Materials Science and Engineering B 269 (2021) 115167

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Materials Science & Engineering B

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

Synthesis and characterization of ZrO2/CeO2 nanocomposites for efficient

removal of Acid Green 1 dye from aqueous solution
Ayman A. Ali a, *, Sayed A. Shama a, Alaa S. Amin a, Sahar R. EL-Sayed a
a
Chemistry Department, Faculty of Science, Benha University, Benha City, Egypt

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

Keywords: ZrO2/CeO2 nanocomposites were prepared using the co-precipitation (ZCP11, ZCP12 and ZCP21 samples) and
Coprecipitation method hybrid combustion-ultrasonication (ZC11, ZC12 and ZC21 samples) methods, following by the calcination. The
Combustion-ultrasonication method characterization of the synthesized ZrO2/CeO2 nanocomposites was achieved by utilizing several analytical
ZrO2/CeO2 nanocomposites
techniques such as High-resolution transmission electron microscopy, X-ray diffraction, Fourier transforms
Adsorption
Acid Green 1
infrared spectra, BET method and Field emission scanning electron microscopy. The optimum conditions were
evaluated from the batch method: pH = 3, 250 mg/L of AG1 dye, 0.05 g dose adsorbents, and equilibrium time
(90–200 min according to the sample). The adsorption isotherm, kinetic and mechanism models analyzed using
the extracted experimental data for the elimination of Acid Green 1 dye over ZCP11 and ZC11 samples. Besides,
the thermodynamic factors were investigated at 293–303 K. The optimum conditions were employed for the
fabricated ZrO2/CeO2 nanocomposite samples and the best adsorbent were reused for the elimination of AG1
dye.

1. Introduction adsorption is considered one of the most effective and confirmed

methods for decolorization in water and effluent [4,5].
Dyes are colored organic compounds based on two main functional Inorganic nanoparticles have attracted immense interest from
groups such as chromophoric group (NR2, NHR, NH2, COOH and OH), different fields because of their unique characteristics [6-10] such as
and auxochromes (N2, NO and NO2) [1] which lead to increasing the high surface reactivity, large surface area, relatively low cost, etc.
organic pollutants inside the water media. Dyes are widely utilized in Among the various available materials, Cerium oxide (CeO2) is one of
different fields such as food processing, textile or leather manufacturing, the rare earth metal oxides and it appeared in a cubic fluorite-structured
rubber and plastics industry, paper printing, cosmetics or medicine in­ (FCC). The cerium oxide structure is more stable due to its melting point
dustry [2]. Inorganic and organic pollutants have existed inside the and the temperature can be raised to 2700 ◦ C [11,12]. The cerium oxide
environment area like heavy metal and dyes which considered the big is formed the cubic structure and each cerium atom is enclosed by eight
problems because of their carcinogenic and toxic characteristics for oxygen sites in FCC and each oxygen position has a tetrahedron cerium
living things on our planet. The trace quantity of the dye that exists in site [13,14]. Cerium oxide nanoparticles have important attention due
the living systems may cause several health problems to mankind as well to their unique characteristics and distinctive properties such as
as animals [3]. Acid Green 1 (naphthol green B) is a derivative of different size and morphology, high refractive index, high thermal sta­
benzidine and naphthalic acid and metabolizes carcinogenic products. It bility, UV absorbing ability, facile electrical conductivity, high hardness,
may affect blood factors, such as induce somnolence and clotting, and specific chemical reactivity, high surface area, large oxygen storage
respiratory problems [3]. Removing colour materials as the dyes and capacity, etc. According to these distinctive and unique properties, it
pigments from wastewater can be done via several methods namely was applied in various types of advanced applications such as gas sensor,
chemical, biological and physical methods such as flocculation, glass polishing, free radical scavenger, catalyst, adsorbent for removal of
adsorption, oxidation, electrolysis, biodegradation, ion-exchange, cata­ pollutants from wastewater, the window for the semiconductor device,
lytic photodegradation, coagulation, ozonation membrane filtration, solar cell, elimination soot from diesel engine exhaust, ceramic material,
etc. Among the various available physical-chemical processes, water splitting and fuel cell [13,15,16]. The chemical formula of the

* Corresponding author.
E-mail address: ayman.abdelrazik@fsc.bu.edu.eg (A.A. Ali).

https://doi.org/10.1016/j.mseb.2021.115167
Received 19 November 2020; Received in revised form 6 March 2021; Accepted 29 March 2021
Available online 19 April 2021
0921-5107/© 2021 Elsevier B.V. All rights reserved.
A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

