CeO2 composite catalyst, resulting in dye decomposition and the gen­ References
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