zirconium oxide is ZrO2, occasionally known as zirconia is a white

crystalline oxide of zirconium [17]. ZrO2 exhibits three important
polymorphic forms: the monoclinic phase is thermodynamically stable
up to 1100 ◦ C, the tetragonal phase exists in the temperature range
1100–2370 ◦ C, and the cubic phase is found above 2370 ◦ C [18]. Zir­
conium oxide is a widely used inorganic material that is chemically
stable, non-toxic, and soluble in water [19] and is of vital importance
due to its thermal and chemical stability, and excellent mechanical
properties, such as high strength and fracture toughness, high melting
point, low thermal conductivity, and high corrosion resistance [20].
Fig. 1. The chemical structure of Acid Green 1 (AG1).
Zirconium oxide nanoparticles illustrate intriguing much attention of
researchers due to their unique physical, chemical, optical, and elec­
2.2. Synthesis of ZrO2/CeO2 nanocomposites via co-precipitation method
trical properties. It used in different applications such as sensing,
catalysis, paint, coatings, wastewater treatment, fuel cells and advanced
CeO2/ZrO2 as mixed oxide nanocomposites were prepared by dis­
ceramics [21].
solved certain amounts of zirconium oxychloride octahydrate and
In recent years, the synthesized composites are used in various
cerium sulphate tetrahydrate with different molar ratios (Zr/Ce = 1:1,
application due to the modified properties and unique characteristics.
1:2 and 2:1) in bidistilled water. The pH of obtained solutions was
Composites consist of two or more phases as a mixture and one of the
controlled by ammonia solution until the precipitate appeared at pH =
components is considered as a matrix or host. One of the obtained
9. The obtained precipitates were washed sundry times and the fabri­
composites can be formed in the term of metal or nanometal or organic
cated precipitates were standing for 2 h. The as-synthesized precipitates
material. The second component in the mixture can be the same type or
were dried at 150 ◦ C overnight (24 h). The crystalline CeO2/ZrO2
different to improve the properties of the obtained composites. The
nanocomposites were fabricated after the calcination of the dried sam­
fabricated composites are considered modified and attractive materials
ples at 400 ◦ C and 500 ◦ C for 2 h and 1 h, respectively. The schematic
for different applications such as zirconium oxide /chitosan composite
flowchart for the synthesized of the ZrO2/CeO2 using the co-
as bone tissue engineering materials [22], ZrO2/TiO2 composites for
precipitation method is shown in Fig. 2. The names of zirconium and
photocatalytic degradation of organic dyes [23], Al2O3/ZrO2 composite
cerium oxide nanocomposites are labelled according to the compositions
as reinforced materials [24], ZrO2/CeO2/Y2O3 ceramic composites with
of the starting materials as the following: (Zr/Ce (sample name) = 1:1
Al2O3 platelets for dental implants [25], Co3O4/ZrO2 composites for the
(ZCP11), 1:2 (ZCP12) and 2:1 (ZCP21)).
elimination of organic dyes [26], Mg(OH)2/ZrO2 composite for the
elimination of phosphate from aqueous solution [27], CeO2/chitosan
composite for the removal of fluoride [28], CeO2/activated carbon 2.3. Fabrication of CeO2/ZrO2 nanocomposites via combustion-
composite for removal of tetrachloride, chloroform and dichloro­ ultrasonication method
methane from water [29], CeO2/graphene quantum dots composite for
the photocatalytic degradation of rhodamine B [30], Manganese/cerium 0.01 mol of zirconium oxychloride octahydrate was dissolved in 20
oxide composite supporting palladium nanoscale for the oxidation of mL distilled water and precipitated by ammonia solution until pH = 9.
toluene [31], CeO2 doped ZnO/reduced graphene oxide composite as The as-prepared white precipitate was washed several times and the
antibacterial material [32], etc. estimated amount of nitric acid (HNO3, 2 M) was added to the obtained
Simple and nanocomposite metal oxide nano-adsorbents synthesized precipitate with stirring for 2 h to obtain zirconium oxynitrate. The
by utilizing multi-methods like hydrothermal synthesis [33,34], com­ obtained solution was mixed with the determined moles of glycine fuel
bustion synthesis [35-38], sol-gel process [39-41], co-precipitation [42- according to the rules of the combustion technique and Eq. No. 1. The
45], etc. Our work shows that the CeO2/ZrO2 nanocomposites were solution was heated on a hot plate at 120 ◦ C until the viscous gel was
synthesized by using co-precipitation and combustion- ultrasonication produced. The obtained gel was ignited at 250 ◦ C for a few minutes, a
methods. The obtained CeO2/ZrO2 nanocomposites were characterized pale-grey powder was prepared. The as-prepared powder was calcined
by different techniques. The obtained CeO2/ZrO2 nanocomposites were at 500 ◦ C for 2 h, following by the calcination at 700 ◦ C for 15 min to get
used as adsorbents for the elimination of Acid Green 1 dye (AG1) from the pure white and crystalline zirconium oxide nanoparticles (ZrO2: ZG).
aqueous media. The kinetics, thermodynamic and isotherm of the 0.01 mol of cerium sulphate tetrahydrate was dissolved in 20 mL
adsorption of Acid Green 1 dye (AG1) over the synthesized nano­ bidistilled water. The pH of the obtained solution controlled by
composites were studied. ammonia solution until the precipitate appeared at pH = 9. The obtained
precipitate was washed several times and a certain amount of nitric acid
2. Experimental was added to the obtained precipitate with stirring at 80 ◦ C for 2 h. After
the clear solution appeared, the calculated amount of glycine fuel was
2.1. Materials and reagents added according to the rules of the combustion technique and Eq. No. 2.
The solution heated up to 100 ◦ C to produce the gel, following by the
Zirconium oxychloride octahydrate (ZrOCl2⋅8H2O, 99.5%), cerium auto-ignition at 250 ◦ C for a few minutes. The fabricated pale-yellow ash
sulphate tetrahydrate (Ce(SO4)2⋅4H2O, 98.5%) and Acid Green 1 collected. The fabricated powder was calcined at 500 ◦ C for 2 h to get the
(naphthol green B: C30H15FeN3Na3O15S3, 99%) were obtained from fine crystalline cerium oxide powder (CeO2: CG).
Sigma–Aldrich Chemical Company. Ammonium hydroxide (NH4OH,
33%), nitric acid (HNO3, 69%) and Glycine (C2H5NO2, 99%) were ob­ 9ZrO(NO3 )2 + 10C2 H5 NO2 →9ZrO2 + 25H2 O + 20CO2 + 14N2 (1)
tained from El Nasr pharmaceutical chemical company. The used ma­
9Ce(NO3 )4 + 20C2 H5 NO2 →9CeO2 + 50H2 O + 40CO2 + 28N2 (2)
terials (chemicals and reagents) in the experimental part were of
analytical grade and used as obtained without any treatment. Freshly Cerium and zirconium oxide nanocomposites were synthesized by
bidistilled water was used through all experiments. The chemical mixing certain amounts of the fabricated zirconium and cerium oxides in
structure of Acid Green 1 is shown in Fig. 1. bidistilled water (50 mL) with stirring for 5 min. The obtained mixtures
ultrasonicated for 15 min followed by constant stirring for 30 min.
Finally, the synthesized samples were dried in an electric oven at 100 ◦ C
for 1 h and calcined at 500 ◦ C for 10 min. A schematic flowchart of the

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 2. Schematic flowchart for the fabrication of the ZrO2/CeO2 nanocomposites.

synthetic procedure for the ZrO2/CeO2 is shown in Fig. 2. The samples of (Jasco; model V 670). The as-synthesized cerium and zirconium oxide
the ZrO2/CeO2 nanocomposites are named according to the percentage nanocomposites (ZC11, ZG, CG and ZCP11 samples) investigated uti­
of starting materials oxides (ZG and CG samples) as the following: ZG:CG lizing the thermal tool (TGA, DTA and DTG) from 25 ◦ C to 600-800 ◦ C.
(sample name) = 1:1 (ZC11), 1:2 (ZC12) and 2:1 (ZC21). The TGA and DTA tests investigated with the air gas atmosphere (the
heating rate = 10 ◦ C/min) utilizing a thermal analyzer Shimadzu in­
strument (model TA-60WS). The surface properties of the fabricated
2.4. Characterization composites samples were investigated from nitrogen adsorption iso­
therms at 77 K using the Brunauer Emmett Teller method (NOVAtouch
The appeared phases were confirmed by recording the lines of XRD model).
pattern for the as-prepared and annealed samples, 18 KW diffractometer
(Bruker; model D 8 advance) with monochromatic Cu-Ka radiation, 3. Result and discussion
1.54178 (Ao) in the angular range of 10-70◦ with step size 0.02◦ (2θ) and
scan step time 0.4 (s). The as-synthesized and annealed products were 3.1. Thermal analysis
recorded using the FTIR spectrometer (Thermo Scientific; model Nicolet
iS10) from 4000 to 400 cm− 1. The morphology of the obtained product Fig. 3(a-d) displays the TGA, DTG and DTA of CG, ZG, ZC11 and
was tested utilizing field emission scanning electron microscopy ZCP11 samples. The thermal recording of the as-prepared cerium oxide
(FESEM, JEOL JSM-6390). The (FE-SEM) and gold coating process by (CG sample) using glycine and combustion method as displayed in Fig. 3
utilizing EMITECH K550X sputter coater. The morphology and particle (a). TGA curve appeared the degradation of CG sample in two steps and
size of the obtained samples were revealed using HR-TEM (model Tecnai the total weight loss percentage estimated to be 6%. The first step occurs
G20, FEI, Netherland) at an electron voltage of 200 kV. The elimination in between 30 and 200 ◦ C and the weight loss percentage was estimated
of the testing dye was tested utilizing a Jasco UV-Vis spectrophotometer

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 3. Thermal analyses (TGA, DTA and DTG) of (a) CG, (b) ZG, (c) ZC11 sample and (d) ZCP11 samples.

to be 3% due to the evolution of the adsorption of water molecules and sample. The third peak is the exothermic peak at 600 ◦ C according to the
any volatile compounds on the surface of the CG sample. The second one elimination of the obtained residual from the ignition process in the ZG
recorded in between 200 and 450 ◦ C (weight loss = 3%) according to the sample. According to these data, the zirconium oxide fabricated after the
elimination of the obtained carbon and volatile organic materials after calcination of the as-prepared CG sample in between 700 and 800 ◦ C.
the combustion with glycine fuel. The DTG curve appeared two peaks at The thermal analysis of the obtained zirconium and cerium oxide
155 ◦ C and 200 ◦ C and it confirms the extracted information from the TG nanocomposite (ZC11 sample) after the mixing as displayed in Fig. 3(c).
curve of the CG sample. DTA curve shows the endothermic peak at 70 ◦ C TGA curve appeared the degradation of CG sample in two steps
according to the elimination of the volatile materials from the CG (30–125 ◦ C, 125–200 ◦ C and 200–550 ◦ C) and the total weight loss
sample. The second one is the exothermic peak at 205 ◦ C according to percentage estimated to be 5.5%. The weight losses percentage of the
the ignition of residual of the cerium nitrate with glycine in the CG first and the second steps were estimated to be 2.5% and 1%, respec­
sample. Form these data, the cerium oxide synthesized after the calci­ tively, according to the evolution of the adsorption of the volatile
nation of the as-prepared CG sample in between 450 and 500 ◦ C. The compounds (eg. water molecules) on the surface of the ZC11 sample.
thermal recording of the as-prepared zirconium oxide (ZG sample) using The weight loss of the third step estimated to be 2% due to the elimi­
glycine and combustion method as displayed in Fig. 3(b). TGA curve nation of the volatile organic materials and the recombination of the
appeared the degradation of the ZG sample in three steps (30–200 ◦ C, hydroxide groups on the surface of the ZC11 nanocomposite. The DTG
200–500 ◦ C and 500–700 ◦ C) and the total weight loss percentage curve appeared three peaks at 110 ◦ C, 175 ◦ C and 275 ◦ C and it matched
estimated to be 7%. The weight loss percentage of the first step was with the information of the TG curve of the ZC11 sample. DTA curve
estimated to be 1.5% according to the elimination of the adsorption of shows the two endothermic peaks at 110 ◦ C and 175 ◦ C due to the
volatile compounds on the surface of the ZG sample. The weight losses elimination of the volatile materials from the ZC11 sample. The third
percentage of the second and third steps displays the elimination of one is the exothermic peak at 220 ◦ C according to the evolution of the
3.25% and 2.25% from the sample, respectively, according to the residual of the recombination of the hydroxide groups and organic
elimination of the obtained volatile organic materials after the com­ materials on the surface of cerium zirconium oxide nanocomposite in
bustion process. The DTG curve appeared three peaks at 40 ◦ C, 300 ◦ C the ZC11 sample. Form these data, the ZC11 composite synthesized after
and 590 ◦ C and it approved that the achieved information from the TG the calcination of the as-fabricated ZC11 sample in between 500 and
curve of the ZG sample. DTA curve shows the endothermic peaks at 600 ◦ C. Fig. 3(d) displays the thermal analysis of the as-synthesized
40 ◦ C according to the elimination of the volatile materials from the CG ZrO2/CeO2 nanocomposites using the co-precipitation method (ZCP11
sample. The second peak is the exothermic peak at 280 ◦ C according to sample). TGA curve displayed that the degradation happens in two steps
the ignition of residual of the zirconium nitrate with glycine in the ZG and the total weight loss percentage was found to be 24.38% in the

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

temperature range of 30–500 ◦ C. The first degradation step (30–175 ◦ C) 3.2. X-ray studies
correlated to the elimination of the physical adsorbed of the volatile
molecules (eg. water molecules). The weight loss percentage of the first Fig. 4a(i and ii) manifests the XRD lines of the obtained ZrO2/CeO2
step was found to be 8.5%. The second degradation step occurred in the nanocomposites with different molar ratios (1:1, 1:2 and 2:1) using auto-
range of 175–550 ◦ C and the weight loss is equal to 17.5%. It explains combustion and coprecipitation methods. The XRD lines of the obtained
that the degradation of the hydroxide groups from the ZCP11 sample ZrO2/CeO2 nanocomposites using the combustion-ultrasonication
and the gases evolved. DTG curve showed two peaks at 83 ◦ C and 242 ◦ C method (ZC11, ZC12 and ZC21 samples) manifested in Fig. 4a(i) after
and it matched with the TGA curve. DTA curve showed one endothermic calcination at 500 ◦ C for 10 min. The calcined ZrO2/CeO2 nano­
peak at 90 ◦ C related to the elimination of volatile molecules. Besides, composites (ZC11, ZC12 and ZC21 samples) are indexed according to
the observed exothermic band in the DTA curve at 258 ◦ C is ascribed to reference card No. 01–079-1796 for the zirconium oxide (Crystal sys­
the degradation of the hydroxide groups and the evolution of the gases tem: Orthorhombic; a = 5.0680 Ao, b = 5.2600 Ao and c = 5.0770 Ao and
from the ZCP11 sample. From the thermal analysis, ZrO2/CeO2 nano­ α = β = γ = 90◦ ) and reference card No. 01–075-0120 for the CeO2
composites (ZCP11 sample) were fabricated after the calcination in (Crystal system: Cubic; a = b = c = 5.4110 Ao and α = β = γ = 90◦ ). The
between 400 and 550 ◦ C. XRD lines of the obtained ZrO2/CeO2 nanocomposites using the co-
precipitation method (ZCP11, ZCP12 and ZCP21 samples) are man­
ifested in Fig. 4a(ii) after calcination at 400 ◦ C for 2 h. The calcined
ZrO2/CeO2 samples are indexed according to reference card No. 01–078-

Fig. 4. XRD patterns (a), FTIR analysis (b), N2 adsorption/desorption isotherms (c) and pore size distribution (d) of the synthesized zirconium and cerium oxide
nanocomposites.

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

0048 for the zirconium oxide (Crystal system: Monoclinic; a = 5.1505 nanocomposites (ZC12 and ZCP21 samples) are manifested in Fig. 4(c).
Ao, b = 5.2031 Ao and c = 5.3154 Ao; α = γ = 90◦ and β = 99.194◦ ) and The shapes of isotherms and hysteresis loops used for the determination
reference card No. 01–075-0120 for the CeO2. After the calcination at of the porous structures of the fabricated samples. The obtained iso­
500 ◦ C, the intensity of XRD peaks of the ZCP11, ZCP12 and ZCP21 therms for the synthesized ZC12 and ZCP21 samples are linked to type
samples increases with the formation of cerium and zirconium oxide IV of Brunauer’s categorization. The isotherm type appeared that the
nanocomposites. The average crystal sizes (S, nm) of ZrO2/CeO2 nano­ fabricated nanocomposites can be indicated to mesopores materials
composites (ZCP11, ZCP12, ZCP21, ZC11, ZC12 and ZC21 samples) according to the heterogeneous feature of the solid surface. BET surface
estimated by utilizing the Debye-Scherrer formula: (S = 0.9λ/β cos θ) area, average pore diameter and total pore volume estimated to be 19.4
[9,46]. The crystallite sizes of ZrO2/CeO2 nanocomposites evaluated as m2/g, 1.812 nm, 0.0349 cc/g and 40 m2/g, 1.808 nm, 0.06862 cc/g for
the following: 3.25, 3.3 and 3 nm for ZCP11, ZCP12 and ZCP21 samples, ZC12 and ZCP21 samples, respectively. The BJH pore size distribution of
respectively after the calcination at 400 ◦ C. Besides, the crystallite sizes ZC12 and ZCP21 samples displayed in Fig. 4(d). The data appeared the
of ZCP11, ZCP12, ZCP21, ZC11, ZC12 and ZC21 samples were estimated peaks in between 1 and 9 nm with the head at 3 nm and the extracted
to be 5, 11, 5, 15, 11, 12 nm, respectively after the calcination at 500 ◦ C. results manifested that the synthesized ZC12 and ZCP21 samples formed
According to the XRD data, the stable ZrO2/CeO2 nanocomposites are the mesopores according to the following classification: micropores (0
formed between 400 and 500 ◦ C and sizes of all samples were found in nm < pore diameter < 2 nm), mesopores (2 nm < pore diameter < 50
the nanosized (5–15 nm). It reflected the elimination of AG1 dye on the nm), and macropores (pore diameter > 50 nm) [49]. The relation be­
obtained nanocomposites (ZCP11, ZCP12, ZCP21, ZC11, ZC12 1 and tween the shape of the hysteresis loop of a type IV isotherm and the
ZC21 samples) without releasing any other contaminations in water texture of the fabricated nanocomposites samples appeared in the
from the used adsorbents. Also, it explains that the high surface area of mesopores structure. According to extracted information from the sur­
the fabricated nanocomposites (ZCP11, ZCP12, ZCP21, ZC11, ZC12 1 face analysis, values of the surface area and the total pore volume for the
and ZC21 samples) according to the small sizes and reflects the removal ZCP21 sample are more than the value for the ZC12 sample. It reflected
capacity values of the AG1 dye on the prepared nanocomposites. on the application of the adsorption of AG1 dye on the ZC12 and ZCP21
samples and an extracted information appeared the removal capacity for
3.3. FTIR spectrum the ZCP21 sample is greater than the ZC12 sample at the applied opti­
mum conditions for the elimination dye.
Fig. 4b(i and ii) show FTIR spectra of ZrO2/CeO2 samples using auto-
combustion and co-precipitation methods. Fig. 4b(i) displays the FTIR 3.5. Morphology studies
spectra of ZrO2/CeO2 nanocomposites (ZC11, ZC12 and ZC21 samples)
utilizing the auto-combustion method after the calcination at 500 ◦ C. The morphology of ZrO2 and CeO2 nanocomposites (ZCP11 and
The weak absorption bands at 3410–3450 cm− 1, 1625–1680 cm− 1, ZC11 samples) are examined using FE-SEM and HR-TEM, as manifested
1050–1140 cm− 1, 1525–1550 cm− 1 and 2850–2925 cm− 1 for obtained in Figs. 5 and 6, respectively. FE-SEM images of the obtained ZrO2/CeO2
ZrO2/CeO2 nanocomposites (ZC11, ZC12 and ZC21 samples) are nanocomposites (ZCP11 sample) are manifested in Fig. 5(i-iii). The FE-
harmonized to the vibration modes of the stretching and bending vi­ SEM micrographs of the ZCP11 sample manifest the uniform spherical
bration of hydroxyl groups, Ce-O-Ce, C-O and CH aliphatic, respectively. shape of zirconium and cerium oxide nanocomposites with hard
The strong absorption bands in the range 400–800 cm− 1 (420 cm− 1, 500 agglomeration. The average grain sizes of the collected and visible
cm− 1, 580–590 cm− 1, 664 cm− 1, 750–760 cm− 1) are corresponding to spherical shape for the calcined ZCP11 sample was estimated to be 300
the stretching and bending vibration mode of Zr-O and Ce-O inside the nm as manifested in Fig. 5(iii). FE-SEM micrographs of the synthesized
ZrO2/CeO2 nanocomposites. Fig. 4b(ii) shows FTIR spectra of ZrO2/ ZrO2/CeO2 nanocomposites (ZC11 sample) are manifested in Fig. 5(iv-
CeO2 nanocomposites (ZCP11, ZCP12 and ZCP21 samples) utilizing the vi). SEM images of the ZC11 sample are consist of soft agglomerations of
co-precipitation method after the drying and calcination at 150 ◦ C and regular and irregular spherical zirconium/cerium oxide nano­
500 ◦ C, respectively. After the drying at 150 ◦ C for the ZCP11, ZCP12, composites. The average grain sizes of the calcined ZC11 sample are
ZCP21 samples. The bands at 3000–3600 cm− 1, 1638–1640 cm− 1, 1400 about 250 nm. Elemental analysis of ZCP11 and ZC11 samples were
cm− 1, 1046–1115 cm− 1 and 400–800 cm− 1 are harmonized to vibra­ examined utilizing the EDX technique as manifested in Fig. 5(vii-viii),
tional modes of the stretching and bending of –OH, C=O, Ce-O-Ce and respectively. Images appeared the four lines: Zr, Ce, C and O elements
Zr-O/Ce-O groups, respectively. After the calcination at 400 ◦ C, the and it reflects the formation of the pure ZrO2/CeO2 nanocomposites for
weak absorption bands at 3220–3320 cm− 1, 1620–1630 cm− 1, the synthesized samples. Carbon appeared according to the carbon grid
1119–1137 cm− 1 for all obtained samples are corresponding to the vi­ of the SEM/EDX technique. Fig. 5(x) manifests the EDXS mapping of the
bration modes of stretching and bending vibration for –OH, Ce-O-Ce, ZC11 sample (Fig. 5(ix)). It appears that the synthesized CeO2/ZrO2
respectively. The strong absorption peaks in the range 400–800 composite contains the cerium (yellow color), zirconium (red color) and
cm− 1 (429–480 cm− 1 and 600 cm− 1) for ZCP11, ZCP12 and ZCP21 oxygen (green color) elements with good distribution. EDXS mapping
samples are harmonized to the Zr-O and Ce-O stretching vibration mode showed that the zirconium oxide homogeneously distributed inside the
of ZrO2 and CeO2 nanocomposites [40,47,48]. Due to the extracted in­ cerium oxide. Besides, it matched with the collected information from
formation from FTIR spectra (400–4000 cm− 1), the stable ZrO2/CeO2 the EDXS pattern of the ZC11 sample for the presence of the zirconium
nanocomposites (ZC11, ZC12, ZC21ZCP11, ZCP12 and ZCP21 samples) oxide and cerium oxide as a mixture inside the composite.
are obtained. It reflected the adsorption of organic dye on the fabricated HR-TEM examination of ZrO2 and CeO2 nanocomposites are man­
nanocomposites (ZC11, ZC12, ZC21ZCP11, ZCP12 and ZCP21 samples) ifested in Fig. 6(i-iii) and (vii-xi) for ZCP11 and ZC11 samples, respec­
without releasing any contaminations inside the media from the surface tively. HR-TEM images of the ZCP11 sample appeared the regular and
of the adsorbent. Also, it explains the activity of the surface of the irregular spherical shapes with hard and dense agglomerations as
synthesized nanocomposite according to the bonding of the hydroxide manifested in Fig. 6(i-iii). The collected information utilized for the
groups on the surface of ZrO2/CeO2 nanocomposites (ZC11, ZC12, construction of the histogram graph is appeared in Fig. 6(vi). From the
ZC21ZCP11, ZCP12 and ZCP21 samples) and it reflects on the pH value TEM image and histogram graph of the ZCP11 sample, the average
of the AG1 dye elimination on the fabricated nanocomposites. particle sizes are estimated be 24 nm (standard deviation (SD) = 7.6 and
mean = 23.7). The calculated particle size differentiated from the
3.4. Surface properties of the synthesized nanocomposites determined crystallite size of the ZCP11 sample. The dense agglomera­
tions of the particles of the synthesized cerium oxide and zirconium
Adsorption-desorption isotherms of the fabricated ZrO2/CeO2 oxide composite (ZCP11 sample) appeared. HR-TEM micrographs of the

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 5. FE-SEM images (i-vi) of the calcined ZrO2/CeO2 nanocomposite: ZCP11 (i-iii) and ZC11 (iv-vi) samples, EDX pattern of ZCP11 (vii) and ZC11 (viii) samples
and the EDXS mapping (x) of ZC11 sample (ix).

calcined ZC11 sample (Fig. 6(vii-xi)) observed that the ZC11 sample average particle sizes are estimated to be 16 nm (standard deviation
consisted of the soft collection for the particles of spherical shapes with (SD) = 7.6 and mean = 15.55). The estimated particle size differentiated
average particle sizes are about 16 nm. Also, the obtained data utilized from the estimated crystallite size of the ZC11 sample and the dense
for the construction of the histogram graph as manifested in Fig. 6(xii). agglomerations of the particles of the fabricated cerium oxide and zir­
From the TEM image and histogram graph of the ZC11 sample, the conium oxide composite (ZC11 sample) appeared.

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 6. HR-TEM images of the calcined ZrO2/CeO2 nanocomposite: ZCP11 (i-v) and ZC11 (vii-xi) samples and histogram graph for ZCP11 (vi) and ZC11 (xii) samples.

3.6. Batch adsorption experiments of Acid Green 1 Where, qe is the amount of dye molecules adsorbed per unit weight of
adsorbent (mg g− 1), Z is the volume of solution (L), Xo is the initial dye
The synthesized ZrO2 and CeO2 nanocomposites in the form of the concentration (mg/L), Xe is the equilibrium dye concentration (mg/L),
ZCP11 and ZC11 utilized as nano-adsorbents for the separation of Acid and M is the weight of the adsorbent (g).
Green 1 from aqueous solution using the batch mode. The amount of the Fig. 7(a) manifests the effect of initial pH (2 to 9) on the removal of
dye adsorbed on the fabricated ZCP11 and ZC11 samples and the 50 mg/L of AG 1 dye solution over 50 mg of the synthesized ZrO2/CeO2
elimination efficiency percentage (R %) were determined from Equa­ nanocomposites (ZCP11 and ZC11 samples) at 293 K. The removal ef­
tions No. 3 and 4, respectively. ficiency appeared a descending direction by the rising of the values of
pH. The elimination dye efficiency recorded at λ max = 714 nm with the
(XO − Xe )Z
qe = (3) maximum values: 78% and 99% at pH = 3 for the elimination of AG1
M
dye over ZCP11 and ZC11 samples, respectively. It is expected because
(XO − Xe ) the surface of the synthesized nanocomposites is more protinated at low
Removal(R%) = × 100 (4) pH values. The partial positive charges are formed on the surface of the
XO

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 7. Influence of pH (a), time (b), initial dye concentration (c), ionic strength (d), adsorbent dose (e), temperature (f) for the AG1 dye removal using ZrO2/CeO2
nanocomposite: (ZCP11 and ZC11 samples).

cerium and zirconium oxide nanocomposites and the obtained charges mg/L for ZC11 sample) at pH = 3 and 293 K. The effect of the presence of
are enough to attract the anionic dye (Acid Green 1) from the solution. KCl salt as ionic strength on the adsorption capability was exhibited in
According to this data, the adsorption capacities are high in acidic media Fig. 7(d). From the extracted data, the dose of KCl increases, the per­
(pH = 3–5). With the increase of pH, deprotination occurs and the centage of AG1 dye elimination efficiency reduces due to the dimin­
surface becomes more negative charge. The presence of the negative ishing of the active positions on the surface of ZrO2/CeO2
charge reduces the adsorption of the anionic dye on to the surface of the nanocomposites because of the rise of the ionic strength of the solution
synthesized nanocomposites. According to this data, the low removal of in the presence of KCl. The effect of adsorbent dosage on the adsorption
the dye appears at high pH values [50]. of AG1 dye was investigated using the various amounts of the adsorbent
The contact time of the 50 mg/L of AG1 removal was investigated (0.01–0.125 g). The adsorbent was added to 25 mL of AG1 dye solutions
using 50 mg of ZCP11 and ZC11 samples at pH 3. Fig. 7(b) shows the of initial concentrations (50 mg/L and 100 mg/L of AG1 dye for ZCP11
elimination efficiencies for the AG1 over of the synthesized ZrO2/CeO2 and ZC11 samples, respectively). After equilibrium time, the obtained
nanocomposites (ZCP11 and ZC11 samples) as a relation with the con­ data from the adsorption of the AG1 dye over the ZCP11 and ZC11
tact times from 15 min to 240 min. In the initial step, the rate of removal samples are depicted in Fig. 7(e). The obtained results appeared that the
was fast following by the slow stage until the surface of the ZCP11 and increase in the amount of ZrO2/CeO2 adsorbent dues to the increasing in
ZC11 samples became a saturation state. The maximum removal of AG1 the elimination of AG1 dye efficiency due to the expanding of the active
dye was recorded to be 19.5 mg/g and 24.8 mg/g in 200 min and 90 min positions in the adsorbent surface. The maximum elimination percent­
for ZCP11 and ZC11 samples, respectively. Fig. 7(c) manifested the ef­ age for the AG1 dye over 50 mg of ZCP11 and ZC11 samples were
fect of various initial concentration (50 and 350 mg/L) of AG1 dye over determined to be 78% and 65%, respectively.
0.05 g of adsorbents (ZCP11 and ZC11 samples) at 293 K and pH = 3. The adsorption process was investigated with the different temper­
The adsorption capacities were determined from the extracted data and ature at 293, 298 and 303 K, separately for the removal of AG1 dye (50
equilibrium time (after 200 min and 90 min for ZCP11 and ZC11 sam­ mg/L for ZCP11 sample) and (100 mg/L for ZC11 sample) using 0.05 g
ples, respectively). The rate of uptake was rapid in the beginning of the ZrO2/CeO2 nano-adsorbents. The experimental data appeared
because the most active sites are free and available on the surface of the that the increase in the solution temperature leads to the increasing of
ZCP11 and ZC11 samples. The active positions on the surface of nano­ the adsorption capacity slowly for the removal of AG1 dye on the ZCP11
composites were blocked and closed with time, the removal rate of the and ZC11 samples as exhibited in Fig. 7(f). It explains that the removal of
dye reduced. From extracted data, the adsorption capacities of ZCP11 AG1 dye on the fabricated ZrO2/CeO2 adsorbents showed an endo­
and ZC11 samples were determined to be 43 and 46 mg/g, respectively. thermic effect. The increase in temperature of the dye solution leads to
The effect of KCl on the adsorption of AG1 dye over 0.05 g of ZCP11 the reduction of the distance of the boundary layer around the ZCP11
and ZC11 adsorbents was investigated using 0.05 to 0.25 g of KCl salt at and ZC11 samples. Also, the resistance from the mass transfer of
a constant dye concentration of (50 mg/L for ZCP11 sample) and (100 adsorbate in the boundary layer around the ZrO2/CeO2 adsorbents

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

reduced with the rise of temperature and it leads to an increase in the parameter can calculate from RL = 1/(1 + S), S = KLXo and the RL values
transportability of the AG1 dye molecules [3,51]. show the nature of the adsorption of the dye. According to the
Freundlich isotherm, the maximum adsorption capacity can calculate
using the relation: qm = KFX1/y
o . If the value of (1/y) < 1, it indicates
3.7. Adsorption isotherms studies normal adsorption. Also, the value of y in between 1 < y < 10, indicates
a favorable adsorption process [59]. According to the Temkin isotherm,
The adsorption isotherm models were carried out by studying the the heat of adsorption determine using (d = RT/B), where T is the
relationship between the different initial concentrations of the dye temperature in kelvin and R is the universal gas constant (8.315 J mol− 1
(50–350 mg/L) and the adsorption capacities. Langmuir, Freundlich and K− 1) [60].
Temkin isotherm models are used for the characterization of the Table 1 is summarized the calculated parameters from Langmuir,
experimental data utilizing the different equilibrium concentrations of
AG1 dye (50–350 mg/L) on 50 mg of the ZCP11 and ZC11 samples at pH
Table 1
= 3 and 293 K as shown in Fig. 8(a-c). Linear plots of Langmuir [52-54]
The extracted parameters from Langmuir, Freundlich and Temkin isotherms for
(Xe/qe with Xe), Freundlich [55,56] (ln qe with ln Xe) and Temkin [57] ZrO2-CeO2 adsorbent (ZCP11 and ZC11 samples).
(qe with ln Xe) isotherm models are manifested in Fig. 8(a, b and c)
isotherm Parameters Values
according to the equations No. 5, 6 and 7, respectively.
ZCP11 ZC11
Xe 1 Xe
= + (5) Langmuir KL (L/mg) 0.0204 0.1144
qe KL qm qm
qm (cal) (mg/g) 47.62 47.40
RL 0.1229–0.4952 0.02437–0.14885
1 R2 0.9429 0.9973
lnqe = lnKf + lnXe (6)
y qm (exp) (mg/g) 43 46

Freundlich KF [(L/mg) (L/mg)1/n] 9.5162 26.285

qe = BlnKT + BlnXe (7) qm (cal) (mg/g) 42 46.5
y (L/mg) 3.9017 10.2775
Where, qe is the equilibrium adsorption capacity of AG1 dye on the R2 0.6262 0.8992
ZCP11 and ZC11 adsorbents, KL is the Langmuir constant (L/mg), qm is qm (exp) (mg/g) 43 46
the maximum amount of adsorbed solute to adsorbent (mg/g). KF is the
Temkin KT (L/g) 1.634 2203.74
Freundlich parameter (mg/g), (1/y) is the heterogeneity factor, B is d (kJ/mol) 0.309 0.713
constant (B = RT/d), KT (L/mg) is Temkin equilibrium binding param­ B 7.884 3.418
eter related to the maximum binding energy and d corresponds to the R2 0.7814 0.8884
heat of adsorption [58]. From the Langmuir isotherm, the equilibrium

Fig. 8. Isotherm (Langmuir (a), Freundlich (b) and Temkin (c) models), pseudo-first-order model (d), pseudo-second-order model (e) and power function model (f)
for the AG1 dye removal using ZrO2/CeO2 nanocomposite: (ZCP11 and ZC11 samples).

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Freundlich and Temkin isotherms. According to the R2 values, the model kinetic parameters determined and summarized in Table 2.
of Langmuir isotherm is the best fitting than the other isotherms. The R2
K1 t
value of the Langmuir equation was found to be 0.9429 and 0.9973 and log(qe − qt ) = logqe − (8)
2.303
it was closer to 1, compared to the R2 value obtained from the other
isotherms model. It explains that the removal of the AG1 dye on the t 1 t
fabricated ZCP11 and ZC11 adsorbents in the form of the homogenous = + (9)
qt K2 qe 2 qe
monolayer [61]. The maximum adsorption capacity was determined to
be 43 and 46 mg/g for the ZCP11 and ZC11 samples, respectively. log(qt ) = logW + Ulog(t) (10)
Also, the determined adsorption capacity from the Langmuir
Where, qe and qt are the amounts of dye adsorbed (mg/g) at equi­
isotherm was calculated and found to be 47.62 and 47.4 mg/g for the
librium and time t (min), respectively, t (min) is contact time, and k1 is
synthesized ZrO2/CeO2 samples (ZCP11 and ZC11 adsorbents) which
the pseudo-first-order rate constant of adsorption (min− 1), k2 (g/mg.
are closed with the experimental values (43 and 46 mg/g). In the current
min) is pseudo-second-order rate adsorption constant, W is the initial
research, the values of the RL parameter were calculated and found in
rate of adsorption, and U is the rate constant of the adsorption process.
between 0.1229 and 0.4952 and 0.02437–0.14885 for ZCP11 and ZC11
According to the R2 values From Table 2, the pseudo-first-order
adsorbents, respectively, related to 50–300 mg/g of AG1 dye as initial
(ZCP11, R2 = 0.935) is a better fitting than the pseudo-second-order
concentration. It explains that the adsorption of the AG1 dye on the
(ZCP11, R2 = 0.8529) for the elimination of the AG1 dye over ZrO2/
fabricated ZCP11 and ZC11 adsorbents is a favorable mode. From the
CeO2 nano-adsorbent. But, the pseudo-second-order model (ZC11, R2 =
obtained data of Freundlich isotherm, the KF is the Freundlich constant
0.9997) is better fitting than the pseudo-first-order (ZC11, R2 = 0.8931)
found to be 9.5162 and 26.285 (mg/g) for ZCP11 and ZC11 adsorbents.
for the AG1 dye separation over ZrO2/CeO2 nano-adsorbent. The AG1
From the obtained information of Temkin isotherm, the values of the
dye separation using the ZCP11 obeys the pseudo-first-order model and
heat of adsorption (d) were found in between 0.309 and 0.713 KJ/mole
the value of the estimated adsorption capacity (cal. 24 mg/g) is in a good
and it explains the weak interaction force between the AG1 dye and the
compact with the extracted data from the experimental (22.5 mg/g).
surface of the ZCP11 and ZC11 adsorbents. Besides, the KT found to be
But, the elimination of AG1 dye over the ZC11 sample follows the
1.63365 and 2203.74 L/g and the Temkin parameter (B) value calcu­
pseudo-second-order model and the calculated adsorption capacity
lated to be 7.884 and 3.418 J/mol for ZCP11 and ZC11 adsorbents.
value (cal. 33.1 mg/g) is in good agreement with the experimental one
(32.8 mg/g). Besides, the power function model was applied to the
3.8. Adsorption kinetic models experimental data for the elimination of the AG1 dye over ZrO2/CeO2
nano-adsorbent for the indication of the initial rate (W) and rate of the
The models of adsorption kinetic examined by the investigation of adsorption process (U). According to the R2 values, the power function
the contact time effect on the AG1 dye removal using the prepared model fits well for the elimination of the dye using the ZCP11 and ZC11
ZCP11 and ZC11 adsorbents. Kinetic factors of the elimination AG1 dye samples as manifested in Fig. 8(d-f). The calculated initial rate and rate
on ZrO2/CeO2 nano-adsorbent were estimated using pseudo-first-order of the adsorption process from the power function model are shown in
equation (Eq. No. 8: plot log (qe - qt) versus t) [62], pseudo-second- Table 2. The data shows that the initial rate of the AG1 dye adsorption
order equation (Eq. No. 9: plot t/ qt versus time t) [63] and power using the synthesized ZC11 sample is faster than the fabricated ZCP11
function kinetic equation (Eq. No. 10: plot log(qt) versus log(t)) [64] as sample. It clarifies that the adsorption process took a short time in the
appeared in equations No. 8–10, respectively. The extracted information case of the ZC11 sample (90 min) than the ZCP11 sample (200 min) until
from the applied relations can get data about the rate of the AG1 dye the equilibrium stage has happened.
removal using the synthesized samples as displayed in Fig. 8(d- f). The

Table 2 3.9. Adsorption mechanism

Kinetic parameters for adsorption of AG1 dye using ZrO2/CeO2 adsorbent
(ZCP11 and ZC11 samples). The AG1 dye adsorption using the synthesized nanocomposite
model Parameter Values (ZCP11 and ZC11 samples) can be studied using the following equations:
ZCP11 ZC11 intraparticle diffusion model (Eq. No. 11: plot qt versus t0.5) [5,8],
Pseudo first order K1(min− 1) 0.01257 0.03815 liquid-film diffusion model (Eq. No 12: Boyd model; -ln(G) against t)
qm (cal) (mg/g) 24 13.85 [65,66], outer and external diffusion model (Eq. No. 13: Spahn and
R2 0.935 0.8931 Schlunder model; lnXt against t) [67-69] and pore diffusion model (Eq.
qm (exp) (mg/g) 22.5 32.8 No. 14: Bangham’s equation: log R against log t) [70] as outlined in
Pseudo second order K2(g/mg.min) 0.000251 0.00785 equations No. 11–14, respectively. These relations used to give data
qm (cal) (mg/g) 31.6 33.1 about the adsorbate amount and the rate of dye removal over the pre­
R2 0.8529 0.9997
pared samples as displayed in Fig. 9(a-d). The kinetic parameters
qm (exp) (mg/g) 22.6 32.8
determined from the various models and the collected data outlined in
Power function W 1.044 19.58 Table 2.
U 0.57324 0.112
R2 0.9648 0.9592 qt = KI t0.5 + C (11)
0.5
Intraparticle diffusion KI (mg/g min ) 1.748 1.0528
C (mg/g) 2.56 22.66 lnG = − KL t (12)
R2 0.9692 0.9011
KE 0.00215 0.002795 lnXt = lnXo − KE t (13)
Outer diffusion Xo 91.72 46.74
R2 0.9861 0.833 logR = log(Ko /P) + αlogt (14)
Ko 0.00608 0.000216
Where, qe and qt are the amounts of dye adsorbed (mg/g) at equi­
pore diffusion 0.17612 0.65283
А
librium and time t (min), respectively, t (min) is contact time, kI is the
R2 0.9664 0.9576
intraparticle diffusion constant (mg/g.min0.5), and C is constant that
liquid-film diffusion KE 0.0129 0.0305 gives an idea about the thickness of boundary layer (mg/g). The values
R2 0.9201 0.9723
of G calculated from the relation: G = [1-(qt/qe)] and KL is liquid film

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

Fig. 9. Intraparticle diffusion model (a), liquid-film diffusion model (b), external diffusion model (c), pore diffusion model (d), FTIR spectra of ZC12 and ZCP21
before (black line) and after adsorption (red and blue lines) (e), Van’t Hoff relation (f), the calculated qe at the applied optimum (g) and recycling the selected
samples for the AG1 dye removal using ZrO2/CeO2 nanocomposites (h).

diffusion rate constant; min− 1. Xo is the initial dye concentration (mg/ separation using the prepared ZCP11 and ZC11 samples. The extracted
L), Xe is the equilibrium dye concentration (mg/L) and KE is the external parameter values from linear relation are summarized in Table 2. Ac­
diffusion rate constant (min− 1). α (mg/g.min) and Ko (g/mg.min) are cording to the plot, the line does not pass the origin, and it is reflected
Bngham constants. R values determined from the relation: R = log[Xo/ that this model is not the only one for the illustration mechanism of the
(Xo-qe m)] and the P value calculated from the relation (P = 2.303 V/m). AG1 dye removal on ZrO2/CeO2 adsorbents (ZCP11 and ZC11 samples).
m is the mass of the adsorbent in gram/litre and V is the volume of dye But the determined R2 values for ZCP11 and ZC11 samples showed the
solution in mL. utility of the intraparticle diffusion model with the other models in the
Fig. 9(a) manifests the intraparticle diffusion model of the AG1 dye adsorption process. Additionally, the dye adsorption can be controlled

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A.A. Ali et al. Materials Science & Engineering B 269 (2021) 115167

by other mechanisms: liquid film diffusion, outer diffusion, and pore Experimental parameters are summarized in Table 3. The elimination of
diffusion. AG1 dye using the fabricated ZCP11 and ZC11 nano-adsorbents was an
Besides, It is clear that the linear plot of the liquid-film diffusion endothermic process because of the positive value of ΔHo. The ΔHo
model (-ln(G) against t) are not passing through the origin and it is not values (cal. 29.46 and 11.8 KJ/mol for ZCP11 and ZC11 samples,
only the rate-controlling step as manifested in Fig. 9(b). For R2 values, It respectively) are lower than 40 KJ/mol, therefore the elimination of
indicates that the liquid film diffusion model can be used for the inter­ AG1 dye using the ZCP11 and ZC11 samples is a physisorption process
pretation mechanism of the AG1 dye adsorption using the synthesized [3,73]. The positive charge of ΔSo associated with the raise in the
ZrO2/CeO2 nano-adsorbent with the other models. Fig. 9(c) manifested freedom degree of solution for the AG1 dye removal. The spontaneous
the outer and external diffusion model (Eq. No. 11; lnXt against t). The dye removal was appeared according to the negative values of ΔGo. Also,
KE and Xo values were founded to be 0.00215 min− 1, 0.002795 min− 1, the AG1 dye removal using the fabricated ZCP11 and ZC11 samples is
91.72 mg/L and 46.74 mg/L for ZCP11 and ZC11 samples, respectively. more favorable at high temperatures because the ΔGo values reduced
It appeared that the extracted information was close to the experimental with the increasing temperature.
concentration (100 mg/L) indicating the validity of this model for the
ZCP11 sample and the inaccuracy for the ZC11 sample as displayed in 3.11. Effect of the obtained nanocomposites on the removal of AG1 dye
Table 2. According to the R2 values, the outer diffusion model can be
explained the AG1 dye adsorption using the ZCP11 sample and it does The obtained ZrO2/ CeO2 nanocomposites from the co-precipitation
not apply to the explanation of the adsorption over the ZC11 sample. and combustion methods (ZCP11, ZCP21, ZCP12, ZC11, ZC21 and ZC12
Furthermore, the plot of log (R) with log (t) was pointed to be a direct samples) were studied at the optimum conditions: pH = 3, 250 mg/L,
linear with an excellent relationship coefficient (R2 = 0.9664 and 0.05 g dose adsorbents, and equilibrium time (200 min for ZCP11,
0.9576) as displayed in Fig. 9(d). it pointed out that the rate- ZCP21 and ZCP12 samples), (90 min for ZC11, ZC21 and ZC12 samples).
determining stage can be governed by the pore diffusion mechanism. The removal capacities of ZrO2/CeO2 nanocomposites are determined
According to the extracted information, the AG1 dye adsorption and represented in Fig. 9(g).
using the synthesized ZCP11 sample can explain using more than one
models according to R2 values like the following: outer diffusion and 3.12. Comparison of adsorption capacities of the synthesized ZrO2/CeO2
liquid-film diffusion models can use for the transfer of dye from the nanocomposites with different adsorbents for the removal of AG1 dye
solution to the surface following by the transfer the AG1 dye to the
prepared ZrO2/CeO2 nanocomposites surface using the interparticle The adsorption capacities of ZrO2/CeO2 adsorbents for the elimina­
diffusion and pore diffusion models. On the other hand, the AG1 dye tion of AG1 dye compared with the adsorbents in the literature
adsorption using the fabricated ZC11 sample is similar to the ZCP11 [3,6,50,51,71,74-78]. The obtained information appeared that the
sample and it concluded as the following: liquid-film diffusion model fabricated ZrO2/CeO2 nanocomposites can be used as adsorbents for the
can utilize for the transfer of the dye from the solution to the surface elimination of AG1 dye according to the determined adsorption capacity
following by the transfer of the AG1 dye to the surface of the prepared as summarized in Table 4.
ZrO2/CeO2 nanocomposites utilizing the interparticle diffusion and pore
diffusion models.
3.13. Recycling and regeneration of the synthesized ZrO2/CeO2 nano-
Fig. 9(e) shows the FTIR spectrum for the ZCP21 and ZC12 samples
adsorbents
after and before the AG1 dye adsorption. According to the obtained FTIR
data of the AG1 dye adsorption using the synthesized samples, the bands
The capability of regeneration of the prepared ZrO2/ CeO2 adsor­
of AG1 dye appeared plus the peaks of the zirconium and cerium oxide
bents (ZCP21 and ZC12 samples) was investigated under the optimum
nanocomposites. The stretching vibrations of S-O of the sulphonic group
conditions. The dyes were eluted by various eluents including ethanol,
appeared at 1050 cm− 1 (shoulder at 1020 cm− 1) and 1120–1150 cm− 1.
methanol, HCl/NaOH solution following by calcination at 300 ◦ C for 10
The bands between 1500 cm− 1 and 1600 cm− 1 referred to the aromatic
min. After four cycles, the fabricated ZrO2/ CeO2 adsorbents can be
rings of naphthalene and the stretching vibration of –C–N=O group.
reused for the elimination of AG1 dye several times with high capacity as
After the elimination process, the peak between 500 and 600 cm− 1 is
illustrated in Fig. 9(h). The extracted information confirms that the
linked to the stretching vibration of Fe-O. According to the extracted
recycling of the fabricated ZrO2/CeO2 nanocomposites (ZCP21 and
information, the spectra manifested that the AG1 dye adsorbed over the
ZC12 samples) can be accepted as adsorbents for cleaning the solution
synthesized ZrO2/CeO2 nanocomposite samples [71].
from AG1 dye under acceptable conditions.

3.10. Thermodynamic studies 4. Conclusions

The temperature effect on the AG1 dye removal using the ZCP11 and ZrO2/CeO2 nano-adsorbents synthesized utilizing co-precipitation
ZC11 nano-adsorbents was investigated ranging from 293 K to 303 K. and hybrid combustion-ultrasonication methods. The fabricated ZrO2/
The thermodynamic parameters ΔHo, ΔSo and ΔGo were examined CeO2 nanocomposites were examined using different tools for the study
utilizing Van’t Hoff relation [5,72], (Equation No.15) as manifested in
Fig. 9(f). The Gibbs free energy values (ΔGo) for the AG1 dye adsorption Table 3
using the prepared ZCP11 and ZC11 nano-adsorbents calculated from Thermodynamic parameters for the AG1 dye adsorption using ZrO2 /CeO2 ad­
equation No. 16. sorbents (ZCP11 and ZC11 samples).
H Adsorbent Temperature, (◦ K) ln Kc ΔG◦ ΔH◦ ΔS◦
lnKc = +A (15)
T (KJ/ (KJ/ (KJ/
mol) mol) mol)
(16)
◦ ◦ ◦
ΔG = ΔH − TΔS
ZCP11 293 0.5672 − 1.3165 29.46 0.105
Where ΔHo is enthalpy change, ΔSo is entropy change, the kc values 298 0.6888 − 1.8416
303 0.9672 − 2.3667
were estimated from qe/Xe and called the equilibrium constant (L/g), T
is the temperature in Kevin (k) and R is the gas constant (8.314 J/ mol). ZC11 293 − 0.0842 0.1934 11.796 0.0396
The plot of (ln kc) against (1/T) shows a straight line as illustrated in 298 0.0116 − 0.0046
303 0.0755 − 0.2026
Fig. 7(f) with slope (H = -ΔHo/R) and intercept (A = ΔSo/R).

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Table 4 References
Comparison of Adsorption capacities of the synthesized ZrO2 /CeO2 adsorbents
with various adsorbents. [1] A. Kausar, M. Iqbal, A. Javed, K. Aftab, H.N. Bhatti, S. Nouren, J. Mol. Liq. 256
(2018) 395–407.
Adsorbents q, (mg/g) Refs [2] L. Bartoňová, L. Ruppenthalová, M. Ritz, Chin. J. Chem. Eng. 25 (2017) 37–44.
[3] M.F. Attallah, I.M. Ahmed, M.M. Hamed, Environ. Sci. Pollut. Res. 20 (2013)
Industrial sludge 10 3
1106–1116.
Halloysite-iron oxide nanocomposite 11.2 6
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